WO2016180297A1 - 一种金属桥位稠环化合物及其中间体和制备方法及应用 - Google Patents

一种金属桥位稠环化合物及其中间体和制备方法及应用 Download PDF

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WO2016180297A1
WO2016180297A1 PCT/CN2016/081392 CN2016081392W WO2016180297A1 WO 2016180297 A1 WO2016180297 A1 WO 2016180297A1 CN 2016081392 W CN2016081392 W CN 2016081392W WO 2016180297 A1 WO2016180297 A1 WO 2016180297A1
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夏海平
卓庆德
林剑锋
周小茜
陈志昕
邵一凡
张弘
何旭敏
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Xiamen University
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Priority claimed from CN201510606889.2A external-priority patent/CN106543232B/zh
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Definitions

  • the present invention relates to the field of organic chemistry and metal organic chemistry, and in particular to a metal bridge fused ring compound and an intermediate of the metal bridge fused ring compound, that is, a chain polyacetylene compound and a preparation method thereof, the present invention It also relates to the use of metal bridge fused ring compounds.
  • the fused aromatic ring is an important class of organic aromatic hydrocarbons. Due to its large conjugated system, planarity and rigidity, it generally has good optoelectronic properties and is widely used as an organic field effect transistor, organic light emitting diode and organic solar cell material (J. Am. Chem. Soc., 2011, 133 (50): 20009-20029). As a electroluminescent material, fused aromatic rings have been widely used in the fields of physiology, pharmacy, information science and materials science. In recent years, the synthesis and application of heteroatom-containing fused aromatic rings have become one of the hot research fields.
  • heteroatoms in the all-carbon fused aromatic ring skeleton can adjust its frontier orbital energy and thus change its photoelectric properties (Chem.Commun., 2015, 51(29): 6257-6274).
  • the hetero atom contained in the heterocyclic aromatic ring skeleton has been reported to be a main group element.
  • the d, s orbital energy of the transition metal outer layer is similar, easy to generate d/s transition, and has an unfilled valence layer d orbit. It is easy to accept electrons in the hybrid orbit to reach 16 or 18 electrons.
  • the stable state forms a complex. Therefore, the transition metal hetero-fused aromatic ring has the characteristics of a transition metal and an aromatic ring, and has more properties and properties than the fused aromatic ring doped with the main group element.
  • metal hetero-fused aromatic rings have good application prospects, there are few types of metal hetero-fused aromatic rings (Coord. Chem. Rev., 2014, 270–271(0): 151-166), and there is no general purpose. resolve resolution.
  • novel metal hetero-fused aromatic ring not only has novel structure, but also has unique optical properties such as ultraviolet-visible-near-infrared light absorption, aggregation-induced fluorescence enhancement, and large Stock shift, and has important application prospects in the field of light and electricity.
  • novel metal hetero-fused aromatic rings of this type of metal which are reported by the Xia group, exhibit unique properties not found in many other materials in the optical and electrical fields, the compounds of this type are currently in a long synthesis step and have poor stability of intermediate products. Difficult to prepare; and its metal variety is limited to metal ruthenium. Compared with bismuth, other metals such as lanthanum, cerium and lanthanum are more abundant, cheaper and more widely used. Therefore, the development of a simple synthesis method of metal heteropentyne, metal heteropentene and its derivatives, it is particularly important to synthesize other metal central metal heteropentyne, metal heteropentene and its derivatives.
  • Pincer ligands refer to a class of compounds containing structures similar to ECE (E, C is any atom that can coordinate with metals), a concept first proposed in the 1970s. Due to its good stability, reactivity and stereoselectivity, the chelate ligands and metal complexes are widely used in the fields of coordination chemistry, organic synthesis, homogeneous catalysis and material chemistry (Angew. Chem. Int. Ed. 2001, 40, 3750-3781). In recent years, the clamp ligands and metal complexes not only play an important role in the fields of C-coupling reaction, inert chemical bond activation, but also important applications in photovoltaic materials, such as terpyridines formed by terpyridine and ruthenium. Complexes (black dyes) are widely used in the field of solar cells.
  • ECE E, C is any atom that can coordinate with metals
  • the present invention provides a chain polyacetylene compound and a preparation method thereof, and the invention also provides a metal hetero-fused ring compound (including a metal hetero-fused aromatic ring) prepared by a chain polyacetylene compound.
  • a metal hetero-fused ring compound including a metal hetero-fused aromatic ring
  • Compounds and non-aromatic metal heterofused ring compounds) and methods of preparation and use are also provided.
  • chain polyacetylene compounds can efficiently construct metal hetero-fused ring compounds under mild conditions.
  • a chain-like polyacetylene compound can be obtained by a metal exchange reaction of a terminal alkyne with an organometallic reagent in an aprotic solvent, and contacting the obtained reaction mixture with an alkyne or an alkyne.
  • the chain polyacetylene compound can be directly reacted with a simple metal complex to obtain a metal heterofused ring compound.
  • the present invention has thus been completed.
  • the present invention provides a chain polyacetylene compound having the structure shown in Formula I below:
  • X is -O-, -S-, -CR 4 R 5 -, -SiR 6 R 7 - or -NR 8 -; and R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen. , C 1-20 alkyl, C 1-20 ester, C 1-20 acyl, C 3-20 cycloalkyl, C 1-20 haloalkyl, nitrile, nitro, substituted or unsubstituted aryl or R 9 is a C 1-8 alkyl group or a substituted or unsubstituted aryl group;
  • R 1 is a nitrile group, a substituted or unsubstituted C 2-30 alkynyl group, a substituted or unsubstituted C 4-30 polyalkynyl group, a substituted or unsubstituted C 3-30 cumulative polyalkenyl group, and does not contain -C ⁇ CCH(OH)C ⁇ C-structural unit;
  • R 2 and R 3 are each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted C 1-8 alkyl, substituted or unsubstituted C 1-8 alkoxy, substituted or unsubstituted C 1-8 alkylthio, substituted or unsubstituted C 3-8 cycloalkyl or substituted or unsubstituted C 2-8 alkynyl, and R 2 and R 3 do not contain -C ⁇ CCH(OH)C ⁇ C-structural unit;
  • n and n are each an integer of 1-6, and m+n ⁇ 8.
  • the present invention provides a process for the preparation of the aforementioned chain polyacetylene compound.
  • the present invention provides a metal bridge fused ring compound having the structure shown by any one of Formulas I*-VI* and I'*-VI'*:
  • [M] 1 is RuAL 2 , RhL 2 or IrL 2 ;
  • [M] 2 is RuL 3 , RhAL 2 or IrAL 2 ;
  • [M] 4 is RuA 2 L, RhAL or IrAL;
  • A is -H, halogen, -SCN or -CN;
  • L is at least one of a phosphine ligand, a CO ligand, a pyridine ligand, a nitrogen heterocyclic carbene ligand, a nitrile ligand, and an isocyanide dual electron ligand;
  • R 1 * is a cationic substituent located on any of the positions of the formula I*-VI* labeled with the number 1-6, and R 1 * is a C 3-30 quaternary phosphonium cation or a C 3-24 quaternary ammonium cation ;
  • R 2 * is located on at least one of the positions of the formula 1*-VI* labeled with the numbers 1-9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent on at least one of the positions of the formula I'*-VI'* labeled with the numbers 1-9;
  • R 2 * and R 3 * are each independently selected from -H, halogen, -SCN, -CN, C 1-20 alkyl, C 1-20 alkoxy, C 1-20 alkylthio, C 1-20 Acyl, C 1-20 ester, C 1-20 amine, C 1-20 amide, C 1-20 carboxyl, C 2-20 amide, C 3-20 cycloalkyl, substituted or unsubstituted aryl A substituted or unsubstituted C 2-20 alkenyl group, a substituted or unsubstituted C 2-20 alkynyl group, a substituted or unsubstituted C 1-20 aryloxy group, a substituted or unsubstituted C 1-20 aromatic sulfur a base, and any one of the substituents capable of increasing water solubility;
  • X 1 is -CR 5 *R 6 *-, -NR 7 *-, -O-, -S-, and -Se-; the range of substituents selected for R 4 *, R 5 *, and R 6 * R 2 * or R 3 * is the same, R 7 * is a substituted or unsubstituted aryl group, a substituted or unsubstituted C 1-20 alkyl group or a substituted or unsubstituted C 3-20 cycloalkyl group;
  • Y 1 is -NR 7 *-, -O- or -S-;
  • Z 1 is Cl - , Br - , I - , BF 4 - , CF 3 SO 3 - , CH 3 COO - , (CF 3 SO 2 ) 2 N - , NO 3 - , ClO 4 - , PF 6 - or BPh 4 - .
  • the present invention provides a process for the preparation of the above metal bridge fused ring compounds.
  • the present invention provides the use of the above metal bridge fused ring compound in the fields of solar cells, photodynamic therapy, photolysis water, and lithium-air batteries.
  • the chain polyacetylene compound provided by the invention contains a plurality of functional groups and is controllable in structure, and can be used for efficiently synthesizing metal heterofused ring compounds.
  • the method for synthesizing the chain polyacetylene compound provided by the present invention is simple, and the chain polyacetylene compound can be obtained quickly and efficiently.
  • the main structure of the metal bridge fused ring compound provided by the invention has good planarity, is a large conjugate system, has aromaticity, good stability, good ultraviolet-visible-near infrared absorption spectrum and better Electrochemical performance, thus It is widely used in solar cells, photodynamic therapy, photolysis water and lithium-air batteries.
  • Fig. 1 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound I*-1 in Test Example 1 of the present invention.
  • Fig. 2 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound II*-1 in Test Example 2 of the present invention.
  • Fig. 3 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound II*-11 in Test Example 2 of the present invention.
  • Figure 5 is a graph showing the effect of the metal bridge fused ring compound II*-2 on the charge potential of a lithium-air battery in Test Example 3 of the present invention.
  • Figure 6 is a graph showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound IV*-1 in Test Example 4 of the present invention.
  • Figure 7 is a graph showing the results of in vitro active oxygen test of the metal bridge fused ring compound IV*-1 in Test Example 4 of the present invention.
  • Figure 8 is a graph showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound V*-3 in Test Example 5 of the present invention.
  • Figure 9 is a graph showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound VI*-1 in Test Example 6 of the present invention.
  • Figure 10 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound III*-9 in Test Example 7 of the present invention.
  • Figure 11 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound I'*-6 in Test Example 8 of the present invention.
  • Figure 12 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound II'*-9 in Test Example 9 of the present invention.
  • Figure 13 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound III'*-4 in Test Example 10 of the present invention.
  • Figure 14 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound IV'*-5 in Test Example 11 of the present invention.
  • Figure 15 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound V'*-1 in Test Example 12 of the present invention.
  • Figure 16 is a chart showing the ultraviolet-visible absorption spectrum of the metal bridge fused ring compound VI'*-11 in Test Example 13 of the present invention.
  • a C 2-30 alkynyl group, a substituted C 2-20 alkynyl group, a substituted C 4-30 polyalkynyl group, a substituted C 2-8 alkynyl group substituted herein represents a carbon.
  • the number of atoms 2-30, 2-20, 4-30, 2-8, etc. only refers to the number of carbon atoms in the main chain containing an alkynyl group or a polyalkynyl group, and does not include a main group containing an alkynyl group or a polyacetylene group.
  • C 1-20 alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl Base, sec-pentyl, tert-amyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, iso Octyl, neooctyl, sec-octyl, tert-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-
  • C 1-20 ester group means that the total number of carbon atoms is between 1 and 20 and contains an ester bond. One-price group.
  • the C 1-20 ester group can be with At least one of them.
  • C 1-20 acyl can be with Any of them.
  • the C 3-20 cycloalkyl group may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclooctadecyl and cycloecosane. At least one of the bases.
  • C 3-20 cycloalkyl may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, cyclooctadecane At least one of a group and a cyclohexadecyl group.
  • the "C 1-20 haloalkyl group” may be a substituent formed by substituting at least one of fluorine, chlorine, bromine, and iodine atoms for at least one hydrogen atom on the above C 1-20 alkyl group.
  • the "substituted or unsubstituted aryl group” may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group. At least one of a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolyl group.
  • the substituent in the substituted or unsubstituted aryl group may be a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 1-20 alkylthio group, a C 1-20 acyl group, a C 1-20 ester group.
  • C 1-8 alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl Base, sec-pentyl, tert-amyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, iso At least one of octyl, neooctyl, sec-octyl and tert-octyl.
  • C 2-30 alkynyl may be ethynyl, with At least one of them.
  • the cumulative polyalkenyl group refers to an olefin residue having more than one pair of adjacent carbon-carbon double bonds (i.e., cumulative double bonds) in the group.
  • the "substituted C 3-30 cumulative polyalkenyl group” means a group having 3 to 30 carbon atoms in a main chain containing a cumulative polyalkenyl group, and the 3 to 30 does not include a carbon which may be contained in a side chain. The number of atoms.
  • substituted C 3-30 cumulative polyalkenyl and "C 3-30 cumulative polyalkenyl” may be with At least one of them.
  • C 1-8 alkoxy may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, positive Pentyloxy, isopentyloxy, neopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, isohexyloxy, neohexyloxy, sec-hexyloxy, tert-hexyloxy, n-heptyloxy At least one of a group, an isoheptyloxy group, a neoheptyloxy group, a sec-heptyloxy group, a terteptenyloxy group, a n-octyloxy group, an isooctyloxy group, a neooctyloxy group, a sec-octyloxy group, and a
  • C 1-8 alkylthio may be methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, positive Butylthio, isopentylthio, neopentylthio, sec-pentylthio, tert-amylthio, n-hexylthio, isohexylthio, neohexylthio, sec-hexylthio, tert-hexylthio, n-heptanesulfate At least one of a base, an isoheptylthio group, a neoheptylthio group, a secondary heptylthio group, a tert-heptylthio group, a n-octylthio group, an
  • the "C 3-8 cycloalkyl group” may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • the "substituted or unsubstituted C 2-8 alkynyl group” may be ethynyl, propynyl, 1-butynyl, 3-methyl-1-butynyl, 1-pentynyl, 3-methyl- 1-Pentynyl, 4-methyl-1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl and phenylethynyl.
  • the "C 1-20 amine group” means an amine group having a total number of carbon atoms of from 1 to 20, and for example, the C 1-20 amine group may be a methylamino group, an ethylamino group, a propylamino group or a butylamine group. , pentylamino, hexylamino, heptylamino, octylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, n-dodecyl, n-hexadecyl, n. At least one of an octaamino group and a n-dosylamino group.
  • C 1-20 amide group means that the total number of carbon atoms is between 1 and 20 and contains an amide bond. Monovalent group, the C 1-20 amide group can be with At least one of them.
  • C 1-20 carboxyl can be with At least one of them.
  • C 2-20 amide group means an amide bond in the above amide group A substituent formed by substituting H attached to an N atom with an alkyl group of 1 to 20 carbon atoms.
  • the C 2-20 amide group can be with At least one of them.
  • Substituted or unsubstituted C 1-20 aryloxy may be selected from phenoxy (-OPh), naphthyloxy, anthracenyloxy, phenanthryloxy, anthracenyloxy, thienyloxy, furanoxy, pyridine Oxyl, pyrroleoxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, p-nitrophenoxy and p-methoxyphenoxy.
  • Substituted or unsubstituted C 1-20 arylthio may be selected from phenylthio (-SPh), naphthylthio, anthracenylthio, phenanthrylthio, sulfonylthio, thiophenethio, furanthio, pyridine Sulfur, pyrrolethio, p-tolylthio, m-tolylthio, o-tolylthio, p-nitrophenylthio and p-methoxyphenylthio.
  • C 1-8 alkoxy may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, positive Pentyloxy, isopentyloxy, neopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, isohexyloxy, neohexyloxy, sec-hexyloxy, tert-hexyloxy, n-heptyloxy Any of any of a group, an isoheptyloxy group, a neoheptyloxy group, a sec-heptyloxy group, a t-heptyloxy group, a n-octyloxy group, an isooctyloxy group, a neooctyloxy group, a sec-octyloxy group, and a
  • C 1-8 alkylthio may be methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, positive Butylthio, isopentylthio, neopentylthio, sec-pentylthio, tert-amylthio, n-hexylthio, isohexylthio, neohexylthio, sec-hexylthio, tert-hexylthio, n-heptanesulfate Any of any of a group, an isoheptylthio group, a neoheptylthio group, a secondary heptylthio group, a tert-heptylthio group, a n-octylthio group, an
  • the "substituent capable of increasing water solubility” may be a residue of a polyethylene glycol residue, a hyaluronic acid residue, a polyacrylic acid, and a saccharide derivative.
  • the polyethylene glycol residue refers to a portion remaining after the hydroxyl group at one end of the polyethylene glycol is removed from H.
  • the polyethylene glycol may have a weight average molecular weight of 200 to 200,000.
  • the hyaluronic acid residue refers to a portion of the hyaluronic acid D-glucuronic acid or N-acetylglucosamine which has the remaining hydroxyl group after the removal of H, or the carboxyl group of the hyaluronic acid D-glucuronic acid removes the hydroxyl group. The remainder after (-OH).
  • the hyaluronic acid may have a weight average molecular weight of from 2,000 to 2,000,000.
  • the saccharide derivative residue means a portion remaining after any one of the hydroxy groups of the saccharide derivative is removed from the hydrogen atom.
  • the saccharide derivative may be any one of derivatives of glucose, sucrose, maltose, galactose, lactose, fructose, and sialic acid.
  • the saccharide derivative may be, for example, glucuronic acid, glucose acetal, glucose hemiacetal, and carboxymethyl lactose.
  • the substituent in the substituted aryl group may be a C 1-8 alkyl group, a C 1-8 alkoxy group, a C 1-8 alkylthio group, a C 1-8 acyl group, a C 1-8 amide group, and C 1 . -8 ester group, C 1-8 carboxyl group, C 1-8 amine group, C 3-8 cycloalkyl group, halogen, nitro group and nitrile group.
  • the C 1-8 acyl group can be with
  • the C 1-8 amide group can be with Any of them.
  • the C 1-8 ester group can be with Any of them.
  • the C 1-8 carboxyl group can be with Any of them.
  • the "C 3-8 cycloalkyl group” may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • the C 1-8 amine group may be methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino, dimethylamino, diethylamino Any one of a dipropylamino group and a dibutylamine group.
  • the halogen may be any one of fluorine, chlorine, bromine and iodine.
  • the present invention provides a chain polyacetylene compound having the structure of Formula I below:
  • X is -O-, -S-, -CR 4 R 5 -, -SiR 6 R 7 - or -NR 8 -; and R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen. , C 1-20 alkyl, C 1-20 ester, C 1-20 acyl, C 3-20 cycloalkyl, C 1-20 haloalkyl, nitrile, nitro, substituted or unsubstituted aryl or R 9 is a C 1-8 alkyl group or a substituted or unsubstituted aryl group;
  • R 1 is a nitrile group, a substituted or unsubstituted C 2-30 alkynyl group, a substituted or unsubstituted C 4-30 polyalkynyl group, a substituted or unsubstituted C 3-30 cumulative polyalkenyl group, and does not contain -C ⁇ CCH(OH)C ⁇ C-structural unit;
  • R 2 and R 3 are each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted C 1-8 alkyl, substituted or unsubstituted C 1-8 alkoxy, substituted or unsubstituted C 1-8 alkylthio, substituted or unsubstituted C 3-8 cycloalkyl or substituted or unsubstituted C 2-8 alkynyl, and R 2 and R 3 do not contain -C ⁇ CCH(OH)C ⁇ C-structural unit;
  • n and n are each an integer of 1-6, and m+n ⁇ 8.
  • Embodiment 1 In the structure of Formula I, X is -O-, -S-, -CR 4 R 5 -, -SiR 6 R 7 - or -NR 8 -; R 4 , R 5 , R 6 And R 7 and R 8 are each independently hydrogen, C 1-17 alkyl, C 1-17 ester, C 1-17 acyl, C 3-17 cycloalkyl, C 1-17 haloalkyl, nitrile, Nitro, substituted or unsubstituted aryl or R 9 is C 1-6 alkyl or substituted or unsubstituted aryl;
  • R 1 is a nitrile group, a substituted or unsubstituted C 2-24 alkynyl group, a substituted or unsubstituted C 4-24 polyalkynyl group, a substituted or unsubstituted C 3-24 cumulative polyalkenyl group, and does not contain -C ⁇ CCH(OH)C ⁇ C-structural unit;
  • R 2 and R 3 are each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 alkylthio, substituted or unsubstituted C 3-6 cycloalkyl or substituted or unsubstituted C 2-6 alkynyl, and R 2 and R 3 do not contain -C ⁇ CCH(OH)C ⁇ C-structural unit;
  • n and n are each an integer of 1-6, and m+n ⁇ 8.
  • Embodiment 2 In the structure of Formula I, X is selected from the group consisting of -O-, -S-, -CH 2 -, -C(CH 3 ) 2 -, -CHCH 3 -, -C(COOMe) 2 - , -C(COOEt) 2 -, -C(COCH 3 )(COOMe)-, -C(Cy)(COOMe)-, -C(CH 2 CH 2 Br) 2 -, -C(CN) 2 -, -C (NO 2) 2 -, - SiH 2 -, - SiMe 2 -, - SiPh 2 -, - NH-, with
  • R 1 is selected from a nitrile group, an ethynyl group, with
  • R 2 and R 3 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, methylthio, ethyl sulphide Base, cyclopropyl, cyclohexyl, Ethynyl, propynyl, Benzyl and phenethyl;
  • n 1, 2, 3, 4, 5 or 6.
  • Embodiment 3 The structure represented by Formula I is at least one of the following compounds:
  • the present invention provides a process for the preparation of the above chain polyacetylene compound, wherein when R 3 is hydrogen, the process comprises: compounding the compound of formula II with organometallic reagent RM 1 and/or RM 2 Z The metal exchange reaction is carried out in a protic solvent, and the obtained reaction mixture is contacted with a compound of the formula III to obtain a Y group-protected chain polyacetylene compound represented by the formula IV; The group-protected chain polyacetylene compound is subjected to a deprotection group treatment to obtain a chain polyacetylene compound of the formula I:
  • Y is a protecting group for protecting an alkynyl group, and Y may be at least one of TMS (trimethylsilyl), TES (triethylsilyl), and TIPS (triisopropylsilyl).
  • TMS trimethylsilyl
  • TES triethylsilyl
  • TIPS triisopropylsilyl
  • R in the organometallic reagent RM 1 or RM 2 Z may be any one of a C 1-8 alkyl group, a phenyl group, and -NR 10 R 11 .
  • the -NR 10 R 11 R 10 and R 11 may each independently be any one of hydrogen, C 1-8 alkyl group and the trimethylsilyl group.
  • the C 1-8 alkyl groups are all the same as described above.
  • M 1 may be lithium, sodium or potassium.
  • M 2 can be magnesium.
  • Z can be chlorine, bromine or iodine.
  • the organometallic reagent RM 1 is methyl lithium, ethyl lithium, n-butyl lithium, t-butyl lithium, phenyl lithium, diisopropylamino lithium and bis(trimethylsilyl)amine. At least one of the base lithium.
  • RM 2 Z is at least one of methyl magnesium bromide, ethyl magnesium bromide, methyl magnesium chloride, and ethyl magnesium chloride.
  • the obtained Y group-protected chain polyacetylene compound represented by Formula IV can be subjected to a deprotection group treatment using a deprotecting agent.
  • the deprotecting agent may be K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , KF, (n-Bu) 4 NF (tetra-n-butylammonium fluoride), (Et) 4 NF (tetraethyl) At least one of ammonium fluoride), (Me) 4 NF (tetramethylammonium fluoride), and (n-Pr) 4 NF (tetra-n-propylammonium fluoride).
  • the Y-protected chain polyacetylene obtained in the step (1) is obtained after the deprotection group treatment of the Y group-protected chain polyacetylene compound represented by the formula IV
  • the mixture of compounds is subjected to a quenching and purifying operation.
  • the quenching agent used in the quenching operation may be saturated ammonium chloride and/or water.
  • the purifying operation may include extracting the obtained mixture containing the Y group-protected chain polyacetylene compound represented by Formula IV using an organic solvent, and extracting the obtained The obtained organic phase is dried, filtered, concentrated, and chromatographed to obtain a chain polyacetylene compound of the formula I.
  • the organic solvent may be at least one of diethyl ether, n-hexane, toluene, ethylene glycol dimethyl ether, 1,4-dioxane, dichloromethane, and chloroform;
  • the organic phase drying operation may include the use of anhydrous magnesium sulfate and/or anhydrous sodium sulfate;
  • the chromatographic separation may include the use of silica gel column chromatography and/or neutral alumina.
  • the mixture containing the chain polyacetylene compound of the formula I obtained after the deprotection group treatment of the Y group-protected chain polyacetyl compound represented by the formula IV is subjected to a quenching and purifying operation.
  • the method of quenching and purifying operation is the same as described above.
  • the preparation method of the above chain polyacetylene compound includes:
  • the compound represented by the formula II is subjected to a metal exchange reaction with the organometallic reagent RM 1 and/or RM 2 Z in an aprotic solvent, and the obtained reaction mixture is contacted with a compound represented by the formula V to obtain a formula I.
  • a metal exchange reaction with the organometallic reagent RM 1 and/or RM 2 Z in an aprotic solvent, and the obtained reaction mixture is contacted with a compound represented by the formula V to obtain a formula I.
  • organometallic reagent RM 1 or RM 2 Z is the same as above; X, R 1 , R 2 , m and n are all the same as described above.
  • the molar ratio of the compound of the formula II to the sum of the organometallic reagents RM 1 and/or RM 2 Z is 1: (0.5-1), preferably 1: (0.9-1).
  • the ratio of the amounts of the organometallic reagents RM 1 and RM 2 Z is not particularly limited, and they may be used in combination at any molar ratio.
  • the aprotic solvent is at least one of benzene, toluene, n-hexane, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane, petroleum ether, and gasoline.
  • the compound of the formula II can be subjected to a metal exchange reaction with an organometallic reagent RM 1 and/or RM 2 Z under the protection of an inert gas.
  • the inert gas is any gas that does not react with the catalyst, raw materials, and products, and does not adversely affect the reaction.
  • the inert gas may be at least one of nitrogen, helium, argon, and helium.
  • the conditions for contacting the compound of the formula II with the organometallic reagent RM 1 and/or RM 2 Z in an aprotic solvent include a temperature of from minus 100 ° C to above 30 ° C, preferably from minus 78 ° C to 0 ° C.
  • the time may be from 0.5 to 10 h, preferably from 1 to 3 h.
  • the reaction mixture obtained by subjecting the compound of the formula II to the metal exchange reaction of the organometallic reagent RM 1 and/or RM 2 Z in an aprotic solvent is contact-reacted with the compound of the formula III or the compound of the formula V.
  • the conditions include a temperature of from 100 ° C to 30 ° C above zero, preferably from 78 ° C to 0 ° C, and a time of from 0.5 to 10 h, preferably from 1 to 5 h.
  • the present invention provides the use of the above chain polyacetylene compound in the synthesis of a metal heterofused ring compound; the use of the chain polyacetylene compound in the synthesis of a metal heterofused ring compound comprises the use of the chain polyacetylene
  • the compound reacts with the metal complex to obtain a metal bridge fused ring compound;
  • the metal complex is DA a L b ; wherein D can be Fe, Co, Ni, Ru, Mn, Re, Cr, Mo, W, V Any one of Nb, Ta, Ti, Zr, Hf, Rh, Pd, Ir, Pt and Os;
  • A may be any one of H, halogen, SCN and CN;
  • L may be a phosphine ligand, CO a ligand, a pyridine ligand, a nitrogen heterocyclic carbene ligand, a nitrile ligand, and an isocyanide bielectron ligand;
  • the metal complex is any one of OsCl 2 (PPh 3 ) 3 , RuCl 2 (PPh 3 ) 3 , RhCl(PPh 3 ) 3 , IrCl(PPh 3 ) 3 and IrHCl 2 (PPh 3 ) 3 .
  • OsCl 2 (PPh 3 ) 3 RuCl 2 (PPh 3 ) 3
  • RhCl(PPh 3 ) 3 RhCl(PPh 3 ) 3
  • IrCl(PPh 3 ) 3 IrHCl 2 (PPh 3 ) 3 .
  • IrHCl 2 (PPh 3 ) 3 IrHCl 2
  • the metal bridge fused ring compound provided by the present invention has the structure shown by any one of Formulas I*-VI* and I'*-VI'*:
  • [M] 1 is RuAL 2 , RhL 2 or IrL 2 ;
  • [M] 2 is RuL 3 , RhAL 2 or IrAL 2 ;
  • [M] 4 is RuA 2 L, RhAL or IrAL;
  • A is -H, halogen, -SCN or -CN;
  • L is at least one of a phosphine ligand, a CO ligand, a pyridine ligand, a N-Heterocyclic Carbenes NHC ligand, a nitrile ligand, and an isocyanide dual electron ligand;
  • R 1 * is a cationic substituent located on any of the positions of the formula I*-VI* labeled with the number 1-6, and R 1 * is a C 3-30 quaternary phosphonium cation or a C 3-24 quaternary ammonium cation ;
  • R 2 * is located on at least one of the positions of the formula 1*-VI* labeled with the numbers 1-9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent on at least one of the positions of the formula I'*-VI'* labeled with the numbers 1-9;
  • R 2 * and R 3 * are each independently selected from -H, halogen, -SCN, -CN, C 1-20 alkyl, C 1-20 alkoxy, C 1-20 alkylthio, C 1-20 Acyl, C 1-20 ester, C 1-20 amine, C 1-20 amide, C 1-20 carboxyl, C 2-20 amide, C 3-20 cycloalkyl, substituted or unsubstituted aryl a substituted or unsubstituted C 2-20 alkenyl group, a substituted or unsubstituted C 2-20 alkynyl group, a substituted or unsubstituted C 6-20 aryloxy group, a substituted or unsubstituted C 6-20 aromatic sulfur a base, and any one of the substituents capable of increasing water solubility;
  • X 1 is -CR 5 *R 6 *-, -NR 7 *-, -O-, -S-, and -Se-; the range of substituents selected for R 4 *, R 5 *, and R 6 * R 2 * or R 3 * is the same, R 7 * is a substituted or unsubstituted aryl group, a substituted or unsubstituted C 1-20 alkyl group or a substituted or unsubstituted C 3-20 cycloalkyl group;
  • Y 1 is -NR 7 *-, -O- or -S-;
  • Z 1 is Cl - , Br - , I - (iodine ion), BF 4 - , CF 3 SO 3 - , CH 3 COO - , (CF 3 SO 2 ) 2 N - , NO 3 - , ClO 4 - , PF 6 - or BPh 4 - .
  • Embodiment 1 In the formulas I*-VI* and I'*-VI'*,
  • R 1 * is a cationic substituent on any of the positions on the formula I*-VI* labeled with the number 1-6, and R 1 * is a C 3-24 quaternary phosphonium cation or a C 3-20 quaternary ammonium cation ;
  • R 2 * is located on at least one of the positions of the formula 1*-VI* labeled with the numbers 1-9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent on at least one of the positions of the formula I'*-VI'* labeled with the numbers 1-9;
  • R 2 * and R 3 * are each independently selected from -H, halogen, -SCN, -CN, C 1-16 alkyl, C 1-16 alkoxy, C 1-16 alkylthio, C 1-16 Acyl, C 1-16 ester, C 1-16 amine, C 1-16 amide, C 1-16 carboxy, C 2-16 amide, C 3-16 cycloalkyl, substituted or unsubstituted aryl A substituted or unsubstituted C 2-16 alkenyl group, a substituted or unsubstituted C 2-16 alkynyl group, a substituted or unsubstituted C 6-16 aryloxy group, a substituted or unsubstituted C 6-16 aromatic sulfur a base, and any one of the substituents capable of increasing water solubility;
  • X 1 is -CR 5 *R 6 *-, -NR 7 *-, -O-, -S-, and -Se-; the range of substituents selected for R 4 *, R 5 *, and R 6 * R 2 * or R 3 * is the same, R 7 * is a substituted or unsubstituted aryl group, a substituted or unsubstituted C 1-16 alkyl group or a substituted or unsubstituted C 3-16 cycloalkyl group;
  • Y 1 is -NR 7 *-, -O- or -S-;
  • Z 1 is Cl - , Br - , I - (iodine ion), BF 4 - , CF 3 SO 3 - , CH 3 COO - , (CF 3 SO 2 ) 2 N - , NO 3 - , ClO 4 - , PF 6 - or BPh 4 - .
  • Embodiment 2 In the formulas I*-VI* and I'*-VI'*,
  • R 1 * is a cationic substituent on any of the positions on the formula I*-VI* labeled with the number 1-6, and R 1 * is a C 3-20 quaternary phosphonium cation or a C 3-16 quaternary ammonium cation ;
  • R 2 * is located on at least one of the positions of the formula 1*-VI* labeled with the numbers 1-9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent on at least one of the positions of the formula I'*-VI'* labeled with the numbers 1-9;
  • R 2 * and R 3 * are each independently selected from -H, halogen, -SCN, -CN, C 1-12 alkyl, C 1-12 alkoxy, C 1-12 alkylthio, C 1-12 Acyl, C 1-12 ester, C 1-12 amine, C 1-12 amide, C 1-12 carboxyl, C 2-12 amide, C 3-12 cycloalkyl, substituted or unsubstituted aryl a substituted or unsubstituted C 2-12 alkenyl group, a substituted or unsubstituted C 2-12 alkynyl group, a substituted or unsubstituted C 6-12 aryloxy group, a substituted or unsubstituted C 6-12 aromatic sulfur a base, and any one of the substituents capable of increasing water solubility;
  • X 1 is -CR 5 *R 6 *-, -NR 7 *-, -O-, -S-, and -Se-; the range of substituents selected for R 4 *, R 5 *, and R 6 * R 2 * or R 3 * is the same, R 7 * is a substituted or unsubstituted aryl group, a substituted or unsubstituted C 1-12 alkyl group or a substituted or unsubstituted C 3-12 cycloalkyl group;
  • Y 1 is -NR 7 *-, -O- or -S-;
  • Z 1 is Cl - , Br - , I - (iodine ion), BF 4 - , CF 3 SO 3 - , CH 3 COO - , (CF 3 SO 2 ) 2 N - , NO 3 - , ClO 4 - , PF 6 - or BPh 4 - .
  • Embodiment 3 In the formulas I*-VI* and I'*-VI'*,
  • R 1 * is a cationic substituent on any of the positions of the formula I*-VI* labeled with the number 1-6, and R 1 * is a C 3-12 quaternary phosphonium cation or a C 3-12 quaternary ammonium cation ;
  • R 2 * is located on at least one of the positions of the formula 1*-VI* labeled with the numbers 1-9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent on at least one of the positions of the formula I'*-VI'* labeled with the numbers 1-9;
  • R 2 * and R 3 * are each independently selected from -H, halogen, -SCN, -CN, C 1-8 alkyl, C 1-8 alkoxy, C 1-8 alkylthio, C 1-8 Acyl, C 1-8 ester, C 1-8 amine, C 1-8 amide, C 1-8 carboxyl, C 2-8 amide, C 3-8 cycloalkyl, substituted or unsubstituted aryl a substituted or unsubstituted C 2-8 alkenyl group, a substituted or unsubstituted C 2-8 alkynyl group, a substituted or unsubstituted C 6-8 aryloxy group, a substituted or unsubstituted C 6-8 aromatic sulfur a base, and any one of the substituents capable of increasing water solubility;
  • X 1 is -CR 5 *R 6 *-, -NR 7 *-, -O-, -S-, and -Se-; the range of substituents selected for R 4 *, R 5 *, and R 6 * R 2 * or R 3 * is the same, R 7 * is a substituted or unsubstituted aryl group, a substituted or unsubstituted C 1-8 alkyl group or a substituted or unsubstituted C 3-8 cycloalkyl group;
  • Y 1 is -NR 7 *-, -O- or -S-;
  • Z 1 is Cl - , Br - , I - (iodine ion), BF 4 - , CF 3 SO 3 - , CH 3 COO - , (CF 3 SO 2 ) 2 N - , NO 3 - , ClO 4 - , PF 6 - or BPh 4 - .
  • Embodiment 4 In the formulas I*-VI* and I'*-VI'*,
  • R 1 * is a cationic substituent located on any of the positions of the formula I*-VI* labeled with the number 1-6, and R 1 * is a C 3-8 quaternary phosphonium cation or a C 3-8 quaternary ammonium cation ;
  • R 2 * is located on at least one of the positions of the formula 1*-VI* labeled with the numbers 1-9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent on at least one of the positions of the formula I'*-VI'* labeled with the numbers 1-9;
  • R 2 * and R 3 * are each independently selected from -H, halogen, -SCN, -CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkylthio, C 1-6 Acyl, C 1-6 ester, C 1-6 amine, C 1-6 amide, C 1-6 carboxyl, C 2-6 amide, C 3-6 cycloalkyl, substituted or unsubstituted aryl a substituted or unsubstituted C 2-6 alkenyl group, a substituted or unsubstituted C 2-6 alkynyl group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted phenylthio group, and a water-soluble one. Any of the substituents;
  • X 1 is -CR 5 *R 6 *-, -NR 7 *-, -O-, -S-, and -Se-; the range of substituents selected for R 4 *, R 5 *, and R 6 * R 2 * or R 3 * is the same, R 7 * is a substituted or unsubstituted aryl group, a substituted or unsubstituted C 1-6 alkyl group or a substituted or unsubstituted C 3-6 cycloalkyl group;
  • Y 1 is -NR 7 *-, -O- or -S-;
  • Z 1 is Cl - , Br - , I - (iodine ion), BF 4 - , CF 3 SO 3 - , CH 3 COO - , (CF 3 SO 2 ) 2 N - , NO 3 - , ClO 4 - , PF 6 - or BPh 4 - .
  • the L may be selected from the group consisting of trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-tert-butylphosphine, Tricyclohexylphosphine, triphenylphosphine, tris(p-methylphenyl)phosphine, tris(m-methylphenyl)phosphine, diphenylphosphine, diphenylmethylphosphine, diphenylethylphosphine , picoline, ethyl pyridine, 1,4-bipyridine, 1,2-bis(4-pyridyl)ethylene, vinyl pyridine, ethynyl pyridine, pyridine boronic acid, aminopyridine, cyanopyridine, decyl pyridine, Dimethylaminopyridine, phenylpyridine, 1,2-
  • L 2 can be considered as a whole.
  • L 2 is any one selected from the group consisting of a bidentate nitrogen ligand, a bidentate phosphine ligand, a bidentate carbon-nitrogen ligand, and a bidentate oxygen-nitrogen ligand.
  • the bidentate nitrogen ligand refers to a ligand having a bidentate nitrogen atom as a coordinating atom.
  • the bidentate nitrogen ligand may be, for example, any one of ethylenediamine, 2,2'-bipyridine, and 1,10-phenanthroline.
  • the bidentate phosphine ligand refers to a ligand having a bidentate phosphorus atom as a coordinating atom.
  • the bidentate phosphine ligand may be, for example, DPPM (Bis-(diphenylphosphino) methane, 1,1-bis(diphenylphosphino)methane), DPPE (1,2-Bis(diphenylphosphino)ethane, 1,2-double Any of (diphenylphosphine)ethane and DPPP (1,3-Bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)propane.
  • the bidentate carbon-nitrogen ligand means a ligand having a bidentate carbon-nitrogen atom as a coordinating atom.
  • the bidentate carbon-nitrogen ligand may be, for example, o-phenylpyridine.
  • the bidentate oxygen-nitrogen ligand refers to a bidentate oxygen-nitrogen atom.
  • the ligand as a coordinating atom.
  • the bidentate oxygen-nitrogen ligand may be, for example, 8-hydroxyquinoline.
  • AL 2 may be regarded as a whole.
  • AL 2 is a terpyridine or other tridentic Pincer (plier)
  • the tridentate Pincer ligand can be, for example, any of PPP, PNP, PCP, NNN, NCN, NPN, ONO, OPO, OCO, SCS, and CCC Pincer ligands.
  • Embodiment 5 In the formulas I*-VI* and I'*-VI'*,
  • R 1 * is a cationic substituent located on any of the positions of the formula I*-VI* labeled with the number 1-6, and R 1 * is selected from the group consisting of trimethyl phosphonium cation, triethyl phosphonium cation, tripropyl propylene Base cation, triisopropyl sulfonium cation, tri-tert-butyl phosphonium cation, tricyclohexyl sulfonium cation, triphenylphosphonium cation, tris(p-methylphenyl)phosphonium cation, tris(m-methylphenyl) a phosphonium cation, a diphenyl phosphonium cation, a diphenylmethyl phosphonium cation, a diphenylethyl phosphonium cation, a trimethyl ammonium cation, a triethyl ammonium cation, a dimethyl mono
  • R 2 * is located on at least one of the positions of the formulas I*-VI* marked with the numbers 1, 3, 4, 5, 6, 8, and 9, and R 2 * is different from the position of R 1 *;
  • R 3 * is a substituent located on at least one of the positions of the formulas I'*-VI'* labeled with the numbers 1, 3, 4, 5, 6, 8, and 9;
  • R 2 * and R 3 * are each independently selected from -H, fluorine, chlorine, bromine, iodine, -SCN, -CN, -OPh, -SPh, methyl, ethyl, n-propyl, isopropyl, positive Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-amyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, N-heptyl, isoheptyl, neoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, sec-octyl, tert-oc
  • the substituent in the substituted alkenyl group and the substituted alkynyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl Base, isopentyl, neopentyl, sec-pentyl, tert-amyl, n-hexyl, isohexyl, neohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, with Any of them.
  • the substituted alkenyl group can be, for example, with
  • the substituted alkynyl group can be, for example, with
  • substituents R 2 * and R 3 * may each be one or more; if plural, a plurality of R 2 * and R 3 * on the same molecule may be the same or Different, as long as it is within the above range.
  • the cyclic substituent is a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring or an eight-membered ring substituent consisting entirely of carbon atoms, or contains oxygen, sulfur, and nitrogen.
  • R 30 * is a C 1-20 alkyl group or a substituted or unsubstituted aryl group; further preferably, the substituted or unsubstituted cyclic substituent is In particular, in the above substituted or unsubstituted cyclic substituent, which is not particularly defined herein, it may be substituted at any position of the above substituted or unsubstituted cyclic substituent
  • the C 1-20 alkyl group is the same as described above.
  • the substituent in the substituted or unsubstituted aryl group is the same as the substituent on the above substituted aryl group.
  • the substituent in the substituted aryl group is a C 1-20 alkyl group or a halogen. Preferably, for with Any of them.
  • the C 1-20 alkyl group, the C 1-20 ester group, the C 1-20 acyl group, the C 1-20 carboxyl group, the substituted or unsubstituted aryl group are all the same as described above.
  • the C 3-8 cycloalkyl group may be any one of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • a cyclic substituent is present at a 2,3-position or a 4,5-position in the formula I*-VI* and I'*-VI'*, and the cyclic substituent is
  • the metal bridge fused ring compound is any one of the following compounds:
  • [Ru] 1 is RuA(PPh 3 ) 2
  • [Ru] 2 is RuCO(PPh 3 ) 2
  • [Ru] 3 is Ru(PPh 3 ) 2
  • [Ru] 4 is RuA 2 PPh 3
  • [Rh] 1 is Rh(PPh 3 ) 2
  • [Rh] 2 is RhA(PPh 3 ) 2
  • [Rh] 3 is RhAPPh 3
  • [Rh] 4 is RhAPPh 3
  • [Ir] 1 is Ir(PPh 3 ) 2
  • [Ir] 2 is IrA(PPh 3 ) 2
  • [Ir] 3 is IrAPPh 3
  • [Ir] 4 is IrAPPh 3 ;
  • A is H, Cl, Br or SCN.
  • Me is a methyl group and Ph is a phenyl group. It is a triphenylphosphonium cation, Et is an ethyl group, BF 4 - is a tetrafluoroborate anion, and CF 3 SO 3 - is a trifluoromethanesulfonate anion.
  • the present invention provides a method for preparing the above metal heterofused ring compound, the method comprising:
  • the compound represented by the formula VII* is subjected to a cycloaddition reaction with a ruthenium complex to obtain a compound of the formula I*, and [M] 1 in the compound of the formula I* is RuAL 2 ;
  • the compound shown is reacted with a base 1 in an organic solvent to give a compound of the formula I*, and [M] 1 in the compound of the formula I* is RhL 2 or IrL 2 ;
  • the compound represented by the formula VII* is subjected to a cycloaddition reaction with a ruthenium complex and a ruthenium complex to obtain a compound represented by the formula II*, and in the compound of the formula II*, [M] 2 is RhAL 2 or IrAL. 2 ; or, a compound represented by the formula I* is subjected to a nucleophilic addition reaction with a nucleophilic reagent to obtain a compound represented by the formula II*;
  • the compound represented by the formula X* is subjected to a cycloaddition reaction with the compound of the formula I* to obtain a compound represented by the formula IV*;
  • a compound represented by formula XI* is subjected to a ring-opening reaction with a compound of formula III* to give a compound of formula V*;
  • the compound represented by the formula IX* is subjected to a cycloaddition reaction with a ruthenium complex, a ruthenium complex and a ruthenium complex to obtain a compound represented by the formula VI*;
  • the compound represented by the formula I'* is subjected to a nucleophilic addition reaction with a nucleophilic reagent to obtain a compound represented by the formula II'*; or the compound of the formula II* is hydrolyzed in an aqueous solution of the base 2 to obtain the formula II. a compound shown by '*;
  • the compound represented by the formula X* is subjected to a cycloaddition reaction with a compound of the formula I'* to obtain a compound represented by the formula IV'*; or the compound of the formula IV* is hydrolyzed in an aqueous solution of the base 2; Obtaining a compound of formula IV'*;
  • the compound represented by the formula XI* is subjected to a ring-opening reaction with a compound represented by the formula III'* to obtain a compound represented by the formula V'*; or the compound represented by the formula V* is hydrolyzed in an aqueous solution of the base 2 to obtain a compound of the formula V'*;
  • G is -O-, -S-, -CR 18 *R 19 *-, -SiR 20 *R 21 *- or -NR 22 *-;
  • R 18 *, R 19 *, R 20 *, R 21 * and R 22 * are each independently hydrogen, C 1-20 alkyl, C 1-20 ester group, C 1-20 acyl group, C 3-20 ring Alkyl, C 1-20 haloalkyl, nitrile, nitro, substituted or unsubstituted aryl or R 23 * is a C 1-8 alkyl group or a substituted or unsubstituted aryl group;
  • M1 and n1 are each an integer of 1-6, and m1+n1 ⁇ 8;
  • the ruthenium complex is at least one of RuCl 2 (PPh 3 ) 3 , RuCl 2 (PMe 3 ) 3 , RuCl 2 (PEt 3 ) 3 and RuCl 2 (PCy 3 ) 3 ;
  • the ruthenium complex is at least one of RhCl(PPh 3 ) 3 , RhHCl 2 (PPh 3 ) 3 , RhCl(PMe 3 ) 3 , RhCl(PEt 3 ) 3 and RhCl(PCy 3 ) 3 ;
  • the ruthenium complex is at least one of IrHCl 2 (PPh 3 ) 3 , IrCl(PPh 3 ) 3 , IrCl(PMe 3 ) 3 , IrCl(PEt 3 ) 3 and IrCl(PCy 3 ) 3 ;
  • the base 1 is an alkali metal carbonate and/or hydride
  • the base 2 is an alkali metal hydroxide
  • the nucleophilic reagent is a halogen element, a C 1-10 alcohol, a C 1-10 sodium alkoxide, a C 1-10 alkoxide, a C 1-10 thiol, a C 1-10 thiol sodium, a C 1-10 thiol At least one of potassium, C 1-10 phenol, C 1-10 phenol sodium, and C 1-10 phenol potassium.
  • the R 18 *, R 19 *, R 20 *, R 21 * and R 22 * are each independently hydrogen, C 1-17 alkyl, C 1-17 ester, C 1-17 acyl, C 3-17 cycloalkyl, C 1-17 haloalkyl, nitrile, nitro, substituted or unsubstituted aryl or R 23 * is a C 1-8 alkyl group or a substituted or unsubstituted aryl group.
  • the R 18 *, R 19 *, R 20 *, R 21 * and R 22 * are each independently hydrogen, C 1-8 alkyl, C 1-8 ester, C 1-8 acyl , C 3-8 cycloalkyl, C 1-8 haloalkyl, nitrile, nitro, substituted or unsubstituted aryl or R 23 * is a C 1-8 alkyl group or a substituted or unsubstituted aryl group.
  • the C 1-20 alkyl group, the C 1-20 ester group, the C 1-20 acyl group, and the C 3-20 cycloalkyl group are all the same as described above.
  • the C 1-20 haloalkyl group is a substituent formed by substituting at least one hydrogen of the above C 1-20 alkyl group with F, Cl, Br or iodine.
  • m1 and n1 are each an integer of 1-6, and m1+n1 ⁇ 8; for example, on the premise that m+n ⁇ 8, m1 and n1 may each independently be 1, 2, 3, 4, 5 or 6. Specifically, m1 is 1, n1 is 1, 2, 3, 4, 5 or 6; or m1 is 2, n1 is 1, 2, 3, 4 or 5; or m1 is 3, n1 is 1, 2, 3 Or 4; or m1 is 4, n1 is 1, 2 or 3; or m1 is 5, n1 is 1 or 2; or m1 is 6, n1 is 1.
  • the range of the optional substituent of R 10 * is the same as that of R 3 in the above formula I, and the range of the optional substituent of R 9 * is the same as R 2 in the above formula I
  • the range of values of m1 is the same as that of m in the above formula I
  • the range of the optional substituent of G is the same as that of X in the above formula I.
  • the base 1 is at least one of Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , CaH 2 and NaH.
  • the base 2 is NaOH and/or KOH.
  • concentration of the aqueous solution of the base 2 may be from 0.01 to 10 mol/liter, preferably from 0.5 to 5 mol/liter.
  • the nucleophilic reagent is Cl 2 , Br 2 , sodium methoxide, sodium ethoxide, sodium phenolate, sodium p-cresol, sodium thiophenolate, sodium p-tolylthiophene and sodium p-methoxythiophenolate. At least one.
  • said For example, it can be with At least one of them.
  • the conditions of the cycloaddition reaction include a reaction temperature of from minus 100 ° C to above 200 ° C, preferably from 0 to 60 ° C; and a reaction time of from 1 minute to 2 days, preferably from 0.5 hour to 1 day.
  • the conditions of the nucleophilic addition reaction comprise a reaction temperature of from minus 100 ° C to above 200 ° C, preferably from 0 to 60 ° C; and a reaction time of from 1 minute to 2 days, preferably from 0.5 hour to 1 day.
  • the conditions for the ring expansion reaction include a reaction temperature of from minus 100 ° C to above 200 ° C, preferably from 0 to 60 ° C; and a reaction time of from 1 minute to 2 days, preferably from 0.5 hour to 1 day.
  • the reaction of the above preparation method is carried out in the presence of an organic solvent; dichloromethane, dichloroethane, chloroform, methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide; At least one of N,N-dimethylformamide, toluene, benzene, dioxane, diethyl ether and acetonitrile.
  • the obtained reaction mixture may be concentrated, precipitated to obtain a solid substance, and the obtained solid substance is subjected to filtration, washing and column chromatography to obtain the metal bridge fused ring compound. .
  • the preparation of the compound of the formula VII*, the formula VIII* and the formula IX* is the same as the preparation of the compound of the above formula I.
  • the method includes:
  • the compound represented by the formula XII* is subjected to a metal exchange reaction with an organometallic reagent R*M 1 * and/or R*M 2 *Z 1 in an aprotic solvent, and the obtained reaction mixture is represented by the formula XIII*
  • the compound is contacted to obtain a chain-protected chain polyacetylene compound represented by the formula XIV*; and the chain-protected chain polyacetylene compound represented by the formula XIV* is subjected to a deprotection group treatment to obtain a formula.
  • J is a protecting group for protecting an alkynyl group.
  • J may be any one of TMS (trimethylsilyl), TES (triethylsilyl), and TIPS (triisopropylsilyl).
  • R* in the organometallic reagent R*M 1 * or R*M 2 *Z 1 is any one of a C 1-8 alkyl group, a phenyl group, and -NR 35 *R 36 *.
  • R 35 * and R 36 * in -NR 35 *R 36 * may each independently be any one of hydrogen, a C 1-8 alkyl group and a trimethylsilyl group.
  • the C 1-8 alkyl group is the same as described above.
  • M 1 * is preferably lithium, sodium or potassium.
  • M 2 * is preferably magnesium.
  • Z 1 is preferably chlorine, bromine or iodine.
  • R*M 1 * is methyl lithium, ethyl lithium, n-butyl lithium, t-butyl lithium, phenyl lithium, diisopropylamino lithium, and bis(trimethylsilyl)amine lithium At least one of them.
  • R*M 2 *Z 1 is at least one of methyl magnesium bromide, ethyl magnesium bromide, methyl magnesium chloride, and ethyl magnesium chloride.
  • the obtained chain-protected chain polyacetylene compound represented by the formula XIV* obtained by the obtained deprotecting agent is preferably subjected to a deprotection group treatment.
  • the deprotecting agent may be K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , KF, (n-Bu) 4 NF (tetra-n-butylammonium fluoride), (Et) 4 NF (tetraethyl) At least one of ammonium fluoride), (Me) 4 NF (tetramethylammonium fluoride), and (n-Pr) 4 NF (tetra-n-propylammonium fluoride).
  • the obtained chain-like polyacetylene compound having a J group protected by the formula XIV* is obtained before the deprotection group treatment of the chain-protected chain polyacetylene compound represented by the formula XIV* is carried out.
  • the mixture is subjected to a quenching and purifying operation.
  • the quenching agent used in the quenching operation may be saturated ammonium chloride and/or water.
  • the purifying operation may include extracting a mixture obtained by the obtained J group-protected chain polyacetylene compound represented by the formula XIV* using an organic solvent, drying the organic phase obtained by the extraction, filtering, concentrating, and separating by chromatography.
  • a compound of the formula VII*, formula VIII* and formula IX* is a compound of the formula VII*, formula VIII* and formula IX*.
  • the organic solvent may be at least one of diethyl ether, n-hexane, toluene, ethylene glycol dimethyl ether, 1,4-dioxane, dichloromethane, and chloroform;
  • the organic phase drying operation may include the use of anhydrous magnesium sulfate and/or anhydrous sodium sulfate;
  • the chromatographic separation may include the use of silica gel column chromatography and/or neutral alumina.
  • the chain polyene compound represented by the formula VII*, the formula VIII* and the formula IX* obtained after the deprotection group treatment of the chain-protected chain polyacetylene compound represented by the formula XIV* is obtained.
  • the mixture is subjected to a quenching and purifying operation.
  • the method of quenching and purifying operation is the same as described above.
  • the compound represented by the formula XII* is subjected to a metal exchange reaction with an organometallic reagent R*M 1 * and/or R*M 2 *Z 1 in an aprotic solvent, and the obtained reaction mixture is represented by the formula XV*
  • the compound is contacted to obtain a compound of the formula VII*, formula VIII* or formula IX*:
  • organometallic reagent R*M 1 * or R*M 2 *Z 1 is the same as defined above; G, R 33 *, m1 and n1 are all the same as defined above, and the optional range of the R 34 * and R The optional range of 9 * corresponds to the same.
  • the molar ratio of the compound represented by the formula XII* to the sum of the organometallic reagents R*M 1 * and/or R*M 2 *Z 1 is 1: (0.5-1), preferably 1: (0.9) -1).
  • the ratio of the amounts of the organometallic reagents R*M 1 * and R*M 2 *Z 1 is not particularly limited, and the two may be in any molar amount. More than mixed use.
  • the aprotic solvent is not particularly limited.
  • the aprotic solvent is at least one of benzene, toluene, n-hexane, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane, petroleum ether, and gasoline.
  • the compound represented by the formula XII* and the organometallic reagent R*M 1 * and/or R*M 2 *Z 1 may be subjected to a metal exchange reaction under the protection of an inert gas.
  • the inert gas is any gas that does not react with the catalyst, raw materials, and products, and does not adversely affect the reaction.
  • the inert gas may be at least one of nitrogen, helium, argon, and helium.
  • the conditions for contacting the compound represented by the formula XII* with the organometallic reagent R*M 1 * and/or R*M 2 *Z 1 in an aprotic solvent include a temperature of from 100 ° C to 30 ° C, It is preferably from 78 ° C to 0 ° C under zero, and the time is from 0.5 to 10 h, preferably from 1 to 3 h.
  • a reaction mixture obtained by subjecting a compound represented by the formula XII* to an organometallic reagent R*M 1 * and/or R*M 2 *Z 1 in an aprotic solvent, and a formula XIII * The compound shown or the compound of the formula XV* is subjected to a reaction reaction comprising a temperature of from 100 ° C to 30 ° C, preferably from about 78 ° C to 0 ° C, for a period of from 0.5 to 10 h, preferably from 1 to 5 h. .
  • the present invention provides the use of the aforementioned metal bridge fused ring compound in the field of solar cells, photodynamic therapy, photolysis water, lithium-air batteries.
  • the compounds of the formulae I*, I'*, II*, II'* and VI* are suitable for use in the field of solar cells.
  • the compound of formula II* is suitable for use in the field of lithium-air batteries
  • the compounds of formula III*, IV*, V*, III'*, IV'*, V'* and VI'* are suitable for photodynamic therapy. area.
  • R 2 * is a substituent numbered 1-6, R 2 * is preferably H; 2,3-position, 3,4 labeled with numbers 1-6 Any one of a position, a 4,5-position and a 5,6-position, preferably a substituted or unsubstituted cyclic substituent at the 4,5-position; preferably the cyclic substituent is composed entirely of carbon atoms a five-membered or six-membered ring substituent, or a five- or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; a substitution on the substituted cyclic substituent
  • the group is preferably a C 1-20 ester group
  • the compound of the formula I* is suitable for use in the field of solar cells, and further preferably as a photosensitizer for solar cells.
  • R 2 * is a substituent numbered 1-6, R 2 * is preferably H; 2,3-position, 3,4 labeled with numbers 1-6 Any one of a position, a 4,5-position and a 5,6-position, preferably a substituted or unsubstituted cyclic substituent at the 4,5-position; preferably the cyclic substituent is composed entirely of carbon atoms a five-membered or six-membered ring substituent, or a five- or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; a substitution on the substituted cyclic substituent
  • the group is preferably a C 1-20 ester group
  • the compound of the formula II* is suitable for use in the field of solar cells or lithium-air batteries, and further, as a photosensitizer for solar cells or as a lithium storage material for lithium - In the air battery.
  • R 2 * is a number 1, 2 , 3 , 7 or 8, preferably labeled with a number 8, preferably R 2 * is a C 1-20 alkoxy group.
  • a base any of the 2,3-position, 3,4-position, 4,5-position, and 5,6-position labeled with numbers 1-6, preferably substituted or unsubstituted at the 4,5-position a cyclic substituent; preferably the cyclic substituent is a four-membered ring, a five-membered ring or a six-membered ring substituent consisting entirely of carbon atoms, or consists of any one of oxygen, nitrogen and silicon atoms together with a carbon atom When a four-membered, five-membered or six-membered ring substituent is used; the compound of formula IV* is suitable for photodynamic therapy.
  • R 2 * is at least one of the numbers 1, 2, 3, 7, 8, and 9, preferably the substituents on the numbers 8 and 9, R 2 * is preferably a C 1-20 alkoxy group or a C 1-20 ester group; in the 2,3-position, 3,4-position, 4,5-position and 5,6-position labeled with numbers 1-6 Any one, preferably a substituted or unsubstituted cyclic substituent at the 4,5-position; preferably the cyclic substituent is a five- or six-membered ring substituent consisting entirely of carbon atoms, or by oxygen, a five-membered or six-membered ring substituent consisting of any one of nitrogen and a silicon atom together with a carbon atom; the substituent on the substituted cyclic substituent is preferably a C 1-20 ester group; Y 1 is -O - or -S-; the compound of formula V* is suitable for use in tumor photodynamic therapy.
  • R 2 * is a number 1, 2 , 3 , 7 or 8, preferably substituted with a substituent on the number 8, and R 2 * is an aryl group, preferably Phenyl; any of the 2,3-position, 3,4-position, 4,5-position, and 5,6-position labeled with numbers 1-6, preferably substituted or unsubstituted at the 4,5-position a cyclic substituent; preferably the cyclic substituent is a five-membered or six-membered ring substituent consisting entirely of carbon atoms, or a five-membered member consisting of any one of oxygen, nitrogen and silicon atoms together with a carbon atom a ring or a six-membered ring substituent; when the substituent on the substituted cyclic substituent is preferably a C 1-20 ester group; the compound of the formula VI* is suitable for use in the field of solar cells, and further, as a solar cell Photosensitizer
  • R 2 * is a substituent numbered 1-6, R 2 * is preferably H; 2,3-position, 3,4 labeled with numbers 1-6 Any one of a position, a 4,5-position and a 5,6-position, preferably a substituted or unsubstituted cyclic substituent at the 4,5-position; preferably the cyclic substituent is composed entirely of carbon atoms a five-membered or six-membered ring substituent, or a five- or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; a substitution on the substituted cyclic substituent
  • the group is preferably a C 1-20 ester group; when X 1 is -O- or -S-; the compound of formula III* is suitable for use in tumor photodynamic therapy.
  • R 3 * is a substituent numbered 1-6, R 3 * is preferably H; 2,3-position, 3, numbered 1-6, Any one of 4-position, 4,5-position and 5,6-position, preferably a substituted or unsubstituted cyclic substituent at the 4,5-position; preferably the cyclic substituent is entirely composed of carbon atoms
  • a compound of the formula I'* is suitable for a five-membered or six-membered ring substituent consisting of a five-membered or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom and a carbon atom. In the field of solar cells, it is further preferred to use as a photosensitizer for solar cells.
  • R 3 * is a substituent numbered 1-6, R 3 * is preferably H; 2,3-position, 3, numbered 1-6, a 4-position, a 4,5-position or a 5,6-position, preferably a substituted or unsubstituted cyclic substituent at the 4,5-position; preferably the cyclic substituent is a five-membered all carbon atom a compound represented by the formula II'* is suitable for use in the field of solar cells when a ring or a six-membered ring substituent or a five-membered or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom and a carbon atom is used together. Further preferably, it is used as a photosensitizer for a solar cell.
  • R 3 * is a substituent numbered 1-6, R 3 * is an aryl group, preferably a phenyl group; 2, 3 labeled with numbers 1-6 a substituted or unsubstituted cyclic substituent at a position, a 3,4-position, a 4,5-position or a 5,6-position, preferably a 4,5-position; preferably the cyclic substituent is all carbon a five-membered or six-membered ring substituent consisting of an atom, or a five-membered or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; X 1 is The compound of formula III'* is suitable for use in tumor photodynamic therapy.
  • R 3 * is a substituent on the numbers 1-8, R 3 * is an aryl group, preferably a phenyl group; 2, 3 labeled with numbers 1-6 a substituted or unsubstituted cyclic substituent at a position, a 3,4-position, a 4,5-position or a 5,6-position, preferably a 4,5-position; preferably the cyclic substituent is all carbon a five-membered or six-membered ring substituent consisting of an atom, or a five-membered or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; said substituted cyclic substituent
  • the substituent is preferably a C 1-20 ester group;
  • X 1 is The compounds of formula IV'* are suitable for use in tumor photodynamic therapy.
  • R 3 * is a substituent on the numbers 1-9, R 3 * is a C 1-20 alkyl group; 2,3-labeled with the numbers 1-6 a substituted, unsubstituted cyclic substituent at a position, a 3,4-position, a 4,5-position or a 5,6-position, preferably a 4,5-position; preferably the cyclic substituent is entirely composed of carbon atoms a five-membered or six-membered ring substituent consisting of, or a five- or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; on the substituted cyclic substituent
  • the substituent is preferably a C 1-20 ester group; when Y 1 is -O- or -S-, the compound of formula V'* is suitable for use in tumor photodynamic therapy.
  • R 3 * is a substituent on the numbers 1-8, R 3 * is a C 1-20 alkoxy group; 2, 3 numbered 1-6 a substituted or unsubstituted cyclic substituent at a position, a 3,4-position, a 4,5-position or a 5,6-position, preferably a 4,5-position; preferably the cyclic substituent is all carbon a five-membered or six-membered ring substituent consisting of an atom, or a five-membered or six-membered ring substituent consisting of any one of oxygen, nitrogen and a silicon atom together with a carbon atom; said substituted cyclic substituent When the substituent is preferably a C 1-20 ester group, the compound of formula VI'* is suitable for use in tumor photodynamic therapy.
  • TMS represents a trimethylsilyl group.
  • EtMgBr is ethyl magnesium bromide (purchased from BEHRINGER TECHNOLOGY CO., LTD., trade name No. 248474).
  • (n-Bu) 4 NF tetra-n-butylammonium fluoride, purchased from BEHRINGER TECHNOLOGY CO., LTD. The grade is A10588).
  • 1,6-heptadiyne (43.63 mmol, purchased from Aladdin Reagent (Shanghai) Co., Ltd., trade name H102744-25 mL) was dissolved in 100 mL of tetrahydrofuran under nitrogen atmosphere and cooled to 0 °C.
  • Add ethyl magnesium bromide solution (1.0M tetrahydrofuran solution, 43.6mL, containing ethyl bromide 43.60mmol)
  • add in 1h react at room temperature for 1h, then cool to 0 °C, quickly add top three Silane propargyl aldehyde (7.30 mL, 43.60 mmol), the reaction was continued for 1 h.
  • n-BuLi is n-butyl lithium (purchased from BEHRINGER TECHNOLOGY CO., LTD., trade name No. 913796).
  • the method for producing the compound 5 is the same as the method for producing the compound 1, except for the following features.
  • Yield of compound 5 75%. (The yield of the compound 5 is the molar amount of the compound 5 / the molar amount of the propargyl ether ⁇ 100%).
  • Yield of compound 6 87%. (The yield of the compound 6 is the molar amount of the compound 6 / the molar amount of the compound 5 ⁇ 100%).
  • the method for producing the compound 7 is the same as the method for producing the compound 3, except for the following features.
  • Yield of compound 7 75%. (The yield of the compound 7 is the molar amount of the compound 7 / the molar amount of the dimethyl 2-dipropargylmalonate ⁇ 100%).
  • the nuclear magnetic data of Compound 7 is as follows:
  • the method for producing the compound 8 is the same as the method for producing the compound 1, except for the following features.
  • Yield of Compound 8 82%. (The yield of Compound 8 is the molar amount of Compound 8 / the molar amount of 1-propargyloxy-2-butyne ⁇ 100%).
  • the nuclear magnetic data of Compound 8 is as follows:
  • Yield of compound 9 86%. (The yield of the compound 9 is the molar amount of the compound 9 / the molar amount of the compound 8 ⁇ 100%).
  • the nuclear magnetic data of Compound 9 is as follows:
  • the method for producing the compound 13 is the same as the method for producing the compound 3, except for the following features.
  • Compound 13 was a pale yellow oily liquid. Yield: 55%. (The yield of the compound 13 is the molar amount of the compound 13 / the molar amount of 4-propargyloxy-1,2-butadiene ⁇ 100%).
  • Compound 14 was a pale yellow oily liquid. Yield: 92%. (The yield of the compound 14 is the molar amount of the compound 14 / the molar amount of the compound 13 ⁇ 100%).
  • the method for producing the compound 15 is the same as the method for producing the compound 3, except for the following features.
  • Compound 15 was a pale yellow solid, yield: 45%. (The yield of Compound 15 is the molar amount of Compound 15 / 2 molar amount of propargyl-2-(5-phenyl-2,4-pentadiynyl)malonate dimethyl ester ⁇ 100%).
  • Compound 16 was a pale yellow solid, yield: 89%. (The yield of the compound 16 is the molar amount of the compound 16 / the molar amount of the compound 15 ⁇ 100%).
  • the method for producing the compound 17 is the same as the method for producing the compound 1, except for the following features.
  • the nuclear magnetic data of Compound 17 is as follows:
  • the method for producing the compound 18 is the same as the method for producing the compound 1, except for the following features.
  • Example 1 The 1,6-heptadiyne used in Example 1 was replaced with an equimolar amount of 1,8-decadiyne (available from Alfa Aesar (China) Chemical Co., Ltd., trade name MFCD00008581).
  • Yield of compound 18 47%. (The yield of Compound 18 is the molar amount of Compound 18 / the molar amount of 1,8-decadiyne ⁇ 100%).
  • the nuclear magnetic data of Compound 18 is as follows:
  • Yield of compound 19 80%. (The yield of the compound 19 is the molar amount of the compound 19 / the molar amount of the compound 18 ⁇ 100%).
  • the nuclear magnetic data of Compound 19 is as follows:
  • the method for producing the compound 20 is the same as the method for producing the compound 3, except for the following features.
  • the nuclear magnetic data of Compound 20 is as follows:
  • Compound 21 was a pale yellow oily liquid. Yield: 93%. (The yield of the compound 21 is the molar amount of the compound 21 / the molar amount of the compound 20 ⁇ 100%).
  • the method for producing the compound 22 is the same as the method for producing the compound 3, except for the following features.
  • the nuclear magnetic data of Compound 22 is as follows:
  • Compound 23 was a pale yellow oily liquid. Yield: 93%. (The yield of the compound 23 is the molar amount of the compound 23 / the molar amount of the compound 22 ⁇ 100%).
  • the nuclear magnetic data of Compound 23 is as follows:
  • the method for producing the compound 24 is the same as the method for producing the compound 3, except for the following features.
  • Compound 24 was a pale yellow solid, yield: 47%. (The yield of the compound 24 is the molar amount of the compound 24 / the molar amount of the dimethyl 2-propargyl-2-(5-(2-thienyl)-2,4-pentadiynyl)malonate ⁇ 100%).
  • the nuclear magnetic data of Compound 24 is as follows:
  • Compound 25 was a pale yellow solid, yield: 83%. (The yield of the compound 25 is the molar amount of the compound 25 / the molar amount of the compound 24 ⁇ 100%).
  • the nuclear magnetic data of Compound 25 is as follows:
  • the method for producing the compound 7-1 is the same as the method for producing the compound 3, except for the following features.
  • the yield of the compound 7-1 is the molar amount of the compound 7-1 / N, the molar amount of the N-dipropargyl p-toluenesulfonamide ⁇ 100%).
  • Yield of compound 8-1 81%. (The yield of the compound 8-1 is the molar amount of the compound 8-1 / the molar amount of the compound 7-1 ⁇ 100%).
  • the method for producing the compound 9-1 is the same as the method for producing the compound 1, except for the following features.
  • Yield of compound 9-1 45%. (The yield of the compound 9-1 is the molar amount of the compound 9-1 / the molar amount of the 1,7-octadiyne ⁇ 100%).
  • Yield of compound 10-1 78%. (The yield of the compound 10-1 is the molar amount of the compound 10-1 / the molar amount of the compound 9-1 ⁇ 100%).
  • the method for producing the compound 11-1 is the same as the method for producing the compound 3 except for the following features.
  • Compound 11-1 was a pale yellow oily liquid. Yield: 81%. (The yield of the compound 11-1 is the molar amount of the compound 11-1/5-molar amount of the hepyneonitrile ⁇ 100%).
  • the compound 3 used in the preparation of the step (2) of the second embodiment was replaced with the compound 11-1 obtained in the step (1) of the example.
  • Compound 12-1 was a pale yellow oily liquid. Yield: 83%. (The yield of the compound 12-1 is the molar amount of the compound 12-1 / the molar amount of the compound 11-1 ⁇ 100%).
  • the preparation method of the compound 17-1 was the same as that of the compound 1, except for the following characteristics.
  • Yield of compound 17-1 70%. (The yield of the compound 17-1 is the molar amount of the compound 17-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the method for producing the compound 18-1 was the same as the method for producing the compound 1, except for the following characteristics.
  • yield of compound 18-1 62%. (The yield of the compound 18-1 is the molar amount of the compound 18-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the method for producing the compound 19-1 was the same as the method for producing the compound 1, except for the following characteristics.
  • the 1,6-heptadiyne used in the step (1) of Preparation Example 1 was replaced by an equimolar amount of propargyl ether, and the trimethylsilylpropanal was replaced by an equimolar amount of 4-phenyl-3-butyne.
  • 2-ketone purchased from Alfa Aesar (China) Chemical Co., Ltd., trade name number MFCD00008776).
  • Yield of compound 19-1 65%. (The yield of the compound 19-1 is the molar amount of the compound 19-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the preparation method of the compound 20-1 was the same as that of the compound 1, except for the following characteristics.
  • Yield of Compound 20-1 60%. (The yield of the compound 20-1 is the molar amount of the compound 20-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the method for producing the compound 21-1 was the same as the method for producing the compound 1, except for the following characteristics.
  • Yield of Compound 21-1 60%. (The yield of the compound 21-1 is the molar amount of the compound 21-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the preparation method of the compound 22-1 was the same as that of the compound 1, except for the following characteristics.
  • yield of compound 22-1 68%. (The yield of the compound 22-1 is the molar amount of the compound 22-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the method for producing the compound 23-1 was the same as the method for producing the compound 1, except for the following characteristics.
  • Yield of compound 23-1 71%. (The yield of the compound 23-1 was the molar amount of the compound 23-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the method for producing the compound 24-1 was the same as the method for producing the compound 1, except for the following characteristics.
  • Yield of compound 24-1 54%. (The yield of the compound 24-1 is the molar amount of the compound 24-1 / the molar amount of the propargyl ether ⁇ 100%).
  • the preparation method of the compound 25-1 was the same as that of the compound 3 except for the following characteristics.
  • Yield of compound 25-1 50%. (The yield of the compound 25-1 is the molar amount of the compound 25-1 / the molar amount of the dimethyl 2-propargyl-2-(5-phenyl-2,4-pentadiynyl)malonate ⁇ 100%).
  • the preparation method of the compound 26-1 was the same as that of the compound 3 except for the following characteristics.
  • Yield of compound 26-1 81%. (The yield of the compound 26-1 is the molar amount of the compound 26-1 / the molar amount of the dimethyl-2-propargyl-2-phenylpropargyl malonate ⁇ 100%).
  • Yield of Compound 27-1 89%. (The yield of the compound 27-1 is the molar amount of the compound 27-1 / the molar amount of the compound 26-1 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Ru] 1 is RuCl(PPh 3 ) 2
  • PPh 3 is triphenylphosphine
  • DCM is dichloromethane
  • Me is methyl.
  • reaction liquid was concentrated to 5 mL with a vacuum pump, and then washed with n-hexane (three times, 50 mL each time) to give 1.23 g of Compound I*-1 as a red solid, yield: 70% (yield of compound I*-1 as compound I) *1 molar amount / RuCl 2 (PPh 3 ) 3 molar amount ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound I*-3 is the same as that of the compound I*-1 in the first embodiment except for the following features:
  • the compound I*-3 was obtained as a red solid, yield: 68% (yield of compound I*-3 was the molar amount of compound I*-3/molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound I*-8 is the same as that of the compound I*-1 in the first embodiment except for the following features:
  • HC ⁇ CCH used in Example 1 of the embodiment (OH) C ⁇ CCH 2 C (COOMe ) 2 CH 2 C ⁇ CH the like into moles of Preparation Example 4 was HC ⁇ CCPh (OH) C ⁇ CCH 2 C (COOMe) 2 CH 2 C ⁇ CH.
  • the compound I*-8 was obtained as a red solid, yield: 70% (yield of compound I*-8 was a molar amount of compound I*-8 / molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound I*-11 is the same as that of the compound I*-1 in the first embodiment:
  • the compound I*-11 was obtained as a red solid, yield: 71% (yield of compound I*-11 was a molar amount of compound I*-11 / molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound I*-5 is the same as that of the compound I*-1 in the first embodiment:
  • Example 1 The reaction temperature in Example 1 was raised from room temperature to 60 ° C, and the time was extended from 1 hour to 1 day.
  • the compound I*-5 was obtained as a red solid in a yield: 62% (yield of compound I*-5 was a molar amount of compound I*-5 / a molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Ir] 2 is IrCl(PPh 3 ) 2 and [Ir] 1 is Ir(PPh 3 ) 2 .
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Rh] 2 is RhCl(PPh 3 ) 2 and [Rh] 1 is Rh(PPh 3 ) 2 .
  • the preparation method of the compound I*-6 is the same as that of the compound I*-7 in the embodiment 6:
  • Example 6 The compound II*-10 used in Example 6 was replaced with an equimolar amount of the compound II*-2 obtained in Example 11.
  • the compound I*-6 was obtained as a red solid in a yield: 83% (yield of compound I*-6 was a molar amount of compound I*-6/molar amount of compound II*-2 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula I*.
  • [Rh] 2 is RhCl(PPh 3 ) 2 and [Rh] 1 is Rh(PPh 3 ) 2 .
  • Example 6 The compound II*-10 used in Example 6 was replaced with an equimolar amount of the compound II*-13 obtained in Example 12.
  • the compound I*-14 was obtained as a red solid in a yield: 81% (yield of compound I*-14 as a molar amount of compound I*-14 / molar amount of compound II*-13 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Ir] 2 is IrCl(PPh 3 ) 2
  • CDCl 3 is deuterated chloroform.
  • the preparation method of the compound II*-10 is the same as the preparation method of the compound I*-1 in the first embodiment except for the following features:
  • Example 1 The HC ⁇ CCH(OH)C ⁇ CCH 2 C(COOMe) 2 CH 2 C ⁇ CH used in Example 1 was replaced with an equimolar amount of HC ⁇ CCH(OH)C ⁇ C (CH) prepared in Preparation Example 1. 2 ) 3 C ⁇ CH, replace DCM with CDCl 3 (deuterated chloroform), and replace RuCl 2 (PPh 3 ) 3 with IrHCl 2 (PPh 3 ) 3 .
  • the compound II*-10 was obtained as a red solid, yield: 35% (yield of compound II*-10 was the molar amount of compound II*-10/molar amount of IrHCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Rh] 2 is RhCl(PPh 3 ) 2
  • HBF 4 ⁇ H 2 O is an aqueous solution of tetrafluoroboric acid.
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Rh] 2 is RhCl(PPh 3 ) 2
  • HBF 4 ⁇ H 2 O is an aqueous solution of tetrafluoroboric acid.
  • the preparation method of the compound II*-2 is the same as the preparation method of the compound II*-1 in the embodiment 10 except for the following features:
  • Example 10 The HC ⁇ CCH(OH)C ⁇ CCH 2 C(COOMe) 2 CH 2 C ⁇ CH used in Example 10 was replaced with an equimolar amount of HC ⁇ CCH(OH)C ⁇ C (CH) prepared in Preparation Example 1. 2 ) 3 C ⁇ CH.
  • the compound II*-2 was obtained as a red solid, yield: 89% (yield of compound II*-2 was a molar amount of compound II*-1 / molar amount of RhCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Rh] 2 is RhCl(PPh 3 ) 2
  • HBF 4 ⁇ H 2 O is an aqueous solution of tetrafluoroboric acid.
  • the preparation method of the compound II*-13 is the same as the preparation method of the compound II*-1 in the embodiment 10 except for the following features:
  • Example 10 The HC ⁇ CCH(OH)C ⁇ CCH 2 C(COOMe) 2 CH 2 C ⁇ CH used in Example 10 was replaced with an equimolar amount of HC ⁇ CCPh(OH)C ⁇ C (CH) prepared in Preparation Example 8. 2 ) 3 C ⁇ CH.
  • the compound II*-13 was obtained as a red solid, yield: 86% (yield of compound II*-13 was the molar amount of compound II*-13/molar amount of RhCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Ir] 2 is IrCl(PPh 3 ) 2
  • HBF 4 ⁇ H 2 O is an aqueous solution of tetrafluoroboric acid.
  • the preparation method of the compound II*-11 is the same as the preparation method of the compound II*-1 in the embodiment 10 except for the following features:
  • RhCl(PPh 3 ) 3 in Example 10 was replaced with an equimolar amount of IrCl(PPh 3 ) 3 .
  • the compound II*-11 was obtained as a red solid, yield: 55% (yield of compound II*-11 was the molar amount of compound II*-11 / molar amount of IrCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Ir] 2 is IrCl(PPh 3 ) 2
  • HBF 4 ⁇ H 2 O is an aqueous solution of tetrafluoroboric acid.
  • the preparation method of the compound II*-21 is the same as the preparation method of the compound II*-1 in the embodiment 10 except for the following features:
  • Example 10 The RhCl(PPh 3 ) 3 in Example 10 was replaced with an equimolar amount of IrCl(PPh 3 ) 3 .
  • the HC ⁇ CCH(OH)C ⁇ CCH 2 C(COOMe) 2 CH 2 C ⁇ CH used in Example 10 was replaced with an equimolar amount of HC ⁇ CCH(OH)C ⁇ C (CH) prepared in Preparation Example 9. 2 ) 5 C ⁇ CH.
  • the compound II*-21 was obtained as a red solid, yield: 53% (yield of compound II*-21 was the molar amount of compound II*-21 / molar amount of IrCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 and [Ru] 2 is RuCO(PPh 3 ) 2 .
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 and [Ru] 2 is RuCO(PPh 3 ) 2 .
  • the preparation method of the compound II*-7 is the same as the preparation method of the compound II*-6 in the embodiment 14 except for the following features:
  • Example 14 The compound I*-1 in Example 14 was replaced with an equimolar amount of the compound I*-8 obtained in Example 3, and the sodium thiophenolate was replaced with an equimolar amount of sodium methylthiolate.
  • the compound II*-7 was obtained as a red solid, yield: 85% (yield of compound II*-7 is the molar amount of compound II*-7 / the molar amount of compound I*-8 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula II*.
  • [Ru] 1 is RuCl(PPh 3 ) 2
  • [Ru] 2 is RuCO(PPh 3 ) 2
  • Bu 4 N + Cl ⁇ is tetra-n-butylammonium chloride.
  • Dichloroacetic acid (0.69 mmol) was added dropwise to a solution of the compound I*-3 (0.46 mmol) obtained in Example 2 in dichloromethane (dichloromethane (30 mL)). After reacting for 20 min, the reaction solution was drained with a vacuum pump, tetra-n-butylammonium chloride (0.72 mmol) was added, and the reaction flask was replaced with a CO atmosphere, and dichloromethane was added thereto, and the reaction liquid was red at room temperature for 1 hour.
  • Compound II*-9, yield: 75% the yield of compound II*-9 is the molar amount of compound II*-9 / the molar amount of compound II*-3 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound III*-1 is the same as the preparation method of the compound I*-1 in the first embodiment except for the following features:
  • the compound III*-1 was obtained as a red solid, yield: 61% (yield of compound III*-1 was a molar amount of compound III*-1/molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound III*-20 is the same as the preparation method of the compound I*-1 in the first embodiment except for the following features:
  • the compound III*-20 was obtained as a brown solid in a yield: 64% (yield of compound III*-20 was a molar amount of compound III*-20 / a molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound III*-8 is the same as the preparation method of the compound III*-6 in the embodiment 20 except for the following features:
  • Example 20 The cyclohexyl isocyanide used in Example 20 was replaced with an equimolar amount of water.
  • the compound III*-8 was obtained as a red solid in a yield: 90% (yield of compound III*-8 was a molar amount of compound III*-8/molar amount of compound I*-1 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound III*-9 is the same as the preparation method of the compound III*-6 in the embodiment 20 except for the following features:
  • Example 20 The cyclohexyl isocyanide used in Example 20 was replaced with an equimolar amount of S 8 (purchased from Angie Chemical).
  • the compound III*-9 was obtained as a red solid in a yield: 90% (yield of compound III*-9 was the molar amount of compound III*-9/molar amount of compound I*-1 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Ir] 1 is Ir(PPh 3 ) 2 .
  • the preparation method of the compound III*-10 is the same as the preparation method of the compound II*-1 in the embodiment 10 except for the following features:
  • RhCl(PPh 3 ) 3 in Example 10 was replaced with an equimolar amount of IrCl(PPh 3 ) 3 .
  • the compound III*-10 was obtained as a brown solid, yield: 41% (yield of compound III*-10 was a molar amount of compound III*-10 / molar amount of IrCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • the preparation method of the compound III*-11 is the same as the preparation method of the compound III*-10 in the embodiment 23 except for the following features:
  • Example 23 The IrCl(PPh 3 ) 3 used in Example 23 was replaced with an equimolar amount of RhCl(PPh 3 ) 3 .
  • the compound III*-11 was obtained as a brown solid, yield: 75% (yield of compound III*-11 was the molar amount of compound III*-11 / molar amount of IrCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula III*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • the preparation method of the compound III*-14 is the same as the preparation method of the compound III*-6 in the embodiment 20 except for the following features:
  • Example 20 The cyclohexyl isocyanide used in Example 20 was replaced with an equimolar amount of selenium powder (purchased from Angie Chemical); the compound of formula I*-1 was replaced by the formula I*- prepared in Example 7. The compound shown in 6.
  • the compound III*-14 was obtained as a red solid in a yield: 90% (yield of compound III*-14 is the molar amount of compound III*-14 / the molar amount of compound I*-6 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula IV*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula IV*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound IV*-5 is the same as the preparation method of the compound IV*-1 in the embodiment 26 except for the following features:
  • Example 26 The ethoxy acetylene used in Example 26 was replaced by an equimolar number. (purchased from Angie Chemical).
  • the compound IV*-5 was obtained as a green solid, yield: 60% (yield of compound IV*-5 is the molar amount of compound IV*-5 / the molar amount of compound I*-6 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula IV*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • the preparation method of the compound IV*-8 was the same as the preparation method of the compound IV*-1 in Example 26 except for the following characteristics:
  • Example 26 The compound I*-3 used in Example 26 was replaced with an equimolar amount of the compound I*-6 obtained in Example 7.
  • the compound IV*-8 was obtained as a green solid, yield: 60% (yield of compound IV*-8 is the molar amount of compound IV*-8/molar amount of compound I*-6 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula IV*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • the preparation method of the compound IV*-12 is the same as the preparation method of the compound IV*-1 in the example 26 except for the following features:
  • Example 26 The compound I*-3 used in Example 26 was replaced with an equimolar amount of the compound I*-7 obtained in Example 6, and the ethoxy acetylene was replaced by an equimolar number.
  • the compound IV*-12 was obtained as a green solid, yield: 59% (yield of compound IV*-12 was the molar amount of compound IV*-12 / the molar amount of compound I*-7 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula V*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 and [Ru] 3 is Ru(PPh 3 ) 2 .
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula V*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 and [Ru] 3 is Ru(PPh 3 ) 2 .
  • Example 30 The butynone used in Example 30 was replaced with an equimolar amount of dimethyl butynediolate.
  • the compound V*-3 was obtained as a red solid, yield: 65% (the yield of compound V*-3 was the molar amount of compound V*-3 / the molar amount of compound III*-1 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula V*.
  • [Rh] 1 is Rh(PPh 3 ) 2 and [Rh] 3 is RhClPPh 3 .
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula V*.
  • [Ir] 1 is Ir(PPh 3 ) 2 and [Ir] 3 is IrClPPh 3 .
  • Example 32 The compound III*-11 used in Example 32 was replaced with an equimolar amount of the compound III*-10 obtained in Example 23, and the methyl phenylpropynoate was replaced with an equimolar amount of methyl propiolate.
  • the compound V*-11 was obtained as a green solid, yield: 73% (yield of compound V*-11 was the molar amount of compound V*-11 / molar amount of IrCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of the formula V*.
  • [Ru] 1 is Ru(PPh 3 ) 2 and [Ru] 3 is Ru ClPPh 3 .
  • Example 32 The compound III*-11 used in Example 32 was replaced with an equimolar amount of the compound III*-1 obtained in Example 18, and the methyl phenylpropynoate was replaced with an equimolar number.
  • the compound V*-7 was obtained as a green solid, yield: 69% (the yield of compound V*-7 was the molar amount of compound V*-7 / the molar amount of compound III*-1 x 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula VI*.
  • [Ru] 4 is RuCl 2 PPh 3 .
  • the preparation method of the compound VI*-1 is the same as the preparation method of the compound I*-1 in the first embodiment except for the following features:
  • HC ⁇ CCH used in Example 1 of the embodiment (OH) C ⁇ CCH 2 C (COOMe ) 2 CH 2 C ⁇ CH the like into moles of Preparation 7 was prepared HC ⁇ CCH (OH) C ⁇ CCH 2 C (COOMe) 2 CH 2 C ⁇ CC ⁇ CPh.
  • the compound VI*-1 was obtained as a red solid, yield: 71% (yield of compound VI*-1 was the molar amount of compound VI*-1/molar amount of RuCl 2 (PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula VI*.
  • [Rh] 4 is RhClPPh 3 .
  • HC ⁇ CCH used in Example 1 of the embodiment (OH) C ⁇ CCH 2 C (COOMe ) 2 CH 2 C ⁇ CH the like into moles of Preparation 7 was prepared HC ⁇ CCH (OH) C ⁇ CCH 2 C (COOMe) 2 CH 2 C ⁇ CC ⁇ CPh, RuCl 2 (PPh 3 ) 3 was replaced by an equimolar amount of RhCl(PPh 3 ) 3 .
  • the compound VI*-13 was obtained as a red solid, yield: 71% (yield of compound VI*-13 was the molar amount of compound VI*-13 / molar amount of RhCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a metal bridge fused ring compound of formula VI*.
  • [Ir] 4 is IrClPPh 3 .
  • the compound VI*-10 was obtained as a red solid, yield: 73% (yield of compound VI*-10 was the molar amount of compound VI*-10/molar amount of RhCl(PPh 3 ) 3 ⁇ 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula I'*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • Example 2 The compound I*-1 (0.1 mmol) obtained in Example 1 was dissolved in 15 mL of chloroform, and then a mixture of sodium hydroxide (NaOH 0.50 mmol) and water (0.1 mL) was added, and the obtained mixture was stirred at room temperature.
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula I'*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound I'*-8 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound I*-8 obtained in Example 3.
  • the compound I'*-8 was obtained as a red solid, yield: 82% (yield of compound I'*-8 was the molar amount of compound I'*-8/molar amount of compound I*-8 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula I'*.
  • [Ir] 1 is IrCl(PPh 3 ) 2 .
  • the preparation method of the compound I'*-7 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound I*-7 obtained in Example 6.
  • the compound I'*-7 was obtained as a red solid, yield: 81% (yield of compound I'*-7 as the molar amount of compound I'*-7/molar amount of compound I*-7 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula I'*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • the compound I'*-14 was prepared in the same manner as the compound I'*-1 in Example 38 except for the following characteristics:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound I*-14 obtained in Example 8.
  • the compound I'*-14 was obtained as a red solid, yield: 77% (yield of compound I'*-14 as a molar amount of compound I'*-14/molar amount of compound I*-14 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula II'*.
  • [Ru] 2 is RuCO(PPh 3 ) 2 .
  • the preparation method of the compound II'*-6 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound II*-6 obtained in Example 15.
  • the compound II'*-6 was obtained as a red solid, yield: 78% (yield of compound II'*-6 was the molar amount of compound II'*-6/molar amount of compound II*-6 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula II'*.
  • [Rh] 2 is RhCO (PPh 3) 2.
  • the preparation method of the compound II'*-2 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound II*-2 obtained in Example 11.
  • the compound II'*-2 was obtained as a red solid, yield: 71% (yield of compound II'*-2 was the molar amount of compound II'*-2/molar amount of compound II*-2 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula II'*.
  • [Ir] 2 is Ir CO(PPh 3 ) 2 .
  • the preparation method of the compound II'*-9 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound II*-10 obtained in Example 9.
  • the compound II'*-9 was obtained as a red solid, yield: 75% (yield of compound II'*-9 was the molar amount of compound II'*-9/molar amount of compound II*-10 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula III'*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound III'*-1 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound III*-20 obtained in Example 19.
  • the compound III'*-1 was obtained as a brown solid, yield: 81% (yield of compound III'*-1 was the molar amount of compound III'*-1 / the molar amount of compound III*-20 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula III'*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound III'*-8 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound III*-8 obtained in Example 21.
  • the compound III'*-8 was obtained as a red solid, yield: 85% (yield of compound III'*-8 was the molar amount of compound III'*-8/molar amount of compound III*-8 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula III'*.
  • [Ir] 1 is Ir(PPh 3 ) 2 .
  • the preparation method of the compound III'*-10 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound III*-10 obtained in Example 23.
  • the compound III'*-10 was obtained as a red solid, yield: 81% (yield of compound III'*-10 was the molar amount of compound III'*-10/molar amount of compound III*-10 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula III'*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • the preparation method of the compound III'*-14 is the same as the preparation method of the compound I'*-1 in the embodiment 38 except for the following features:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound III*-14 obtained in Example 25.
  • the compound III'*-14 was obtained as a red solid, yield: 81% (yield of compound III'*-14 was the molar amount of compound III'*-14/molar amount of compound III*-10 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula IV'*.
  • [Rh] 1 is Rh(PPh 3 ) 2 .
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound IV*-8 obtained in Example 28.
  • the compound IV'*-9 was obtained as a green solid, yield: 86% (yield of compound IV'*-9 was the molar amount of compound IV'*-9/molar amount of compound IV*-8 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula IV'*.
  • [Ru] 1 is RuCl(PPh 3 ) 2 .
  • the preparation method of the compound IV'*-5 was the same as the preparation method of the compound I'*-1 in Example 38 except for the following characteristics:
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound IV*-5 obtained in Example 27.
  • the compound IV'*-5 was obtained as a green solid, yield: 84% (yield of compound IV'*-5 is the molar amount of compound IV'*-5/molar amount of compound IV*-5 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of formula IV'*.
  • [Ir] 1 is Ir(PPh 3 ) 2 .
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound IV*-12 obtained in Example 29.
  • the compound IV'*-12 was obtained as a green solid, yield: 87% (yield of compound IV'*-12 was the molar amount of compound IV'*-12/molar amount of compound IV*-12 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of the formula V'*.
  • [Ru] 3 is Ru(PPh 3 ) 2 .
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound V*-1 obtained in Example 30.
  • the compound V'*-1 was obtained as a green solid, yield: 80% (the yield of compound V'-1 was the molar amount of compound V'*-1 / the molar amount of compound V*-1 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of the formula V'*.
  • [Ir] 3 is IrClPPh 3 .
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound V*-11 obtained in Example 33.
  • the compound V'*-11 was obtained as a green solid, yield: 88% (the yield of compound V'*-11 was the molar amount of compound V'*-11 / the molar amount of compound V*-11 x 100%).
  • This example is intended to illustrate the preparation of a doped fused ring compound of the formula V'*.
  • [Rh] 3 is RhClPPh 3 .
  • Example 38 The compound I*-1 used in Example 38 was replaced with an equimolar amount of the compound V*-22 obtained in Example 32.

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Abstract

本发明涉及有机化学和金属有机化学领域，公开了一种金属桥位稠环化合物及其中间体和制备方法及应用，该金属桥位稠环化合物具有式I*-VI*和I'*-VI'*中的任意一个所示的结构，本发明的金属桥位稠环化合物的中间体具有式I所示的结构。本发明提供的链状多炔化合物含有多个官能团，结构可控，可用于高效率地合成金属杂稠环化合物。本发明的金属桥位稠环化合物在太阳能电池、光动力学治疗、光解水、锂-空气电池领域有应用前景，本发明提供的金属桥位稠环化合物的主结构具有良好的平面性，是一个大的共轭体系，具有芳香性，稳定性好，具有良好的紫外-可见-近红外吸收光谱和较好的电化学性能。

Description

一种金属桥位稠环化合物及其中间体和制备方法及应用 技术领域
本发明涉及有机化学和金属有机化学领域，具体地，涉及一种金属桥位稠环化合物及该金属桥位稠环化合物的中间体即一种链状多炔化合物以及它们的制备方法，本发明还涉及金属桥位稠环化合物的应用。
背景技术
稠芳环是一类重要的有机芳烃。由于其具有大共轭体系、平面性和刚性，因此通常具有良好的光电性能，被广泛用作有机场效应晶体管、有机发光二极管和有机太阳能电池材料(J.Am.Chem.Soc.,2011,133(50):20009-20029)。稠芳环作为电致发光材料已广泛应用于生理学、药学、信息科学和材料科学等领域。近年来，含杂原子稠芳环的合成与应用研究已成为热门研究领域之一，在全碳稠芳环骨架引入杂原子可调节其前线轨道能量，从而改变其光电性能(Chem.Commun.,2015,51(29):6257-6274)。目前，已报道的杂稠芳环骨架所含的杂原子通常为主族元素。
与主族元素相比，过渡金属外层的d、s轨道能量相近，易发生d/s跃迁，且具有未充满的价层d轨道，很容易采用杂化轨道接受电子以达到16或18电子的稳定状态而形成配合物。因此，过渡金属杂稠芳环兼具过渡金属和芳环的特性，与主族元素掺杂的稠芳环相比，其性质、性能更加丰富。虽然金属杂稠芳环具有很好的应用前景，但是目前金属杂稠芳环种类很少(Coord.Chem.Rev.,2014,270–271(0):151-166)，且尚无通用的合成方法。
2013年以来，Xia组报道了一系列金属位于桥头的新型金属杂稠芳环：金属杂戊搭炔(Nat.Chem.2013,5,698-703；Angew.Chem.Int.Ed.,2015,54(24):7189-7192)、金属杂戊搭烯及其衍生物(Nat.Commun.,2014,5,3265；Angew.Chem.Int.Ed.,2015,54(10):3102-3106；Angew.Chem.Int.Ed.,2014,53(24):6232-6236.)。上述新型金属杂稠芳环不仅结构新颖，还具有对紫外-可见-近红外光宽吸收、聚集诱导荧光增强、大的Stock位移等独特的光学性能，在光、电领域具有重要的应用前景。
尽管Xia组报道的这类金属位于桥头的新型金属杂稠芳环在光、电领域表现出诸多其他材料不具备的独特性能，但是目前这一种类的化合物合成步骤长、中间产物稳定性差、因此制备困难；并且其金属品种的仅限于金属锇。而相对于锇，其它金属如钌、铑、铱的性能更加丰富、价格更加低廉、应用更加广泛。因此，发展金属杂戊搭炔、金属杂戊搭烯及其衍生物的简便合成方法，合成其它金属中心金属杂戊搭炔、金属杂戊搭烯及其衍生物显得尤为重要。
钳形(Pincer)配体是指一类含有类似于ECE(E、C为任何可与金属配位的原子)结构的化合物，该概念最早提出于20世纪70年代。由于钳形配体与金属配位形成的鳌合物具有良好的稳定性，反应活性以及立体选择性，因此目前广泛应用于配位化学、有机合成、均相催化和材料化学等领域(Angew.Chem.Int.Ed.2001,40,3750-3781)。近年来，钳形配体与金属络合物不仅在C-耦联反应、惰性化学键活化等领域发挥了重要作用，同时在光电材料方面也有重要的应用，如三联吡啶与钌形成的三联吡啶钌配合物(黑染料)广泛应用于太阳能电池领域。
自1976年Moulton和shawt报道了第一个钳形配体与金属的络合物以来，这些化合物在合成、结构、反应性以及其应用均取得了显著的进展(J.Chem.Soc.Dalton Trans.1976, 1020-1024)。目前，关于三齿钳形配体的报道主要有NCN(氮碳氮)型(Coord.Chem.Rev.,2007,251,610-641；Coord.Chem.Rev.,2004,248,2275-2282.)，NNN(氮氮氮)型，PCP(磷碳磷)型(Chem.Rev.,2003,103,1759-1792.)，PCO(磷碳氧)型，SCS(硫碳硫)型等，而NCC(氮碳碳)和CCC(碳碳碳)型钳形配体与金属的络合物报道很少。
发明内容
为了解决金属杂稠芳环化合物合成的问题，本发明提供了链状多炔化合物及其制备方法，本发明还提供了链状多炔化合物制备的金属杂稠环化合物(包括金属杂稠芳环化合物和非芳香性金属杂稠环化合物)以及制备方法和应用。
发明人经研究后发现，链状多炔化合物能够在温和条件下高效构筑金属杂稠环化合物。通过进一步的研究，发明人发现可以通过末端炔烃与有机金属试剂在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与炔醛或炔酮接触反应，可以获得链状多炔化合物，该链状多炔化合物可以直接与简单金属配合物反应，从而获得金属杂稠环化合物。从而完成了本发明。
第一方面，本发明提供一种链状多炔化合物，该化合物具有以下式I所示的结构：
Figure PCTCN2016081392-appb-000001
其中，X为-O-、-S-、-CR4R5-、-SiR6R7-或-NR8-；R4、R5、R6、R7和R8各自独立地为氢、C1-20烷基、C1-20酯基、C1-20酰基、C3-20环烷基、C1-20卤代烷基、腈基、硝基、取代或未取代的芳基或者
Figure PCTCN2016081392-appb-000002
R9为C1-8烷基或者取代或未取代的芳基；
R1为腈基、取代或未取代的C2-30炔基、取代或未取代的C4-30多炔基、取代或未取代的C3-30累积多烯基，且不含-C≡CCH(OH)C≡C-结构单元；
R2和R3各自独立地为氢、取代或未取代的芳基、取代或未取代的C1-8烷基、取代或未取代的C1-8烷氧基、取代或未取代的C1-8烷硫基、取代或未取代的C3-8环烷基或者取代或未取代的C2-8炔基，且R2和R3中不含-C≡CCH(OH)C≡C-结构单元；
m和n分别为1-6的整数，且m+n<8。
第二方面，本发明提供前述链状多炔化合物的制备方法。
第三方面，本发明提供一种金属桥位稠环化合物，该化合物具有式I*-VI*和I'*-VI'*中的任意一个所示的结构：
Figure PCTCN2016081392-appb-000003
Figure PCTCN2016081392-appb-000004
其中，式I*、III*、IV*、I'*、III'*和IV'*中，[M]1为RuAL2、RhL2或IrL2；
式II*和II'*中，[M]2为RuL3、RhAL2或IrAL2；
式V*和V'*中，[M]3为RuL2、RhAL或IrAL；
式VI*和VI'*中，[M]4为RuA2L、RhAL或IrAL；
A为-H、卤素、-SCN或-CN；
L为膦配体、CO配体、吡啶类配体、氮杂环卡宾配体、腈类配体和异氰类双电子配体中的至少一种；
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-30季鏻阳离子或C3-24季铵阳离子；
R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-20烷基、C1-20烷氧基、C1-20烷硫基、C1-20酰基、C1-20酯基、C1-20胺基、C1-20酰胺基、C1-20羧基，C2-20酰胺基，C3-20环烷基，取代或未取代的芳基，取代或未取代的C2-20烯基，取代或未取代的C2-20炔基，取代或未取代的C1-20芳氧基、取代或未取代的C1-20芳硫基，以及能提高水溶性的取代基中的任意一种；
式III*和III'*中，X1为
Figure PCTCN2016081392-appb-000005
-CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种；R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-20烷基或取代或未取代的C3-20环烷基；
式V*和V'*中，Y1为-NR7*-、-O-或-S-；
式I*-VI*中，Z1为Cl-、Br-、I-、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
第四方面，本发明提供制备上述金属桥位稠环化合物的方法。
第五方面，本发明提供上述金属桥位稠环化合物在太阳能电池、光动力学治疗、光解水、锂-空气电池领域中的应用。
本发明提供的链状多炔化合物含有多个官能团，结构可控，可用于高效率地合成金属杂稠环化合物。本发明提供的链状多炔化合物的合成方法简单，可快速、高效地获得链状多炔化合物。
本发明提供的金属桥位稠环化合物的主结构具有良好的平面性，是一个大的共轭体系，具有芳香性，稳定性好，具有良好的紫外-可见-近红外吸收光谱和较好的电化学性能，因而可 以广泛应用于太阳能电池、光动力学治疗、光解水和锂-空气电池等领域。
附图说明
图1为本发明测试例1中的金属桥位稠环化合物I*-1的紫外-可见吸收光谱图。
图2为本发明测试例2中的金属桥位稠环化合物II*-1的紫外-可见吸收光谱图。
图3为本发明测试例2中的金属桥位稠环化合物II*-11的紫外-可见吸收光谱图。
图4为本发明测试例3中的金属桥位稠环化合物II*-2的循环-伏安曲线。
图5为本发明测试例3中的金属桥位稠环化合物II*-2对锂-空气电池的充电电位影响情况曲线。
图6为本发明测试例4中的金属桥位稠环化合物IV*-1的紫外-可见吸收光谱图。
图7为本发明测试例4中的金属桥位稠环化合物IV*-1的体外活性氧测试结果。
图8为本发明测试例5中的金属桥位稠环化合物V*-3的紫外-可见吸收光谱图。
图9为本发明测试例6中的金属桥位稠环化合物VI*-1的紫外-可见吸收光谱图。
图10为本发明测试例7中的金属桥位稠环化合物III*-9的紫外-可见吸收光谱图。
图11为本发明测试例8中的金属桥位稠环化合物I'*-6的紫外-可见吸收光谱图。
图12为本发明测试例9中的金属桥位稠环化合物II'*-9的紫外-可见吸收光谱图。
图13为本发明测试例10中的金属桥位稠环化合物III'*-4的紫外-可见吸收光谱图。
图14为本发明测试例11中的金属桥位稠环化合物IV'*-5的紫外-可见吸收光谱图。
图15为本发明测试例12中的金属桥位稠环化合物V'*-1的紫外-可见吸收光谱图。
图16为本发明测试例13中的金属桥位稠环化合物VI'*-11的紫外-可见吸收光谱图。
具体实施方式
在没有相反说明的情况下，本文中取代的C2-30炔基、取代的C2-20炔基、取代的C4-30多炔基、取代的C2-8炔基中的表示碳原子数目的2-30、2-20、4-30、2-8等均仅指含有炔基或者多炔基的主链上的碳原子数，而不包括含有炔基或者多炔基的主链上的取代基(或者侧链)中的碳原子数目。
本发明中的主要术语分别定义如下：
“C1-20烷基”可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基、叔辛基、正十二烷基、正十六烷基、正十八烷基、正二十烷基、
Figure PCTCN2016081392-appb-000006
Figure PCTCN2016081392-appb-000007
和
Figure PCTCN2016081392-appb-000008
中的至少一种。
“C1-20酯基”是指碳原子总数在1-20个之间，且含有酯键
Figure PCTCN2016081392-appb-000009
的一价基团。例如，所述C1-20酯基可以为
Figure PCTCN2016081392-appb-000010
Figure PCTCN2016081392-appb-000011
Figure PCTCN2016081392-appb-000012
和
Figure PCTCN2016081392-appb-000013
中的至少一种。
“C1-20酰基”可以为
Figure PCTCN2016081392-appb-000014
Figure PCTCN2016081392-appb-000015
和
Figure PCTCN2016081392-appb-000016
中的任意一种。所述C3-20环烷基可以为环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环十二烷基、环十八烷基和环二十烷基中的至少一种。
“C3-20环烷基”可以为环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环十二烷基、环十六烷基、环十八烷基和环二十烷基中的至少一种。
“C1-20卤代烷基”可以为氟、氯、溴、和碘原子中的至少一个取代上述C1-20烷基上的至少一个氢原子所形成的的取代基。
“取代或未取代的芳基”可以为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的噻吩基、取代或未取代的呋喃基、取代或未取代的吡啶基、取代或未取代的吡咯基中的至少一种。所述取代或未取代的芳基中的取代基可以为C1-20烷基、C1-20烷氧基、C1-20烷硫基、C1-20酰基、C1-20酯基、C1-20胺基、C1-20酰胺基、C1-20羧基，C1-17烷基、C1-17烷氧基、C1-17烷硫基、C1-17酰基、C1-17酯基、C1-17胺基、C1-17酰胺基、C1-17羧基，C1-14烷基、C1-14烷氧基、C1-14烷硫基、C1-14酰基、C1-14酯基、C1-14胺基、C1-14酰胺基、C1-14羧基，取代的C2-20酰胺基、优选C2-17酰胺基、更优选C2-8酰胺基，C3-20环烷基、优选C3-17环烷基、更优选C3-8环烷基，C2-20烯基、C2-20炔基、优选C2-17烯基、C2-17炔基、更优选C2-14烯基、C2-14炔基，硝基，氰基和卤素中的至少一种。优选地，所述取代的芳基可以为
Figure PCTCN2016081392-appb-000017
Figure PCTCN2016081392-appb-000018
Figure PCTCN2016081392-appb-000019
和
Figure PCTCN2016081392-appb-000020
中的至少一种。
“C1-8烷基”可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基和叔辛基中的至少一种。
“C2-30炔基”可以为乙炔基、
Figure PCTCN2016081392-appb-000021
Figure PCTCN2016081392-appb-000022
Figure PCTCN2016081392-appb-000023
和
Figure PCTCN2016081392-appb-000024
中的至少一种。
“取代的C4-30多炔基”和“C4-30多炔基”可以为
Figure PCTCN2016081392-appb-000025
Figure PCTCN2016081392-appb-000026
Figure PCTCN2016081392-appb-000027
和
Figure PCTCN2016081392-appb-000028
所述累积多烯基是指基团中具有超过一对相邻碳碳双键(即累积双键)的烯烃残基。
所述“取代的C3-30累积多烯基”是指含有累积多烯基的主链上的碳原子数为3-30的基团，该3-30不包括侧链上可能含有的碳原子数。
优选地，“取代的C3-30累积多烯基”和“C3-30累积多烯基”可以为
Figure PCTCN2016081392-appb-000029
Figure PCTCN2016081392-appb-000030
Figure PCTCN2016081392-appb-000031
和
Figure PCTCN2016081392-appb-000032
中的至少一种。
“C1-8烷氧基”可以为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、仲戊氧基、叔戊氧基、正己氧基、异己氧基、新己氧基、仲己氧基、叔己氧基、正庚氧基、异庚氧基、新庚氧基、仲庚氧基、叔庚氧基、正辛氧基、异辛氧基、新辛氧基、仲辛氧基和叔辛氧基中的至少一种。
“C1-8烷硫基”可以为甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基、正戊硫基、异戊硫基、新戊硫基、仲戊硫基、叔戊硫基、正己硫基、异己硫基、新己硫基、仲己硫基、叔己硫基、正庚硫基、异庚硫基、新庚硫基、仲庚硫基、叔庚硫基、正辛硫基、异辛硫基、新辛硫基、仲辛硫基和叔辛硫基中的至少一种。
“C3-8环烷基”可以为环丙基、环丁基、环戊基、环己基、环庚基和环辛基。
“取代或未取代的C2-8炔基”可以为乙炔基、丙炔基、1-丁炔基、3-甲基-1-丁炔基、1-戊炔基、3-甲基-1-戊炔基、4-甲基-1-戊炔基、1-己炔基、1-庚炔基、1-辛炔基和苯乙炔基。
“C1-20胺基”是指碳原子总数在1-20个之间的胺基，例如，所述C1-20胺基可以为甲胺基、乙胺基、丙胺基、丁胺基、戊胺基、己胺基、庚胺基、辛胺基、二甲胺基、二乙胺基、二丙胺基、二丁胺基、正十二胺基、正十六胺基、正十八胺基、正二十胺基中的至少一种。
“C1-20酰胺基”是指碳原子总数在1-20个之间，且含有酰胺键
Figure PCTCN2016081392-appb-000033
的一价基团，所述C1-20酰胺基可以为
Figure PCTCN2016081392-appb-000034
Figure PCTCN2016081392-appb-000035
Figure PCTCN2016081392-appb-000036
和
Figure PCTCN2016081392-appb-000037
中的至少一种。
“C1-20羧基”可以为
Figure PCTCN2016081392-appb-000038
Figure PCTCN2016081392-appb-000039
和
Figure PCTCN2016081392-appb-000040
中的至少一种。
“C2-20酰胺基”是指上述的酰胺基中的酰胺键
Figure PCTCN2016081392-appb-000041
上与N原子相连的H被1-20个碳原子烷基取代后形成的取代基。例如，所述C2-20酰胺基可以为
Figure PCTCN2016081392-appb-000042
Figure PCTCN2016081392-appb-000043
Figure PCTCN2016081392-appb-000044
和
Figure PCTCN2016081392-appb-000045
中的至少一种。
“取代或未取代的C2-20烯基”可以为
Figure PCTCN2016081392-appb-000046
Figure PCTCN2016081392-appb-000047
“取代或未取代的C2-20炔基”可以为
Figure PCTCN2016081392-appb-000048
Figure PCTCN2016081392-appb-000049
“取代或未取代的C1-20芳氧基”可以选自苯氧基(-OPh)、萘氧基、蒽氧基、菲氧基、芘氧基、噻吩氧基、呋喃氧基、吡啶氧基、吡咯氧基、对-甲苯氧基、间-甲苯氧基、邻甲苯氧基、对-硝基苯氧基和对-甲氧基苯氧基。
“取代或未取代的C1-20芳硫基”可以选自苯硫基(-SPh)、萘硫基、蒽硫基、菲硫基、芘硫基、噻吩硫基、呋喃硫基、吡啶硫基、吡咯硫基、对-甲苯硫基、间-甲苯硫基、邻甲苯硫基、对-硝基苯硫基和对-甲氧基苯硫基。
“C1-8烷氧基”可以为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、仲戊氧基、叔戊氧基、正己氧基、异己氧基、新己氧基、仲己氧基、叔己氧基、正庚氧基、异庚氧基、新庚氧基、仲庚氧基、叔庚氧基、正辛氧基、异辛氧基、新辛氧基、仲辛氧基和叔辛氧基中的的任意一种。
“C1-8烷硫基”可以为甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲 丁硫基、叔丁硫基、正戊硫基、异戊硫基、新戊硫基、仲戊硫基、叔戊硫基、正己硫基、异己硫基、新己硫基、仲己硫基、叔己硫基、正庚硫基、异庚硫基、新庚硫基、仲庚硫基、叔庚硫基、正辛硫基、异辛硫基、新辛硫基、仲辛硫基和叔辛硫基中的的任意一种。
“能提高水溶性的取代基”可以为聚乙二醇残基、透明质酸残基、聚丙烯酸和糖类衍生物残基。所述聚乙二醇残基是指聚乙二醇的其中一个末端上的羟基去掉H后剩余的部分。所述聚乙二醇的重均分子量可以为200-200000。所述透明质酸残基是指透明质酸的D-葡萄糖醛酸或N-乙酰葡糖胺的任意一个羟基去掉H后剩余的部分，或透明质酸的D-葡萄糖醛酸的羧基去掉羟基(-OH)后剩余部分。所述透明质酸的重均分子量可以为2000-2000000。所述糖类衍生物残基是指糖类衍生物的任意一个羟基去掉氢原子后剩余的部分。所述糖类衍生物可以为葡萄糖、蔗糖、麦芽糖、半乳糖、乳糖、果糖和唾液酸的衍生物中的任意一种。所述糖类衍生物例如可以为葡萄糖醛酸、葡萄糖缩醛、葡萄糖半缩醛和羧甲基乳糖。
所述取代的芳基中的取代基可以为C1-8烷基、C1-8烷氧基、C1-8烷硫基、C1-8酰基、C1-8酰胺基、C1-8酯基、C1-8羧基、C1-8胺基、C3-8环烷基、卤素、硝基和腈基。
所述C1-8酰基可以为
Figure PCTCN2016081392-appb-000050
Figure PCTCN2016081392-appb-000051
和
Figure PCTCN2016081392-appb-000052
所述C1-8酰胺基可以为
Figure PCTCN2016081392-appb-000053
Figure PCTCN2016081392-appb-000054
和
Figure PCTCN2016081392-appb-000056
中的任意一种。
所述C1-8酯基可以为
Figure PCTCN2016081392-appb-000057
Figure PCTCN2016081392-appb-000058
Figure PCTCN2016081392-appb-000059
和
Figure PCTCN2016081392-appb-000060
中的任意一种。
所述C1-8羧基可以为
Figure PCTCN2016081392-appb-000061
和
Figure PCTCN2016081392-appb-000062
中的任意一种。
“C3-8环烷基”可以为环丙基、环丁基、环戊基、环己基、环庚基和环辛基。
所述C1-8胺基可以为甲胺基、乙胺基、丙胺基、丁胺基、戊胺基、己胺基、庚胺基、辛胺基、二甲胺基、二乙胺基、二丙胺基和二丁胺基中的任意一种。
所述卤素可以为氟、氯、溴和碘中的任意一种。
第一方面，本发明提供了一种链状多炔化合物，该化合物具有以下式I所示的结构：
Figure PCTCN2016081392-appb-000063
其中，X为-O-、-S-、-CR4R5-、-SiR6R7-或-NR8-；R4、R5、R6、R7和R8各自独立地为氢、C1-20烷基、C1-20酯基、C1-20酰基、C3-20环烷基、C1-20卤代烷基、腈基、硝基、取代或未取代的芳基或者
Figure PCTCN2016081392-appb-000064
R9为C1-8烷基或者取代或未取代的芳基；
R1为腈基、取代或未取代的C2-30炔基、取代或未取代的C4-30多炔基、取代或未取代的C3-30累积多烯基，且不含-C≡CCH(OH)C≡C-结构单元；
R2和R3各自独立地为氢、取代或未取代的芳基、取代或未取代的C1-8烷基、取代或未取代的C1-8烷氧基、取代或未取代的C1-8烷硫基、取代或未取代的C3-8环烷基或者取代或未取代的C2-8炔基，且R2和R3中不含-C≡CCH(OH)C≡C-结构单元；
m和n分别为1-6的整数，且m+n<8。
本发明提供以下几种优选的具体实施方式：
实施方式1：在式I所示的结构中，X为-O-、-S-、-CR4R5-、-SiR6R7-或-NR8-；R4、R5、R6、R7和R8各自独立地为氢、C1-17烷基、C1-17酯基、C1-17酰基、C3-17环烷基、C1-17卤代烷基、腈基、硝基、取代或未取代的芳基或者
Figure PCTCN2016081392-appb-000065
R9为C1-6烷基或者取代或未取代的芳基；
R1为腈基、取代或未取代的C2-24炔基、取代或未取代的C4-24多炔基、取代或未取代的C3-24累积多烯基，且不含-C≡CCH(OH)C≡C-结构单元；
R2和R3各自独立地为氢、取代或未取代的芳基、取代或未取代的C1-6烷基、取代或未取代的C1-6烷氧基、取代或未取代的C1-6烷硫基、取代或未取代的C3-6环烷基或者取代或未取代的C2-6炔基，且R2和R3中不含-C≡CCH(OH)C≡C-结构单元；
m和n分别为1-6的整数，且m+n<8。
实施方式2：在式I所示的结构中，X选自-O-、-S-、-CH2-、-C(CH3)2-、-CHCH3-、-C(COOMe)2-、-C(COOEt)2-、-C(COCH3)(COOMe)-、-C(Cy)(COOMe)-、-C(CH2CH2Br)2-、-C(CN)2-、-C(NO2)2-、-SiH2-、-SiMe2-、-SiPh2-、-NH-、
Figure PCTCN2016081392-appb-000066
和
Figure PCTCN2016081392-appb-000067
R1选自腈基、乙炔基、
Figure PCTCN2016081392-appb-000068
Figure PCTCN2016081392-appb-000069
Figure PCTCN2016081392-appb-000070
和
Figure PCTCN2016081392-appb-000071
R2和R3各自独立地选自氢、甲基、乙基、正丙基、异丙基、甲氧基、乙氧基、正丙氧基、异丙氧基、甲硫基、乙硫基、环丙基、环己基、
Figure PCTCN2016081392-appb-000072
Figure PCTCN2016081392-appb-000073
Figure PCTCN2016081392-appb-000074
乙炔基、丙炔基、
Figure PCTCN2016081392-appb-000075
Figure PCTCN2016081392-appb-000076
Figure PCTCN2016081392-appb-000077
苯甲基和苯乙基；
m+n<8，且m和n各自独立地为1、2、3、4、5或6。
实施方式3：式I所示的结构为如下化合物中的至少一种：
Figure PCTCN2016081392-appb-000078
Figure PCTCN2016081392-appb-000079
第二方面，本发明提供了上述链状多炔化合物的制备方法，当R3为氢时，该方法包括：将式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与式III所示的化合物接触反应，获得式IV所示的Y基团保护的链状多炔化合物；再将式IV所示的Y基团保护的链状多炔化合物进行脱保护基团处理，获得式I所示的链状多炔化合物：
Figure PCTCN2016081392-appb-000080
Y为用来保护炔基的保护基团，Y可以为TMS(三甲基硅基)、TES(三乙基硅基)和TIPS(三异丙基硅基)中的至少一种。X、R1、R2、m和n的定义均与本发明的前述相同。
所述有机金属试剂RM1或RM2Z中的R可以为C1-8烷基、苯基和-NR10R11中的任意一种。其中，-NR10R11中的R10和R11可以各自独立地为氢、C1-8烷基和三甲基硅基中的任意一种。所述C1-8烷基均与上述相同。M1可以为锂、钠或钾。M2可以为镁。Z可以为氯、溴或碘。优选地，所述有机金属试剂RM1为甲基锂、乙基锂、正丁基锂、叔丁基锂、苯基锂、二异丙基胺基锂和双(三甲基硅基)胺基锂中的至少一种。优选地，RM2Z为甲基溴化镁、乙基溴化镁、甲基氯化镁和乙基氯化镁中的至少一种。
根据本发明，可以使用脱保护试剂对获得的式IV所示的Y基团保护的链状多炔化合物进行脱保护基团处理。所述脱保护试剂可以为K2CO3、Na2CO3、Cs2CO3、KF、(n-Bu)4NF(四正丁基氟化铵)、(Et)4NF(四乙基氟化铵)、(Me)4NF(四甲基氟化铵)和(n-Pr)4NF(四正丙基氟化铵)中的至少一种。
优选地，在对式IV所示的Y基团保护的链状多炔化合物进行脱保护基团处理之前，对步骤(1)获得的含有式IV所示的Y基团保护的链状多炔化合物的混合物进行淬灭和提纯操作。其中，所述淬灭操作中使用的淬灭剂可以为饱和氯化铵和/或水。所述提纯操作可以包括使用有机溶剂对获得的含有式IV所示的Y基团保护的链状多炔化合物的混合物进行萃取，将萃取获 得的有机相干燥后过滤、浓缩、层析分离获得式I所示的链状多炔化合物。其中，所述有机溶剂可以为乙醚、正己烷、甲苯、乙二醇二甲醚、1,4-二氧六环、二氯甲烷和三氯甲烷中的至少一种；所述对萃取获得的有机相干燥的操作可以包括使用无水硫酸镁和/或无水硫酸钠；所述层析分离的操作可以包括使用硅胶柱层析和/或中性氧化铝。
优选地，在对式IV所示的Y基团保护的链状多炔化合物进行脱保护基团处理之后获得的含有式I所示的链状多炔化合物的混合物进行淬灭和提纯操作。所述淬灭和提纯操作的方法同上所述。
当R3不为氢时，上述链状多炔化合物的制备方法包括：
将式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与式V所示的化合物接触反应，获得式I所示的链状多炔化合物：
Figure PCTCN2016081392-appb-000081
其中，有机金属试剂RM1或RM2Z与上述相同；X、R1、R2、m和n均与上述相同。
优选地，所述式II所示的化合物与有机金属试剂RM1和/或RM2Z的总和的摩尔比为1:(0.5-1)，优选1：(0.9-1)。当同时含有RM1和RM2Z时，对所述有机金属试剂RM1和RM2Z的用量比例没有特别限定，二者可以以任意摩尔比混合使用。
优选地，所述非质子性溶剂为苯、甲苯、正己烷、乙醚、乙二醇二甲醚、四氢呋喃和1,4-二氧六环、石油醚、汽油中的至少一种。
所述式II所示的化合物与有机金属试剂RM1和/或RM2Z可以在惰性气体保护下进行金属交换反应。所述惰性气体为任何不与催化剂、原料和产物反应，并且对反应不产生任何负面影响的气体。所述惰性气体可以为氮气、氦气、氩气和氖气中的至少一种。所述式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中接触的条件包括温度可以为零下100℃至零上30℃，优选为零下78℃至0℃，时间可以为0.5-10h，优选为1-3h。
将式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中进行金属交换反应得到的反应混合物与式III所示的化合物或式V所示的化合物接触反应的条件包括温度可以为零下100℃至零上30℃，优选为零下78℃至0℃，时间可以为0.5-10h，优选为1-5h。
第三方面，本发明提供了上述链状多炔化合物在合成金属杂稠环化合物中的应用；所述链状多炔化合物在合成金属杂稠环化合物中的应用包括使用所述链状多炔化合物与金属配合物反应，获得金属桥位稠环化合物；所述金属配合物为DAaLb；其中，D可以为Fe、Co、Ni、Ru、Mn、Re、Cr、Mo、W、V、Nb、Ta、Ti、Zr、Hf、Rh、Pd、Ir、Pt和Os中的任意一种；A可以为H、卤素、SCN和CN中的任意一种；L可以为膦配体、CO配体、吡啶类配体、氮杂环卡宾配体、腈类配体和异氰类双电子配体中的任意一种；a和b分别为0-6的整数；当a≥2时，A可以相同也可以不同，当b≥2时，L可以相同也可以不同。
优选地，所述金属配合物为OsCl2(PPh3)3、RuCl2(PPh3)3、RhCl(PPh3)3、IrCl(PPh3)3和IrHCl2(PPh3)3中的任意一种。
根据一种优选的实施方式，本发明提供的所述金属桥位稠环化合物具有式I*-VI*和I'*-VI'*中的任意一个所示的结构：
Figure PCTCN2016081392-appb-000082
其中，式I*、III*、IV*、I'*、III'*和IV'*中，[M]1为RuAL2、RhL2或IrL2；
式II*和II'*中，[M]2为RuL3、RhAL2或IrAL2；
式V*和V'*中，[M]3为RuL2、RhAL或IrAL；
式VI*和VI'*中，[M]4为RuA2L、RhAL或IrAL；
A为-H、卤素、-SCN或-CN；
L为膦配体、CO配体、吡啶类配体、氮杂环卡宾(N-Heterocyclic Carbenes NHC)配体、腈类配体和异氰类双电子配体中的至少一种；
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-30季鏻阳离子或C3-24季铵阳离子；
R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-20烷基、C1-20烷氧基、C1-20烷硫基、C1-20酰基、C1-20酯基、C1-20胺基、C1-20酰胺基、C1-20羧基，C2-20酰胺基，C3-20环烷基，取代或未取代的芳基，取代或未取代的C2-20烯基，取代或未取代的C2-20炔基，取代或未取代的C6-20芳氧基、取代或未取代的C6-20芳硫基，以及能提高水溶性的取代基中的任意一种；
式III*和III'*中，X1为
Figure PCTCN2016081392-appb-000083
-CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种； R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-20烷基或取代或未取代的C3-20环烷基；
式V*和V'*中，Y1为-NR7*-、-O-或-S-；
式I*-VI*中，Z1为Cl-、Br-、I-(碘离子)、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
本发明提供所述金属桥位稠环化合物的以下具体的优选实施方式：
实施方式1：在式I*-VI*和I'*-VI'*中，
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-24季鏻阳离子或C3-20季铵阳离子；
R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-16烷基、C1-16烷氧基、C1-16烷硫基、C1-16酰基、C1-16酯基、C1-16胺基、C1-16酰胺基、C1-16羧基，C2-16酰胺基，C3-16环烷基，取代或未取代的芳基，取代或未取代的C2-16烯基，取代或未取代的C2-16炔基，取代或未取代的C6-16芳氧基、取代或未取代的C6-16芳硫基，以及能提高水溶性的取代基中的任意一种；
式III*和III'*中，X1为
Figure PCTCN2016081392-appb-000084
-CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种；R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-16烷基或取代或未取代的C3-16环烷基；
式V*和V'*中，Y1为-NR7*-、-O-或-S-；
式I*-VI*中，Z1为Cl-、Br-、I-(碘离子)、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
实施方式2：在式I*-VI*和I'*-VI'*中，
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-20季鏻阳离子或C3-16季铵阳离子；
R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-12烷基、C1-12烷氧基、C1-12烷硫基、C1-12酰基、C1-12酯基、C1-12胺基、C1-12酰胺基、C1-12羧基，C2-12酰胺基，C3-12环烷基，取代或未取代的芳基，取代或未取代的C2-12烯基，取代或未取代的C2-12炔基，取代或未取代的C6-12芳氧基、取代或未取代的C6-12芳硫基，以及能提高水溶性的取代基中的任意一种；
式III*和III'*中，X1为
Figure PCTCN2016081392-appb-000085
-CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种；R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-12烷基或取代或未取代的C3-12环烷基；
式V*和V'*中，Y1为-NR7*-、-O-或-S-；
式I*-VI*中，Z1为Cl-、Br-、I-(碘离子)、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
实施方式3：在式I*-VI*和I'*-VI'*中，
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-12季鏻阳离子或C3-12季铵阳离子；
R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-8烷基、C1-8烷氧基、C1-8烷硫基、C1-8酰基、C1-8酯基、C1-8胺基、C1-8酰胺基、C1-8羧基，C2-8酰胺基，C3-8环烷基，取代或未取代的芳基，取代或未取代的C2-8烯基，取代或未取代的C2-8炔基，取代或未取代的C6-8芳氧基、取代或未取代的C6-8芳硫基，以及能提高水溶性的取代基中的任意一种；
式III*和III'*中，X1为
Figure PCTCN2016081392-appb-000086
-CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种；R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-8烷基或取代或未取代的C3-8环烷基；
式V*和V'*中，Y1为-NR7*-、-O-或-S-；
式I*-VI*中，Z1为Cl-、Br-、I-(碘离子)、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
实施方式4：在式I*-VI*和I'*-VI'*中，
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-8季鏻阳离子或C3-8季铵阳离子；
R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-6烷基、C1-6烷氧基、C1-6烷硫基、C1-6酰基、C1-6酯基、C1-6胺基、C1-6酰胺基、C1-6羧基，C2-6酰胺基，C3-6环烷基，取代或未取代的芳基，取代或未取代的C2-6烯基，取代或未取代的C2-6炔基，取代或未取代的苯氧基、取代或未取代的苯硫基，以及能提高水溶性的取代基中的任意一种；
式III*和III'*中，X1为
Figure PCTCN2016081392-appb-000087
-CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种；R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-6烷基或取代或未取代的C3-6环烷基；
式V*和V'*中，Y1为-NR7*-、-O-或-S-；
式I*-VI*中，Z1为Cl-、Br-、I-(碘离子)、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
在式I*-VI*和I'*-VI'*中，所述L可以选自三甲基膦、三乙基膦、三丙基膦、三异丙基膦、三叔丁基膦、三环己基膦、三苯基膦、三(对-甲基苯基)膦、三(间-甲基苯基)膦、二苯基膦、二苯基甲基膦、二苯基乙基膦、甲基吡啶、乙基吡啶、1,4-联吡啶、1,2-二(4-吡啶基)乙烯、乙烯基吡啶、乙炔基吡啶、吡啶硼酸、氨基吡啶、氰基吡啶、巯基吡啶、二甲胺基吡啶、苯基吡啶、1,2-双(4-吡啶基)乙烷、咪唑型氮杂环卡宾、咪唑啉型氮杂环卡宾、噻唑型氮杂环卡宾、三唑型氮杂环卡宾、乙腈、丙腈、苯腈、环己基异氰、叔丁基异氰和苯基异氰。或者L2可视为一个整体。优选地，L2为选自双齿氮配体、双齿膦配体、双齿碳-氮配体和双齿氧-氮配体中的任意一种。所述双齿氮配体是指以双齿氮原子作为配位原子的配体。所述双齿氮配体例如可以为乙二胺、2,2'-联吡啶和1,10-菲罗啉中的任意一种。所述双齿膦配体是指以双齿磷原子作为配位原子的配体。所述双齿膦配体例如可以为DPPM(Bis-(diphenylphosphino)methane，1,1-双(二苯基膦)甲烷)、DPPE(1,2-Bis(diphenylphosphino)ethane，1,2-双(二苯基膦)乙烷和DPPP(1,3-Bis(diphenylphosphino)propane，1,3-双(二苯基膦)丙烷中的任意一种。所述双齿碳-氮配体是指以双齿碳-氮原子作为配位原子的配体。所述双齿碳-氮配体例如可以为邻苯基吡啶。所述双齿氧-氮配体是指以双齿氧-氮原子作为配位原子的配体。所述双齿氧-氮配体例如可以为8-羟基喹啉。或者AL2可视为一个整体。优选地，AL2为三联吡啶或其它三齿Pincer(钳形)配体。所述三齿Pincer配体例如可以为PPP、PNP、PCP、NNN、NCN、NPN、ONO、OPO、OCO、SCS和CCC Pincer配体中的任意一种。
实施方式5：在式I*-VI*和I'*-VI'*中，
R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*选自三甲基鏻阳离子、三乙基鏻阳离子、三丙基鏻阳离子、三异丙基鏻阳离子、三叔丁基鏻阳离子、三环己基鏻阳离子、三苯基鏻阳离子、三(对-甲基苯基)鏻阳离子、三(间-甲基苯基)鏻阳离子、二苯基鏻阳离子、二苯基甲基鏻阳离子、二苯基乙基鏻阳离子、三甲基铵阳离子、三乙基铵阳离子、二甲基一乙基铵阳离子、三丙基铵阳离子、三异丙基铵阳离子和三叔丁基铵阳离子；
R2*位于式I*-VI*上标有数字1、3、4、5、6、8和9的位置中的至少一个上，且R2*与R1*所在位置不同；
R3*为位于式I'*-VI'*上标有数字1、3、4、5、6、8和9的位置中的至少一个上的取代基；
R2*和R3*各自独立地选自-H、氟、氯，溴，碘，-SCN，-CN，-OPh、-SPh、甲基、乙基、 正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基、叔辛基、正十二烷基、正十六烷基、正十八烷基、正二十烷基、
Figure PCTCN2016081392-appb-000088
Figure PCTCN2016081392-appb-000089
甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、仲戊氧基、叔戊氧基、正己氧基、异己氧基、新己氧基、仲己氧基、叔己氧基、正庚氧基、异庚氧基、新庚氧基、仲庚氧基、叔庚氧基、正辛氧基、异辛氧基、新辛氧基、仲辛氧基、叔辛氧基、正十二烷氧基、正十六烷氧基、正十八烷氧基、正二十烷氧基、甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基、正戊硫基、异戊硫基、新戊硫基、仲戊硫基、叔戊硫基、正己硫基、异己硫基、新己硫基、仲己硫基、叔己硫基、正庚硫基、异庚硫基、新庚硫基、仲庚硫基、叔庚硫基、正辛硫基、异辛硫基、新辛硫基、仲辛硫基、叔辛硫基、正十二烷硫基、正十六烷硫基、正十八烷硫基、正二十烷硫基、
Figure PCTCN2016081392-appb-000090
Figure PCTCN2016081392-appb-000091
Figure PCTCN2016081392-appb-000092
Figure PCTCN2016081392-appb-000093
甲胺基、乙胺基、丙胺基、丁胺基、戊胺基、己胺基、庚胺基、辛胺基、二甲胺基(NMe2)、二乙胺基(NEt2)、二丙胺基、二丁胺基、正十二胺基、正十六胺基、正十八胺基、正二十胺基、
Figure PCTCN2016081392-appb-000094
Figure PCTCN2016081392-appb-000095
Figure PCTCN2016081392-appb-000096
Figure PCTCN2016081392-appb-000097
环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环十二烷基、环十六烷基、环十八烷基、环二十烷基、苯基、萘基、蒽基、菲基、芘基、噻吩基、呋喃基、吡啶基、吡咯基、
Figure PCTCN2016081392-appb-000098
Figure PCTCN2016081392-appb-000099
Figure PCTCN2016081392-appb-000100
Figure PCTCN2016081392-appb-000101
苯氧基、萘氧基、蒽氧基、菲氧基、芘氧基、噻吩氧基、呋喃氧基、吡啶氧基、吡咯氧基、对-甲苯氧基、间-甲苯氧基、邻甲苯氧基、对-硝基苯氧基、对-甲氧基苯氧基、苯硫基、萘硫基、蒽硫基、菲硫基、芘硫基、噻吩硫基、呋喃硫基、吡啶硫基、吡咯硫基、对-甲苯硫基、间-甲苯硫基、邻甲苯硫基、对-硝基苯硫基、对-甲氧基苯硫基、聚乙二醇残基、透明质酸残基、聚丙烯酸、糖类衍生物残基；X1选自
Figure PCTCN2016081392-appb-000102
Figure PCTCN2016081392-appb-000103
-NH-、
Figure PCTCN2016081392-appb-000104
Figure PCTCN2016081392-appb-000105
式V*和V'*中，Y1选自-NH-、
Figure PCTCN2016081392-appb-000106
Figure PCTCN2016081392-appb-000107
-O-和-S-；式I*-VI*中，Z1为Cl-、Br-、I-(碘离子)、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
所述取代的烯基和取代的炔基中的取代基例如可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、
Figure PCTCN2016081392-appb-000108
Figure PCTCN2016081392-appb-000109
Figure PCTCN2016081392-appb-000110
和
Figure PCTCN2016081392-appb-000111
中的任意一种。所述取代的烯基例如可以为
Figure PCTCN2016081392-appb-000112
Figure PCTCN2016081392-appb-000113
和
Figure PCTCN2016081392-appb-000114
所述取代的炔基例如可以为
Figure PCTCN2016081392-appb-000115
Figure PCTCN2016081392-appb-000116
Figure PCTCN2016081392-appb-000117
和
Figure PCTCN2016081392-appb-000118
需要说明的是，在本发明中，取代基R2*和R3*均可以为一个或多个；如果为多个，同一个分子上的多个R2*和R3*各自可以相同或不同，只要在上述范围内即可。
优选地，在式I*-VI*和I'*-VI'*中，标有数字1-8的1,2-位置、2,3-位置、3,4-位置、4,5-位置、5,6-位置和7,8-位置中的至少一个上有取代或未取代的环状取代基；更优选地，2,3-位置和/或4,5-位置处有取代或未取代的环状取代基。优选地，所述环状取代基为全部由碳原子组成的三元环、四元环、五元环、六元环、七元环或八元环取代基，或者由含有氧、硫、氮和硅中的至少一个杂原子组成的三元环、四元环、五元环、六元环、七元环或八元环取代基；优选地，所述取代的环状取代基的取代基为C1-20烷基、C1-20酯基、C1-20酰基、C1-20羧基、取代或未取代的芳基、C3-8环烷基、腈基、硝基和
Figure PCTCN2016081392-appb-000119
中的至少一种；R30*为C1-20烷基或者取代或未 取代的芳基；进一步优选地，所述取代或未取代的环状取代基为
Figure PCTCN2016081392-appb-000120
Figure PCTCN2016081392-appb-000121
Figure PCTCN2016081392-appb-000122
特别地，在上述取代或未取代的环状取代基中，本文中没有特别定义的情况下，可以在上述取代或未取代的环状取代基的任意能够被取代的位置进行取代。优选地，所述C1-20烷基与上述相同。所述取代或未取代的芳基中的取代基与上述取代的芳基上的取代基相同。优选地，所述取代的芳基中的取代基为C1-20烷基或卤素。优选地，
Figure PCTCN2016081392-appb-000123
为
Figure PCTCN2016081392-appb-000124
Figure PCTCN2016081392-appb-000125
和
Figure PCTCN2016081392-appb-000126
中的任意一种。所述C1-20烷基、C1-20酯基、C1-20酰基、C1-20羧基、取代或未取代的芳基均与上述相同。所述C3-8环烷基可以为环丙基、环丁基、环戊基、环己基、环庚基和环辛基中的任意一种。
优选地，式I*-VI*和I'*-VI'*中的2,3-位置或4,5-位置处具有环状取代基，且所述环状取代基为
Figure PCTCN2016081392-appb-000127
进一步优选地，所述金属桥位稠环化合物为如下化合物中的任意一种：
Figure PCTCN2016081392-appb-000128
Figure PCTCN2016081392-appb-000129
Figure PCTCN2016081392-appb-000130
Figure PCTCN2016081392-appb-000131
Figure PCTCN2016081392-appb-000132
Figure PCTCN2016081392-appb-000133
Figure PCTCN2016081392-appb-000134
Figure PCTCN2016081392-appb-000135
Figure PCTCN2016081392-appb-000136
Figure PCTCN2016081392-appb-000137
Figure PCTCN2016081392-appb-000138
Figure PCTCN2016081392-appb-000139
Figure PCTCN2016081392-appb-000140
Figure PCTCN2016081392-appb-000141
Figure PCTCN2016081392-appb-000142
以上化合物中，[Ru]1为RuA(PPh3)2，[Ru]2为RuCO(PPh3)2，[Ru]3为Ru(PPh3)2，[Ru]4为RuA2PPh3，[Rh]1为Rh(PPh3)2，[Rh]2为RhA(PPh3)2，[Rh]3为RhAPPh3，[Rh]4为RhAPPh3，[Ir]1为Ir(PPh3)2，[Ir]2为IrA(PPh3)2，[Ir]3为IrAPPh3，[Ir]4为IrAPPh3；
A为H、Cl、Br或SCN。
其中，Me为甲基，Ph为苯基，
Figure PCTCN2016081392-appb-000143
为三苯基鏻阳离子，Et为乙基，BF4 -为四氟硼酸阴离子，CF3SO3 -为三氟甲磺酸阴离子。
第四方面，本发明提供了上述金属杂稠环化合物的制备方法，该方法包括：
将式VII*所示的化合物与钌配合物进行环加成反应，得到式I*所示的化合物，且式I*所示的化合物中的[M]1为RuAL2；将式II*所示的化合物与碱1在有机溶剂中反应，得到式I*所示的化合物，且式I*所示的化合物中的[M]1为RhL2或IrL2；
将式VII*所示的化合物分别与铑配合物和铱配合物进行环加成反应，得到式II*所示的化合物，且式II*所示的化合物中[M]2为RhAL2或IrAL2；或者，将式I*所示的化合物与亲核试剂进行亲核加成反应，得到式II*所示的化合物；
将式I*所示的化合物与
Figure PCTCN2016081392-appb-000144
进行亲核加成反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为
Figure PCTCN2016081392-appb-000145
将式VIII*所示的化合物分别与钌配合物、铑配合物和铱配合物进行环加成反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-CR5R6-；将 式I*所示的化合物与水或氧气反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-O-；将式I*所示的化合物与H2S、NaHS和S中的至少一种反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-S-；将式I所示的化合物与Na2Se、NaHSe和Se中的至少一种反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-Se-；将式I*所示的化合物与R7 *NH2反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-NR7 *-；
将式X*所示的化合物与式I*所示的化合物进行环加成反应，得到式IV*所示的化合物；
将式XI*所示的化合物与式III*所示的化合物进行扩环反应，得到式V*所示的化合物；
将式IX*所示的化合物分别与钌配合物、铑配合物和铱配合物进行环加成反应，得到式VI*所示的化合物；
将式I*所示的化合物在碱2的水溶液中水解，得到式I'*所示的化合物；
将式I'*所示的化合物与亲核试剂进行亲核加成反应，得到式II'*所示的化合物；或者将式II*所示的化合物在碱2的水溶液中水解，得到式II'*所示的化合物；
将式I'*所示的化合物与
Figure PCTCN2016081392-appb-000146
进行亲核加成反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为
Figure PCTCN2016081392-appb-000147
将式I'*所示的化合物与水或氧气反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-O-；将式I'*所示的化合物与H2S、NaHS和S中的至少一种反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-S-；将式I'*所示的化合物与Na2Se、NaHSe和Se中的至少一种反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-Se-；将式I'*所示的化合物与R7*NH2反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-NR7*-；或者，将式III*所示的化合物在碱2的水溶液中水解，得到式III'*所示的化合物；
将式X*所示的化合物与式I'*所示的化合物进行环加成反应，得到式IV'*所示的化合物；或者将式IV*所示的化合物在碱2的水溶液中水解，得到式IV'*所示的化合物；
将式XI*所示的化合物与式III'*所示的化合物进行扩环反应，得到式V'*所示的化合物；或者将式V*所示的化合物在碱2的水溶液中水解，得到式V'*所示的化合物；
将式VI*所示的化合物在碱2的水溶液中水解，得到式VI'*所示的化合物；
Figure PCTCN2016081392-appb-000148
式VII*-XI*中，G为-O-、-S-、-CR18*R19*-、-SiR20*R21*-或-NR22*-；
R18*、R19*、R20*、R21*和R22*各自独立地为氢、C1-20烷基、C1-20酯基、C1-20酰基、C3-20环烷基、C1-20卤代烷基、腈基、硝基、取代或未取代的芳基或
Figure PCTCN2016081392-appb-000149
R23*为C1-8烷基或取代或未取代的芳基；
R8*、R9*、R10*、R11*、R12*、R13*、R14*、R15*、R16*和R17*能选择的取代基的范围与R2*或R3*相同；
m1和n1分别为1-6的整数，且m1+n1<8；
所述钌配合物为RuCl2(PPh3)3、RuCl2(PMe3)3、RuCl2(PEt3)3和RuCl2(PCy3)3中的至少一种；
所述铑配合物为RhCl(PPh3)3、RhHCl2(PPh3)3、RhCl(PMe3)3、RhCl(PEt3)3和RhCl(PCy3)3中的至少一种；
所述铱配合物为IrHCl2(PPh3)3、IrCl(PPh3)3、IrCl(PMe3)3、IrCl(PEt3)3和IrCl(PCy3)3中的至少一种；
所述碱1为碱金属的碳酸盐和/或氢化物；
所述碱2为碱金属的氢氧化物；
所述亲核试剂为卤素单质，C1-10醇、C1-10醇钠、C1-10醇钾、C1-10硫醇、C1-10硫醇钠、C1-10硫醇钾、C1-10酚、C1-10酚钠和C1-10酚钾中的至少一种。
优选地，所述R18*、R19*、R20*、R21*和R22*各自独立地为氢、C1-17烷基、C1-17酯基、C1-17酰基、C3-17环烷基、C1-17卤代烷基、腈基、硝基、取代或未取代的芳基或
Figure PCTCN2016081392-appb-000150
R23*为C1-8烷基或取代或未取代的芳基。更优选地，所述R18*、R19*、R20*、R21*和R22*各自独立地为氢、C1-8烷基、C1-8酯基、C1-8酰基、C3-8环烷基、C1-8卤代烷基、腈基、硝基、取代或未取代的芳基或
Figure PCTCN2016081392-appb-000151
R23*为C1-8烷基或取代或未取代的芳基。所述C1-20烷基、C1-20酯基、C1-20酰基、C3-20环烷基均与上述相同。所述C1-20卤代烷基为F、Cl、Br或碘取代上述C1-20烷基中的至少一个氢所形成的取代基。
所述m1和n1分别为1-6的整数，且m1+n1<8；例如，在m+n<8的前提下，m1和n1可以各自独立地为1、2、3、4、5或6。具体地，m1为1，n1为1、2、3、4、5或6；或者m1为2，n1为1、2、3、4或5；或者m1为3，n1为1、2、3或4；或者m1为4，n1为1、2或3；或者m1为5，n1为1或2；或者m1为6，n1为1。
更优选地，VII*-XI*中，R10*的可选取代基的范围与前述式I中的R3对应相同，R9*的可选取代基的范围与前述式I中的R2对应相同，m1的取值范围与前述式I中的m对应相同，G的可选取代基的范围与前述式I中的X对应相同。
优选地，所述碱1为Na2CO3、K2CO3、Cs2CO3、CaH2和NaH中的至少一种。
优选地，所述碱2为NaOH和/或KOH。所述碱2的水溶液的浓度可以为0.01-10摩尔/升，优选0.5-5摩尔/升。
优选地，所述亲核试剂为Cl2、Br2、甲醇钠、乙醇钠、苯酚钠、对甲苯酚钠、苯硫酚钠、对甲苯硫酚钠和对甲氧基苯硫酚钠中的至少一种。
优选地，所述
Figure PCTCN2016081392-appb-000152
例如可以为
Figure PCTCN2016081392-appb-000153
和
Figure PCTCN2016081392-appb-000154
中的至少一种。
优选地，所述环加成反应的条件包括反应温度为零下100℃至零上200℃，优选0-60℃；反应时间为1分钟至2天，优选0.5小时至1天。
优选地，所述亲核加成反应的条件包括反应温度为零下100℃至零上200℃，优选0-60℃；反应时间为1分钟至2天，优选0.5小时至1天。
所述扩环反应的条件包括反应温度为零下100℃至零上200℃，优选0-60℃；反应时间为1分钟至2天，优选0.5小时至1天。
优选地，上述制备方法的所述反应均在有机溶剂存在下进行；所述有机溶剂为二氯甲烷、二氯乙烷、氯仿、甲醇、乙醇、丙酮、丁酮、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、甲苯、苯、二氧六环、乙醚和乙腈中的至少一种。
优选地，所述反应完成后，可以将获得的反应后混合物进行浓缩、沉淀后获得固体物质，再将获得的固体物质经过滤、洗涤和柱色谱分离后获得所述的金属桥位稠环化合物。
优选地，所述式VII*、式VIII*和式IX*所示的化合物的制备方法与前述制备式I所示的化合物的制备方法相同。具体地，当R10*为氢时，该方法包括：
将式XII*所示的化合物与有机金属试剂R*M1*和/或R*M2*Z1在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与式XIII*所示的化合物接触反应，获得式XIV*所示的J基团保护的链状多炔化合物；再将式XIV*所示的J基团保护的链状多炔化合物进行脱保护基团处理，获得式VII*、式VIII*和式IX*所示的链状多炔化合物：
Figure PCTCN2016081392-appb-000155
式XIII*中，J为用来保护炔基的保护基团。J可以为TMS(三甲基硅基)、TES(三乙基硅基)和TIPS(三异丙基硅基)中的任意一种。
式XIII*和XIV*中，G、m1、n1和Z1均与前述定义相同。
VII*、式VIII*和式IX*中，R33*为
Figure PCTCN2016081392-appb-000156
所述有机金属试剂R*M1*或R*M2*Z1中的R*为C1-8烷基、苯基和-NR35*R36*中的任意一种。其中，-NR35*R36*中的R35*和R36*可以分别独立地为氢、C1-8烷基和三甲基硅基中的任意一种。所述C1-8烷基与上述相同。
M1*优选为锂、钠或钾。M2*优选为镁。Z1优选为氯、溴或碘。
优选地，R*M1*为甲基锂、乙基锂、正丁基锂、叔丁基锂、苯基锂、二异丙基胺基锂和双(三甲基硅基)胺基锂中的至少一种。
优选地，R*M2*Z1为甲基溴化镁、乙基溴化镁、甲基氯化镁和乙基氯化镁中的至少一种。
优选使用脱保护剂对获得的式XIV*所示的J基团保护的链状多炔化合物进行脱保护基团处理。所述脱保护剂可以为K2CO3、Na2CO3、Cs2CO3、KF、(n-Bu)4NF(四正丁基氟化铵)、(Et)4NF(四乙基氟化铵)、(Me)4NF(四甲基氟化铵)和(n-Pr)4NF(四正丙基氟化铵)中的至少一种。
优选地，在对式XIV*所示的J基团保护的链状多炔化合物进行脱保护基团处理之前，对获得的含有式XIV*所示的J基团保护的链状多炔化合物的混合物进行淬灭和提纯操作。其中，所述淬灭操作中使用的淬灭剂可以为饱和氯化铵和/或水。所述提纯操作可以包括使用有机溶剂对获得的含有式XIV*所示的J基团保护的链状多炔化合物的混合物进行萃取，将萃取获得的有机相干燥后过滤、浓缩、层析分离获得式VII*、式VIII*和式IX*所示的化合物。其中，所述有机溶剂可以为乙醚、正己烷、甲苯、乙二醇二甲醚、1,4-二氧六环、二氯甲烷和三氯甲烷中的至少一种；所述对萃取获得的有机相干燥的操作可以包括使用无水硫酸镁和/或无水硫酸钠；所述层析分离的操作可以包括使用硅胶柱层析和/或中性氧化铝。
优选地，在对式XIV*所示的J基团保护的链状多炔化合物进行脱保护基团处理之后获得的含有式VII*、式VIII*和式IX*所示的链状多炔化合物的混合物进行淬灭和提纯操作。所述淬灭和提纯操作的方法同上所述。
当R10*不为氢时，所述式VII*、式VIII*和式IX*所示的化合物的制备方法如下：
将式XII*所示的化合物与有机金属试剂R*M1*和/或R*M2*Z1在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与式XV*所示的化合物接触反应，获得式VII*、式VIII*或式IX*所示的化合物：
Figure PCTCN2016081392-appb-000157
其中，有机金属试剂R*M1*或R*M2*Z1与上述定义相同；G、R33*、m1和n1均与上述定义相同，且所述R34*的可选范围与R9*的可选范围对应相同。
优选地，所述式XII*所示的化合物与有机金属试剂R*M1*和/或R*M2*Z1的总和的摩尔比为1:(0.5-1)，优选1：(0.9-1)。当同时含有R*M1*和R*M2*Z1时，对所述有机金属试剂R*M1*和R*M2*Z1的用量比例没有特别限定，二者可以以任意摩尔比混合使用。
在所述方法中，对所述非质子性溶剂没有特别限定。优选地，所述非质子性溶剂为苯、甲苯、正己烷、乙醚、乙二醇二甲醚、四氢呋喃和1,4-二氧六环、石油醚、汽油中的至少一种。
在所述方法中，所述式XII*所示的化合物与有机金属试剂R*M1*和/或R*M2*Z1可以在惰性气体保护下进行金属交换反应。所述惰性气体为任何不与催化剂、原料和产物反应，并且对反应不产生任何负面影响的气体。所述惰性气体可以为氮气、氦气、氩气和氖气中的至少一种。所述式XII*所示的化合物与有机金属试剂R*M1*和/或R*M2*Z1在非质子性溶剂中接触的条件包括温度可以为零下100℃至零上30℃，优选为零下78℃至0℃，时间为0.5-10h，优选为1-3h。
在所述方法中，将式XII*所示的化合物与有机金属试剂R*M1*和/或R*M2*Z1在非质子性溶剂中进行金属交换反应得到的反应混合物与式XIII*所示的化合物或式XV*所示的化合物接触反应的条件包括温度可以为零下100℃至零上30℃，优选为零下78℃至0℃，时间为0.5-10h，优选为1-5h。
第五方面，本发明提供了前述金属桥位稠环化合物在太阳能电池、光动力学治疗、光解水、锂-空气电池领域中的应用。
优选地，式I*、I'*、II*、II'*和VI*所示的化合物适用于太阳能电池领域。
优选地，式II*所示的化合物适用于锂-空气电池领域；
优选地，式III*、IV*、V*、III'*、IV'*、V'*和VI'*所示的化合物适用于光动力学治疗领 域。
优选地，式I*所示的化合物中，R2*为标有数字1-6上的取代基，R2*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基时，式I*所示的化合物适用于太阳能电池领域，进一步优选地，用作太阳能电池的光敏化剂。
优选地，式II*所示的化合物中，R2*为标有数字1-6上的取代基，R2*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基时，式II*所示的化合物适用于太阳能电池领域或锂-空气电池领域，进一步地，用作太阳能电池的光敏化剂或作为储锂材料应用于锂-空气电池中。
优选地，式IV*所示的化合物中，R2*为标有数字1、2、3、7或8，优选标有数字8上的取代基，优选R2*为C1-20烷氧基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的四元环、五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的四元环、五元环或六元环取代基时；式IV*所示的化合物适用于光动力学治疗。
优选地，式V*所示的化合物中，R2*为标有数字1、2、3、7、8和9中的至少一个上，优选为标有数字8和9上的取代基，R2*优选为C1-20烷氧基或C1-20酯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；Y1为-O-或-S-时；式V*所示的化合物适用于肿瘤光动力学治疗。
优选地，式VI*所示的化合物中，R2*为标有数字1、2、3、7或8上，优选标有数字8上的取代基，且R2*为芳基，优选为苯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基时；式VI*所示的化合物适用于太阳能电池领域，进一步地，用作太阳能电池的光敏化剂。
优选地，式III*所示的化合物中，R2*为标有数字1-6上的取代基，R2*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；X1为-O-或-S-时；式III*所示的化合物适用于肿瘤光动力学治疗。
优选地，式I'*所示的化合物中，R3*为标有数字1-6上的取代基，R3*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由 氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基时，式I'*所示的化合物适用于太阳能电池领域，进一步优选地，用作太阳能电池的光敏化剂。
优选地，式II'*所示的化合物中，R3*为标有数字1-6上的取代基，R3*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基时，式II'*所示的化合物适用于太阳能电池领域，进一步优选地，用作太阳能电池的光敏化剂。
优选地，式III'*所示的化合物中，R3*为标有数字1-6上的取代基，R3*为芳基，优选为苯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；X1为
Figure PCTCN2016081392-appb-000158
时，式III'*所示的化合物适用于肿瘤光动力学治疗。
优选地，式IV'*所示的化合物中，R3*为标有数字1-8上的取代基，R3*为芳基，优选为苯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；X1为
Figure PCTCN2016081392-appb-000159
时，式IV'*所示的化合物适用于肿瘤光动力学治疗。
优选地，式V'*所示的化合物中，R3*为标有数字1-9上的取代基，R3*为C1-20烷基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；Y1为-O-或-S-时，式V'*所示的化合物适用于肿瘤光动力学治疗。
优选地，式VI'*所示的化合物中，R3*为标有数字1-8上的取代基，R3*为C1-20烷氧基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基时，式VI'*所示的化合物适用于肿瘤光动力学治疗。
以下将通过具体的制备例、实施例和测试例对本发明进行详细描述。
以下实施例中，所使用的具体的式VII*、式VIII*和式IX*所示的化合物分别按照如下制备例中的方法制备。
制备例1
Figure PCTCN2016081392-appb-000160
其中，TMS代表三甲基硅基。EtMgBr为乙基溴化镁(购自百灵威科技有限公司，商品牌 号为248474)，
Figure PCTCN2016081392-appb-000161
(三甲基硅丙炔醛，购自百灵威科技有限公司，商品牌号为2975-46-4)，(n-Bu)4NF(四正丁基氟化铵，购自百灵威科技有限公司，商品牌号为A10588)。
(1)化合物1的制备
在氮气氛围下，在磁力搅拌下，将1,6-庚二炔(43.63mmol，购自阿拉丁试剂(上海)有限公司，商品牌号为H102744-25mL)溶于100mL四氢呋喃中，冷却至0℃，逐滴加入乙基溴化镁溶液(1.0M的四氢呋喃溶液，43.6mL，含乙基溴化镁43.60mmol)，1h内加完，室温下反应1h后再冷却至0℃，快速加入三甲基硅丙炔醛(7.30mL，43.60mmol)，继续反应1h，反应结束后，用饱和氯化铵溶液淬灭，乙醚萃取，合并有机相，无水硫酸镁干燥，过滤，浓缩，硅胶柱层析(洗脱剂：正己烷/乙酸乙酯＝6/1体积比)，得5.71g无色油状液体化合物1，产率：60％。(化合物1的产率为化合物1的摩尔量/1,6-庚二炔的摩尔量×100％)。
化合物1的核磁和高分辨质谱数据如下：
1H NMRδ＝5.04(t,J＝1.80Hz,1H),2.69(br,1H),2.31(td,J＝6.99Hz,J＝1.80Hz,2H),2.25(td,J＝6.99Hz,J＝2.60Hz,2H),1.93(t,J＝2.60Hz,1H),1.69(m,2H),0.14(s,9H)；13C NMRδ＝102.71,88.81,84.24,83.45,78.31,69.12,52.59,27.25,17.82,17.56,-0.26.HRMS-ESI(m/z)计算值C13H18OSiNa[M+Na]+241.1019,实际值241.1025.
(2)化合物2的制备
把化合物1(22.90mmol)溶于120mL四氢呋喃，冷却至0℃，慢慢加入四正丁基氟化铵溶液(1.0M的四氢呋喃溶液，27.48mL，含四正丁基氟化铵27.48mmol)，反应至原料消失(30min)，反应液用饱和氯化铵溶液淬灭，乙醚萃取，有机相用无水硫酸镁干燥，再通过柱层析法分离(洗脱剂：正己烷/乙酸乙酯＝4/1体积比)得2.85g无色油状液体化合物2，产率：85％。(化合物2的产率为化合物2的摩尔量/化合物1的摩尔量×100％)。
化合物2的核磁和高分辨质谱数据如下：
1H NMRδ＝5.08(m,1H),2.69(br,1H),2.53(t,J＝2.20Hz,1H),2.34(td,J＝7.00Hz,J＝1.85Hz,2H),2.25(td,J＝7.00Hz,J＝2.57Hz,2H),1.95(t,J＝2.57Hz,1H),1.71(m,2H)；13C NMRδ＝84.65,83.49,81.52,77.91,72.39,69.22,52.06,27.18,17.77,17.62.HRMS-ESI(m/z)计算值C10H10OSiNa[M+Na]+169.0624,实际值169.0651.
制备例2
Figure PCTCN2016081392-appb-000162
其中，n-BuLi为正丁基锂(购自百灵威科技有限公司，商品牌号为913796)。
(1)化合物3的制备
在氮气氛围下，在磁力搅拌下，把2,2-二炔丙基丙二酸二甲酯(24.0mmol，根据文献J.Am.Chem.Soc.2013,135,8133.合成)溶于200mL四氢呋喃中，冷却至-78℃，逐滴加入正丁基锂(2.2M的四氢呋喃溶液，10.90mL，含正丁基锂24.0mmol)，1h内加完，-78℃下反应15min后，逐滴加入三甲基硅丙炔醛(24.0mmol)，继续反应2h，反应结束后，用饱和氯化铵溶液淬灭，乙醚萃取，合并有机相，无水硫酸镁干燥，过滤，浓缩，硅胶柱层析(洗脱剂：正己烷/乙酸乙酯＝5/1体积比)，得4.82g淡黄色油状液体化合物3，产率：60％。(化合物3的产率为化合物3的摩尔量/2,2-二炔丙基丙二酸二甲酯的摩尔量×100％)。
化合物3的核磁和高分辨质谱数据如下：
1H NMRδ＝5.03(s,1H),3.76(s,6H),3.03(d,J＝2.00Hz,2H),2.97(d,J＝2.64Hz,2H),2.37(br,1H),2.03(t,J＝2.60Hz,1H),0.19(s,9H)；13C NMRδ＝169.05,102.11,88.97,81.08,79.06,78.28,71.88,56.59,53.14,52.30,22.93,22.77,-0.41；HRMS-ESI(m/z)计算值C17H22O5SiNa[M+Na]+357.1129,实际值357.1130.
(2)化合物4的制备
将化合物3(14.4mmol)溶于150mL四氢呋喃中，冷却至-30℃，慢慢加入四正丁基氟化铵溶液(1.0M的四氢呋喃溶液，21.6mL，含四正丁基氟化铵21.6mmol)，反应至原料消失(20min)，反应液用饱和氯化铵溶液淬灭，乙醚萃取，有机相用无水硫酸镁干燥，再通过柱层析法分离(洗脱剂：正己烷/乙酸乙酯＝3/1体积比)得3.21g淡黄色油状液体化合物4，产率：85％。(化合物4的产率为化合物4的摩尔量/化合物3的摩尔量×100％)。
化合物4的核磁和高分辨质谱数据如下：
1H NMRδ＝5.05(ddt,J＝7.51Hz,J＝2.25Hz,J＝2.11Hz,1H),3.76(s,1H),3.02(d,J＝2.11Hz,2H),2.95(d,J＝2.72Hz,2H),2.81(d,J＝7.51Hz,1H),2.53(d,J＝2.25Hz,1H),2.03(t,J＝2.68Hz,1H)；13C NMRδ＝169.11,80.99,80.78,79.03,78.19,72.44,72.10,56.48,53.25,51.54,22.84,22.75；HRMS-ESI(m/z)计算值C14H14O5Na[M+Na]+285.0733,实际值285.0734.
制备例3
Figure PCTCN2016081392-appb-000163
(1)除以下特征外，化合物5的制备方法与化合物1的制备方法相同。
将制备例1中使用的1,6-庚二炔换成等摩尔数的丙炔醚(购自阿法埃莎(中国)化学有限公司，商品牌号为MFCD00048108)。
化合物5的产率：75％。(化合物5的产率为化合物5的摩尔量/炔丙醚的摩尔量×100％)。
化合物5的核磁和高分辨质谱数据如下：
1H NMRδ＝5.14(t,J＝1.67Hz,1H),4.31(d,J＝1.67Hz,1H),4.24(b,J＝2.37Hz,2H),2.47(br,1H),2.46(t,J＝2.37Hz,1H),0.17(s,9H)；13C NMRδ＝101.60,89.95,84.19,79.74,78.85,75.40,56.81,56.75,52.59,-0.22；HRMS-ESI(m/z)计算值C12H16O2SiNa[M+Na]+243.0812,实际值248.0805.
(2)除以下特征外，化合物6的制备方法与化合物2的制备方法相同。
将制备例1步骤(2)中使用的化合物1换成本制备例步骤(1)中获得的化合物5。
化合物6的产率：87％。(化合物6的产率为化合物6的摩尔量/化合物5的摩尔量×100％)。
化合物6的核磁和高分辨质谱数据如下：
1H NMRδ＝5.16(s,1H),2.69(br,1H),4.31(d,J＝1.52Hz,1H),4.25(d,J＝2.25Hz,2H),2.80(br,2H),2.57(d,J＝2.25Hz,1H),2.47(t,J＝2.25Hz,1H)；13C NMRδ＝83.81,80.69,80.09,78.82,75.47,73.13,56.87,56.76,52.05；HRMS-ESI(m/z)计算值C9H8O2Na[M+Na]+171.0417,实际值171.0411.
制备例4
Figure PCTCN2016081392-appb-000164
(1)除以下特征外，化合物7的制备方法与化合物3的制备方法相同。
将制备例2中使用的三甲基硅炔丙醛换成等摩尔数的1-苯基-2-丙炔-1-酮(根据文献Guang-Cun Ge,Dong-Liang Mo,Chang-Hua Ding,Li-Xin Dai,Xue-Long Hou，Palladacycle-Catalyzed Reaction of Bicyclic Alkenes with Terminal Ynones:Regiospecific Synthesis of Polysubstituted Furans,Org.Lett.2012,14,5756合成)。
化合物7的产率：75％。(化合物7的产率为化合物7的摩尔量/2,2-二炔丙基丙二酸二甲酯的摩尔量×100％)。
化合物7的核磁数据如下：
1H NMRδ＝7.29-7.47(m,5H),3.75(s,6H),3.02(s,2H),2.96(d,J＝2.63Hz,2H),2.50(br,1H),2.11(s,1H),2.02(t,J＝2.63Hz,1H)；13C NMRδ＝169.14,132.54,129.15,128.34,121.41,89.07,81.18,79.07,78.29,75.23,71.89,56.60,53.15,52.31,22.94,22.78.
制备例5
Figure PCTCN2016081392-appb-000165
(1)除以下特征外，化合物8的制备方法与化合物1的制备方法相同。
将制备例1中使用的1,6-庚二炔换成等摩尔数的1-炔丙氧基-2-丁炔(根据文献Hong-Tai Chang,Masilamani Jeganmohan,Chien-Hong Cheng,Cobalt-Catalyzed Intramolecular[2+2+2]Cocyclotrimerization of Nitrilediynes:An Efficient Route to Tetra-and Pentacyclic Pyridine Derivatives,Org.Lett.2007,9,505合成)。
化合物8的产率：82％。(化合物8的产率为化合物8的摩尔量/1-炔丙氧基-2-丁炔的摩尔量×100％)。
化合物8的核磁数据如下：
1H NMRδ＝5.13(t,J＝1.68Hz,1H),4.32(d,J＝1.68Hz,1H),4.25(q,J＝1.65Hz,2H),2.48(br,1H),1.80(t,J＝1.65Hz,3H),0.16(s,9H)；13C NMRδ＝101.49,89.94,84.18,79.73,78.84,75.39,56.80,56.14,52.48,3.80,-0.21.
(2)除以下特征外，化合物9的制备方法与化合物2的制备方法相同。
将制备例1步骤(2)中使用的化合物1换成本制备例步骤(1)中获得的化合物8。
化合物9的产率：86％。(化合物9的产率为化合物9的摩尔量/化合物8的摩尔量×100％)。
化合物9的核磁数据如下：
1H NMRδ＝5.12(s,1H),4.30(d,J＝1.51Hz,1H),4.24(q,J＝1.54Hz,2H),2.85(br,1H),2.56(d,J＝2.24Hz,1H),1.75(t,J＝1.54Hz,1H)；13C NMRδ＝83.80,80.68,80.08,78.71,75.36,73.02,56.76,56.65,52.17,3.85.
制备例6
Figure PCTCN2016081392-appb-000166
(1)除以下特征外，化合物13的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的4-炔丙氧基-1,2-丁二烯(根据文献Hongwen Luo,Shengming Ma,CuI-Catalyzed Synthesis of Functionalized Terminal Allenes from 1-Alkynes,Eur.J.Org.Chem.2013,15,3041.及PCT Int.Appl.,2011050016合成)。
化合物13为淡黄色油状液体，产率：55％。(化合物13的产率为化合物13的摩尔量/4-炔丙氧基-1,2-丁二烯的摩尔量×100％)。
化合物13的核磁和高分辨质谱数据如下：
1H NMRδ＝5.20(tt,J＝6.69Hz,J＝6.69Hz,1H),5.15(t,J＝1.84,1H),4.78(dt,J＝6.69Hz,J＝2.34Hz,2H),4.23(d,J＝1.84Hz,2H),4.12(dt,J＝6.69Hz,J＝2.34Hz,2H),2.68(br,1H),0.11(s,9H)；13C NMRδ＝209.36,101.23,86.51,83.24,80.67,80.12,75.67,72.53,67.32,56.91,52.35；HRMS-ESI(m/z)计算值C13H18O2SiNa[M+Na]+257.0968,实际值257.0986.
(2)除以下特征外，化合物14的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物13。
化合物14为淡黄色油状液体，产率：92％。(化合物14的产率为化合物14的摩尔量/化合物13的摩尔量×100％)。
化合物14的核磁和高分辨质谱数据如下：
1H NMRδ＝5.22(tt,J＝6.71Hz,J＝6.71Hz,1H),5.16(dt,J＝1.84Hz,J＝1.84,1H),4.81(dt,J＝6.71Hz,J＝2.35Hz,2H),4.23(d,J＝1.84Hz,2H),4.09(dt,J＝6.71Hz,J＝2.35Hz,2H),2.71(br,1H),2.57(d,J＝1.84Hz,1H)；13C NMRδ＝209.57,86.81,83.45,80.77,80.13,76.01,72.81,67.46,56.81,51.50；HRMS-ESI(m/z)计算值C10H10O2Na[M+Na]+185.0573,实际值185.0574.
制备例7
Figure PCTCN2016081392-appb-000167
(1)除以下特征外，化合物15的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的2-炔丙基-2-(5-苯基-2,4-戊二炔基)丙二酸二甲酯(根据文献Wei Shi,Yingdong Luo,Xiancai Luo,Lei Chao,Heng Zhang,Jian Wang,Aiwen Lei,Investigation of an Efficient Palladium-Catalyzed C(sp)-C(sp)Cross-Coupling Reaction Using Phosphine-Olefin Ligand:Application and Mechanistic Aspects,J.Am.Chem.Soc.2008,130,14713.合成)。
化合物15为淡黄色固体，产率：45％。(化合物15的产率为化合物15的摩尔量/2-炔丙基-2-(5-苯基-2,4-戊二炔基)丙二酸二甲酯的摩尔量×100％)。
化合物15的核磁和高分辨质谱数据如下：
1H NMRδ＝7.30-7.48(m,5H),5.04(dt,J＝7.61Hz,J＝2.02Hz,1H),3.79(s,6H),3.16(s,2H),3.07(d,J＝2.02Hz,2H),2.35(d,J＝7.61Hz,1H),0.19(s,9H)；13C NMRδ＝168.86,132.57,129.16,128.56,101.99,89.28,81.30,79.12,77.82,75.92,68.30,56.73,53.29,52.45,24.06,23.29, -0.36；HRMS-ESI(m/z)计算值C25H26O5SiNa[M+Na]+457.1442,实际值457.1450.
(2)除以下特征外，化合物16的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物15。
化合物16为淡黄色固体，产率：89％。(化合物16的产率为化合物16的摩尔量/化合物15的摩尔量×100％)。
化合物16的核磁和高分辨质谱数据如下：
1H NMRδ＝7.29-7.48(m,5H),5.07(dt,J＝2.25,J＝2.29,1H),3.80(s,6H),3.16(s,2H),3.07(d,J＝2.29Hz,2H),2.55(d,J＝2.25Hz,1H),2.19(br,1H)；13C NMRδ＝168.89,132.59,129.20,128.40,121.52,80.93,79.33,77.74,75.99,73.78,72.56,68.37,56.67,53.39,51.86,24.10,23.25；HRMS-ESI(m/z)计算值C22H18O5Na[M+Na]+385.1046,实际值385.1049.
制备例8
Figure PCTCN2016081392-appb-000168
除以下特征外，化合物17的制备方法与化合物1的制备方法相同。
将制备例1中使用的三甲基硅炔丙醛换成等摩尔数的1-苯基-2-丙炔-1-酮(根据文献Guang-Cun Ge,Dong-Liang Mo,Chang-Hua Ding,Li-Xin Dai,Xue-Long Hou，Palladacycle-Catalyzed Reaction of Bicyclic Alkenes with Terminal Ynones:Regiospecific Synthesis of Polysubstituted Furans,Org.Lett.2012,14,5756合成)。
化合物17的产率：61％。(化合物17的产率为17摩尔量/1,6-庚二炔的的摩尔量×100％)。
化合物17的核磁数据如下：
1H NMRδ＝7.31-7.49(m,5H),2.65(br,1H),2.41(s,1H),2.32(t,J＝6.98Hz,2H),2.23(td,J＝6.98Hz,J＝2.55Hz,2H),1.97(t,J＝2.55Hz,1H),1.69(m,2H)；13C NMRδ＝132.53,129.14,128.34,121.48,84.61,83.45,81.48,77.87,72.35,69.47,52.12,27.14,17.72,17.58.
制备例9
Figure PCTCN2016081392-appb-000169
(1)除以下特征外，化合物18的制备方法与化合物1的制备方法相同。
将实施例1中使用的1,6-庚二炔换成等摩尔数的1,8-壬二炔(购自阿法埃莎(中国)化学有限公司，商品牌号为MFCD00008581)。
化合物18的产率：47％。(化合物18的产率为化合物18的摩尔量/1,8-壬二炔的摩尔量×100％)。
化合物18的核磁数据如下：
1H NMRδ＝5.04(t,J＝1.85Hz,1H),2.58(br,1H)，2.22(td,J＝6.99Hz,J＝1.85Hz,2H),2.17(td,J＝6.99Hz,J＝2.83Hz,2H),1.92(t,J＝2.83Hz,1H),1.60(m,6H),0.14(s,9H)；13C NMRδ＝102.59,88.72,84.88,84.02,77.58,68.64,52.51,27.36,27.10,18.15,17.04,16.98,-0.25.
(2)除以下特征外，化合物19的制备方法与化合物2的制备方法相同。
将实施例1步骤(2)中使用的化合物1换成本实施例步骤(1)中获得的化合物18。
化合物19的产率：80％。(化合物19的产率为化合物19的摩尔量/化合物18的摩尔量×100％)。
化合物19的核磁数据如下：
1H NMRδ＝5.05(d,J＝2.22Hz,1H),2.87(br,1H),2.51(d,J＝2.22Hz,1H),2.20(td,J＝6.78Hz,J＝1.94Hz,2H),2.16(td,J＝6.75Hz,J＝2.56Hz,2H,2H),1.97(d,J＝2.56Hz,1H),1.62(m,6H)；13C NMRδ＝85.18,84.11,76.74,72.38,68.87,51.82,27.35,27.07,18.11,17.85,17.52.
制备例10
Figure PCTCN2016081392-appb-000170
(1)除以下特征外，化合物20的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的HC≡CCH2C(COOMe)2CH2CH＝C＝CH2(根据文献Ramaiah Kumareswaran,Seunghoon Shin,Isabelle Gallou,and T.V.RajanBabu,Silylstannylation of Allenes and Silylstannylation-Cyclization of Allenynes.Synthesis of Highly Functionalized Allylstannanes and Carbocyclic and Heterocyclic Compounds,J.Org.Chem.2004,69,7157合成)。
化合物20为淡黄色油状液体，产率：60％。(化合物20的产率为化合物20的摩尔量/HC≡CCH2C(COOMe)2CH2CH＝C＝CH2的摩尔量×100％)。
化合物20的核磁数据如下：
1H-NMRδ＝5.05(t,J＝1.85Hz,1H),4.95(tt,J＝8.00Hz,J＝6.64Hz,1H),4.71(dt,J＝6.64Hz,J＝2.41Hz,2H),3.74(s,6H),2.90(dt,J＝8.00Hz,J＝2.41Hz,1H),2.70(dt,J＝7.95Hz,J＝2.41Hz,1H),2.30(br,1H)；13C NMRδ＝210.12,170.07,102.18,88.79,83.65,80.85,79.42,74.82,57.23,52.82,52.30,31.80,22.97,-0.39.
(2)除以下特征外，化合物21的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物20。
化合物21为淡黄色油状液体，产率：93％。(化合物21的产率为化合物21的摩尔量/化合物20的摩尔量×100％)。
化合物21的核磁数据如下：1H-NMRδ＝5.07(br,1H),4.97(m,1H),4.71(dt,J＝6.66Hz,J＝2.44Hz,2H),3.77(s,6H),2.92(d,J＝2.00Hz,1H),2.77(dt,J＝8.01Hz,J＝2.44Hz,1H),2.55(d,J＝2.40Hz,1H),2.54(br,1H)；13C NMRδ＝210.07,170.10,83.60,81.11,80.57,79.49,74.84,73.28,57.10,52.86,51.61,31.80,22.91.
制备例11
Figure PCTCN2016081392-appb-000171
(1)除以下特征外，化合物22的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的HC≡CCH2C(COOMe)2CH2CH＝C＝CHPh(根据文献Ramaiah Kumareswaran,Seunghoon Shin,Isabelle Gallou,and T.V.RajanBabu,Silylstannylation of Allenes and Silylstannylation-Cyclization of Allenynes.Synthesis of Highly Functionalized Allylstannanes and Carbocyclic and Heterocyclic Compounds,J.Org.Chem.2004,69,7157合成)。
化合物22为淡黄色油状液体，产率：62％。(化合物22的产率为化合物22的摩尔量/HC≡CCH2C(COOMe)2CH2CH＝C＝CHPh的摩尔量×100％)。
化合物22的核磁数据如下：
1H-NMRδ＝7.30-7.49(m,5H),5.02(t,J＝1.84Hz,1H),4.93(td,J＝7.95Hz,J＝6.61Hz,1H),4.71(dt,J＝6.61Hz,J＝2.28Hz,2H),3.72(s,6H),2.88(d,J＝1.84Hz,1H),2.68(dt,J＝7.95Hz,J＝2.38Hz,1H),2.28(br,1H),0.19(s,1H)；13C NMRδ＝210.09,170.05,132.54,129.15,128.35,121.47,102.13,88.74,83.61,80.81,79.37,74.77,57.12,52.85,52.32,31.65,22.95,-0.25.
(2)除以下特征外，化合物23的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物22。
化合物23为淡黄色油状液体，产率：93％。(化合物23的产率为化合物23的摩尔量/化合物22的摩尔量×100％)。
化合物23的核磁数据如下：
1H-NMRδ＝7.35-7.54(m,5H),5.12(br,1H),4.92(tt,J＝8.01Hz,J＝6.63Hz,1H),4.76(dt,J＝6.63Hz,J＝2.43Hz,2H),3.75(s,6H),2.97(d,J＝2.01Hz,1H),2.72(dt,J＝8.01Hz,J＝2.43Hz,1H),2.45(d,J＝2.39Hz,1H),2.40(br,1H)；13C NMRδ＝210.17,170.17,132.64,129.35,128.45,121.58,83.62,81.41,80.64,79.63,74.92,73.34,57.25,52.74,51.53,31.94,22.73.
制备例12
Figure PCTCN2016081392-appb-000172
(1)除以下特征外，化合物24的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的2-炔丙基-2-(5-(2-噻吩基)-2,4-戊二炔基)丙二酸二甲酯(根据文献Wei Shi,Yingdong Luo,Xiancai Luo,Lei Chao,Heng Zhang,Jian Wang,Aiwen Lei,Investigation of an Efficient Palladium-Catalyzed C(sp)-C(sp)Cross-Coupling Reaction Using Phosphine-Olefin Ligand:Application and Mechanistic Aspects,J.Am.Chem.Soc.2008,130,14713.合成)。
化合物24为淡黄色固体，产率：47％。(化合物24的产率为化合物24的摩尔量/2-炔丙基-2-(5-(2-噻吩基)-2,4-戊二炔基)丙二酸二甲酯的摩尔量×100％)。
化合物24的核磁数据如下：
1H NMRδ＝7.16-7.48(m,3H),5.03(dt,J＝7.60Hz,J＝2.03Hz,1H),3.77(s,6H),3.14(s,2H),3.08(d,J＝2.03Hz,2H),2.34(d,J＝7.60Hz,1H),0.18(s,9H)；13C NMRδ＝170.21,132.57,128.16,127.56,122.31,101.91,89.07,81.32,79.04,77.75,75.85,68.24,56.65,53.47,52.53,24.14,23.31,-0.31.
(2)除以下特征外，化合物25的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物24。
化合物25为淡黄色固体，产率：83％。(化合物25的产率为化合物25的摩尔量/化合物24的摩尔量×100％)。
化合物25的核磁数据如下：
1H NMRδ＝7.18-7.46(m,3H),5.08(dt,J＝2.25,J＝2.29,1H),3.81(s,6H),3.12(s,2H),3.01(d,J＝2.29Hz,2H),2.54(d,J＝2.25Hz,1H),2.13(br,1H)；13C NMRδ＝169.99,132.42,129.11,128.42,121.25,80.37,79.76,77.56,75.47,73.85,72.86,68.14,56.16,53.35,51.45,24.28, 23.46.
制备例13
Figure PCTCN2016081392-appb-000173
(1)除以下特征外，化合物7-1的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的N,N-二炔丙基对甲苯磺酰胺(根据文献J.Am.Chem.Soc.2000,122,11529.合成)。
化合物7-1的产率：60％。(化合物7-1的产率为化合物7-1的摩尔量/N,N-二炔丙基对甲苯磺酰胺的摩尔量×100％)。
化合物7-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.64(d,J＝12.34Hz,2H),7.35(d,J＝12.34Hz,2H),5.16(t,J＝1.64Hz,1H),3.95(d,J＝1.64Hz,2H),3.87(d,J＝2.37Hz,2H),2.65(br,1H),2.49(t,J＝2.37Hz,1H),2.34(s,3H),0.13(s,9H)；13C NMRδ＝137.50,136.79,129.87,128.37,102.50,87.85,84.11,80.74,78.64,74.80,52.64,34.83,34.55,21.56,-0.32；HRMS-ESI(m/z)计算值C19H23NSO3SiNa[M+Na]+396.1060,实际值396.1058.
(2)除以下特征外，化合物8-1的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物7-1。
化合物8-1的产率：81％。(化合物8-1的产率为化合物8-1的摩尔量/化合物7-1的摩尔量×100％)。
化合物8-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.63(d,J＝12.37Hz,2H),7.32(d,J＝12.37Hz,2H),5.19(dt,J＝2.35Hz,J＝1.64Hz,1H),3.93(d,J＝1.64Hz,2H),3.85(d,J＝2.36Hz,2H),2.55(br,1H),2.52(d,J＝2.35Hz,1H),2.47(t,J＝2.36Hz,1H),2.33(s,3H)；13C NMRδ＝137.48,136.72,129.77,128.27,87.835,84.01,80.33,78.54,74.58,72.76,52.53,34.92,34.48,21.57；HRMS-ESI(m/z)计算值C16H15NSO3Na[M+Na]+324.0665,实际值324.0661.
制备例14
Figure PCTCN2016081392-appb-000174
(1)除以下特征外，化合物9-1的制备方法与化合物1的制备方法相同。
将制备例1中使用的1,6-庚二炔换成等摩尔数的1,7-辛二炔(购自阿法埃莎(中国)化学有限公司，商品牌号为MFCD00008580)。
化合物9-1的产率：45％。(化合物9-1的产率为化合物9-1的摩尔量/1,7-辛二炔的摩尔量×100％)。
化合物9-1的核磁和高分辨质谱数据如下：
1H NMRδ＝5.07(t,J＝1.97Hz,1H),2.55(br,1H)，2.25(td,J＝7.00Hz,J＝1.85Hz,2H),2.20(td,J＝7.00Hz,J＝2.80Hz,2H),1.95(t,J＝2.51Hz,1H),1.63(m,4H),0.17(s,9H)；13C NMRδ＝102.62,88.75,84.91,84.06,77.82,68.67,52.55,27.40,27.13,18.22,17.09,-0.33；HRMS-ESI(m/z)计算值C14H20OSiNa[M+Na]+255.1176,实际值.255.1152.
(2)除以下特征外，化合物10-1的制备方法与化合物2的制备方法相同。
将制备例1步骤(2)中使用的化合物1换成本制备例步骤(1)中获得的化合物9-1。
化合物10-1的产率：78％。(化合物10-1的产率为化合物10-1的摩尔量/化合物9-1的摩尔量×100％)。
化合物10-1的核磁和高分辨质谱数据如下：
1H NMRδ＝5.08(d,J＝2.20Hz,1H),2.90(br,1H),2.54(d,J＝2.25Hz,1H),2.23(td,J＝6.57Hz,J＝1.97Hz,2H),2.19(td,J＝6.65Hz,J＝2.54Hz,2H,2H),1.95(d,J＝2.59Hz,1H),1.60(m,4H)；13C NMRδ＝85.21,84.14,76.83,72.28,68.77,51.91,27.38,27.10,18.15,17.88；HRMS-ESI(m/z)计算值C11H12ONa[M+Na]+183.0780,实际值183.0785.
制备例15
Figure PCTCN2016081392-appb-000175
(1)除以下特征外，化合物11-1的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的5-己炔腈(购自百灵威科技有限公司，商品牌号为009109)。
化合物11-1为淡黄色油状液体，产率：81％。(化合物11-1的产率为化合物11-1的摩尔量/5-己炔腈的摩尔量×100％)。
化合物11-1的核磁和高分辨质谱数据如下：
1H NMRδ＝5.07(t,J＝1.85Hz,1H),2.54(br,1H),2.48(t,J＝7.08Hz,2H),2.41(td,J＝6.74Hz,J＝1.85Hz,2H),1.87(tt,J＝7.08Hz,J＝6.74Hz,2H),0.17(s,9H)；13C NMRδ＝119.23,102.22,89.39,82.51,79.59,52.60,24.29,17.99,16.23,-0.22.HRMS-ESI(m/z)计算值C12H17NOSiNa[M+Na]+242.0972,实际值242.0968.
(2)除以下特征外，化合物12-1的制备方法与化合物4的制备方法相同。
将制备施例2步骤(2)中使用的化合物3换成本实施例步骤(1)中获得的化合物11-1。
化合物12-1为淡黄色油状液体，产率：83％。(化合物12-1的产率为化合物12-1的摩尔量/化合物11-1的摩尔量×100％)。
化合物12-1的核磁和高分辨质谱数据如下：
1H NMRδ＝5.09(dd,J＝2.00Hz,J＝1.70Hz,1H),2.65(br,1H),2.56(d,J＝2.00Hz,1H),2.49(t,J＝7.13Hz,2H),2.42(td,J＝6.73Hz,J＝1.70Hz,2H),1.88(tt,J＝7.13Hz,J＝6.73Hz,1H)；13C NMRδ＝119.28,82.79,81.24,79.25,72.63,52.01,24.21,17.94,16.29.HRMS-ESI(m/z)计算值C9H9NONa[M+Na]+170.0576,实际值170.0583.
制备例16
Figure PCTCN2016081392-appb-000176
除以下特征外，化合物17-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成 等摩尔数的苯基丙炔醛
Figure PCTCN2016081392-appb-000177
(根据文献Org.Lett.2012,14,4906.合成)。
化合物17-1的产率：70％。(化合物17-1的产率为化合物17-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物17-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.43-7.45(m,2H),7.29-7.33(m,3H),5.20(t,J＝1.65Hz,1H),4.33(d,J＝1.65Hz,2H),4.26(d,J＝2.23Hz 2H),2.70(br,1H),2.46(t,J＝2.23Hz,1H)；13C NMRδ＝131.79,128.72,128.32,122.01,89.93,88.26,82.62,78.85,77.71,75.42,52.12,56.72,56.61；HRMS-ESI(m/z)计算值C15H12O2Na[M+Na]+247.0730,实际值247.0726.
制备例17
Figure PCTCN2016081392-appb-000178
除以下特征外，化合物18-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成等摩尔数的对甲苯基丙炔醛
Figure PCTCN2016081392-appb-000179
(根据文献Org.Lett.2012,14,4906.合成)。
化合物18-1的产率：62％。(化合物18-1的产率为化合物18-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物18-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.42-7.44(m,2H),7.26-7.30(m,2H),5.21(t,J＝1.66Hz,1H),4.30(d,J＝1.66Hz,2H),4.27(d,J＝2.24Hz 2H),2.66(br,1H),2.45(t,J＝2.24Hz,1H),2.35(s,3H)；13C NMRδ＝131.74,128.70,128.29,122.11,89.92,88.29,82.60,78.83,77.73,75.45,52.16,56.73,56.62,27.45；HRMS-ESI(m/z)计算值C16H14O2Na[M+Na]+261.0886,实际值261.0882.
制备例18
Figure PCTCN2016081392-appb-000180
除以下特征外，化合物19-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成等摩尔数的4-苯基-3-丁炔-2-酮
Figure PCTCN2016081392-appb-000181
(购自阿法埃莎(中国)化学有限公司，商品牌号为MFCD00008776)。
化合物19-1的产率：65％。(化合物19-1的产率为化合物19-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物19-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.44-7.46(m,2H),7.30-7.34(m,3H),4.34(s,2H),4.27(d,J＝2.22Hz 2H),2.59(br,1H),2.46(t,J＝2.22Hz,1H),1.87(s,3H)；13C NMRδ＝131.81,128.74,128.31,122.03,89.94,88.27,82.61,78.87,77.70,75.40,60.23,56.74,56.62,31.89；HRMS-ESI(m/z)计算值C16H14O2Na [M+Na]+261.0886,实际值261.0879.
制备例19
Figure PCTCN2016081392-appb-000182
除以下特征外，化合物20-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成等摩尔数的3-戊炔-2-酮
Figure PCTCN2016081392-appb-000183
(根据文献J.Am.Chem.Soc.2008,130,14713.合成)。
化合物20-1的产率：60％。(化合物20-1的产率为化合物20-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物20-1的核磁和高分辨质谱数据如下：
1H NMRδ＝4.35(s,2H),4.29(d,J＝2.30Hz 2H),2.85(br,1H),2.46(t,J＝2.30Hz,1H),1.85(s,3H),1.92(s,3H)；13C NMRδ＝86.64,85.27,82.01,78.57,77.50,75.20,59.73,56.62,56.50,31.59,5.4；HRMS-ESI(m/z)计算值C11H12O2Na[M+Na]+199.0730,实际值199.0727.
制备例20
Figure PCTCN2016081392-appb-000184
除以下特征外，化合物21-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成等摩尔数的1-苯基-2-丁炔-1-酮
Figure PCTCN2016081392-appb-000185
(根据文献Angew.Chem.,Int.Ed.2011,50,7183.合成)。
化合物21-1的产率：60％。(化合物21-1的产率为化合物21-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物21-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.35-7.31(m,2H),7.11-7.15(m,3H),4.36(s,2H),4.29(d,J＝2.28Hz 2H),2.85(br,1H),2.48(t,J＝2.28Hz,1H),1.93(s,3H)；13C NMRδ＝131.20,129.34,127.11,121.72,86.82,85.05,82.11,78.93,77.81,75.52,65.71,56.24,56.12,8.29；HRMS-ESI(m/z)计算值C16H14O2Na[M+Na]+261.0886,实际值261.0878.
制备例21
Figure PCTCN2016081392-appb-000186
除以下特征外，化合物22-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成 等摩尔数的4-苯基-2-丁炔-1-醛
Figure PCTCN2016081392-appb-000187
(根据文献Angew.Chem.,Int.Ed.2014,53,4154.合成)。
化合物22-1的产率：68％。(化合物22-1的产率为化合物22-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物22-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.24-7.26(m,2H),7.13-7.22(m,3H),5.14(br,1H),2.65(br,1H),4.30(d,J＝1.57Hz,2H),4.25(d,J＝2.27Hz,2H),2.59(d,J＝2.25Hz,1H),3.25(d,J＝1.60Hz,2H)；13C NMRδ＝83.85,80.75,80.55,80.13,78.82,75.47,56.85,56.746,52.13；HRMS-ESI(m/z)计算值C16H14O2Na[M+Na]+261.0886,实际值261.0878.
制备例22
Figure PCTCN2016081392-appb-000188
除以下特征外，化合物23-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成等摩尔数的环己基丙炔醛
Figure PCTCN2016081392-appb-000189
(根据文献Angew.Chem.,Int.Ed.2014,53,4154.合成)。
化合物23-1的产率：71％。(化合物23-1的产率为化合物23-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物23-1的核磁和高分辨质谱数据如下：
1H NMRδ＝5.12(t,J＝1.53Hz,1H),2.75(br,1H),4.33(d,J＝1.53Hz,2H),4.27(d,J＝2.23Hz,2H),2.57(d,J＝2.23Hz,1H),1.75(m,4H),1.56(m,6H)；13C NMRδ＝87.53,83.85,80.83,80.63,78.87,75.67,56.86,56.75,52.76,33.52,28.94,25.63,25.19；HRMS-ESI(m/z)计算值C15H18O2Na[M+Na]+253.1199,实际值253.1198.
制备例23
Figure PCTCN2016081392-appb-000190
除以下特征外，化合物24-1的制备方法与化合物1的制备方法相同。
将制备例1步骤(1)中使用的1,6-庚二炔换成等摩尔数的炔丙醚，三甲基硅丙炔醛换成等摩尔数的苯基戊二炔醛
Figure PCTCN2016081392-appb-000191
(根据文献J.Org.Chem.2013,78,12018.合成)。
化合物24-1的产率：54％。(化合物24-1的产率为化合物24-1的摩尔量/炔丙醚的摩尔量×100％)。
化合物24-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.30-7.48(m,5H),5.17(t,J＝1.69Hz,1H),4.32(d,J＝1.69Hz,2H),4.28(d,J＝2.27Hz,2H),2.60(d,J＝2.27Hz,1H),2.53(br,1H)；13C NMRδ＝132.48,129.19,128.35,121.32,81.23,79.53,77.64,75.87,73.54,73.15,72.56,71.76,56.85,56.67,52.86；HRMS-ESI(m/z)计算值C17H12O2Na[M+Na]+271.0730,实际值271.0726.
制备例24
Figure PCTCN2016081392-appb-000192
除以下特征外，化合物25-1的制备方法与化合物3的制备方法相同。
将制备例2步骤(1)中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的2-炔丙基-2-(5-苯基-2,4-戊二炔基)丙二酸二甲酯(根据文献J.Am.Chem.Soc.2008,130,14713.合成)，三甲基硅丙炔醛换成等摩尔数的3-戊炔-2-酮
Figure PCTCN2016081392-appb-000193
(根据文献J.Am.Chem.Soc.2007,129,3826.合成)。
化合物25-1的产率：50％。(化合物25-1的产率为化合物25-1的摩尔量/2-炔丙基-2-(5-苯基-2,4-戊二炔基)丙二酸二甲酯的摩尔量×100％)。
化合物25-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.30-7.48(m,5H),3.77(s,6H),3.15(s,2H),3.09(s,2H),2.65(br,1H),1.75(s,3H),1.80(s,3H)；13C NMRδ＝168.87,132.55,129.16,128.35,121.42,80.90,79.31,77.69,75.87,73.43,72.24,56.66,53.35,51.92,31.58,24.20,23.31,10.67；HRMS-ESI(m/z)计算值C24H22O5Na[M+Na]+413.1359,实际值413.1358.
制备例25
Figure PCTCN2016081392-appb-000194
除以下特征外，化合物26-1的制备方法与化合物3的制备方法相同。
将制备例2中使用的2,2-二炔丙基丙二酸二甲酯换成等摩尔数的2-炔丙基-2-苯基炔丙基丙二酸二甲酯(根据文献J.Am.Chem.Soc.2000,122,11529.合成)。
化合物26-1的产率：81％。(化合物26-1的产率为化合物26-1的摩尔量/2-炔丙基-2-苯基炔丙基丙二酸二甲酯的摩尔量×100％)。
化合物26-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.34(dt,J＝7.56Hz,J＝5.13Hz,5H),5.12(d,J＝2.10Hz,1H),3.78(s,6H),3.23(s,2H),3.11(s,2H),3.04(d,J＝7.14Hz,1H),-0.11(s,9H)；13C NMRδ＝169.31,169.37,131.66,128.22,128.14,122.81,101.23,83.98,83.58,80.91,80.64,79.57,56.94,53.22,51.84,23.85,23.16,-0.36；HRMS-ESI(m/z)计算值C23H26SiNaO5[M+Na]+433.1442,实际值433.1441.
(2)除以下特征外，化合物27-1的制备方法与化合物4的制备方法相同。
将制备例2步骤(2)中使用的化合物3换成本制备例步骤(1)中获得的化合物26-1。
化合物27-1的产率：89％。(化合物27-1的产率为化合物27-1的摩尔量/化合物26-1的摩尔量×100％)。
化合物27-1的核磁和高分辨质谱数据如下：
1H NMRδ＝7.38(dt,J＝7.62Hz,J＝5.15Hz,5H),5.10(d,J＝5.27Hz,1H),3.80(s,6H),3.20(s,2H),3.10(s,2H),3.07(d,J＝7.11Hz,1H)；13C NMRδ＝169.33,169.31,131.68,128.25,128.17,122.86,83.97,83.57,80.99,80.69,79.58,72.50,56.97,53.28,51.83,23.81,23.13；HRMS-ESI(m/z)计算值C20H18NaO5[M+Na]+361.1046,实际值361.1044.
实施例1
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000195
上式中，[Ru]1为RuCl(PPh3)2，PPh3为三苯基膦，DCM为二氯甲烷，Me为甲基。
在氮气氛围下，在磁力搅拌下，往RuCl2(PPh3)3(1.46mmol)与PPh3(7.3mmol)的二氯甲烷(二氯甲烷的用量为20mL)溶液中逐滴加入制备例2制得的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH(2.19mmol)的二氯甲烷(二氯甲烷的用量为2mL)溶液，室温下反应1h，溶液颜色为红色。反应液用真空泵浓缩至5mL，然后用正己烷洗涤(洗涤三次，每次50mL)得1.23g红色固体状化合物I*-1，产率：70％(化合物I*-1的产率为化合物I*-1的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.06(s,1H,C7H),7.33(1H,C3H),6.99-7.81(46H,苯基及C3H),3.64(s,6H,COOCH3),2.96(t,J(H,H)＝3.63,C10H),2.76(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝29.59(d,J(P,P)＝5.89Hz,RuPPh3),6.38(t,J(P,P)＝5.89Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝356.95(br,C1),251.89(t,J(P,C)＝11.96,C7),190.23(dt,J(P,C)＝25.65Hz,J(P,C)＝4.90Hz,C4),180.98(d,J(P,C)＝1.97Hz,C5),171.77(s,COOCH3),164.57(t,J(P,C)＝4.24Hz,C6),154.99(dt,J(P,C)＝14.44Hz,J(P,C)＝3.07Hz,C3),128.18-135.76(其它芳香碳),122.86(dt,J(P,C)＝92.99Hz,J(P,C)＝4.02Hz,C2),119.57(芳香碳),64.14(s,C9),53.63(s,COOCH3),39.06(s,C8),37.35(s,C10)；HRMS(ESI):m/z理论值[C68H57ClO4P3Ru]+,1167.2212；实测值1167.2215.
实施例2
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000196
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物I*-3的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例3制得的HC≡CCH(OH)C≡CCH2OCH2C≡CH。
获得红色固体状化合物I*-3，产率：68％(化合物I*-3的产率为化合物I*-3的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.17(s,1H,C7H),7.35(s,1H,C3H),7.01-7.81(46H,苯基及C3H),4.36(s,2H,C8H),4.13(d,J(H,H)＝5.82,C9H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝28.48(d,J(P,P)＝5.83Hz,RuPPh3),6.83(t,J(P,P)＝5.83Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝355.49(br,C1),246.21(t,J(P,C)＝12.93,C7),187.72(dt,J(P,C)＝25.69Hz,J(P,C)＝4.87Hz,C4),181.02(d,J(P,C)＝2.03Hz,C5),166.31(t,J(P,C)＝3.95Hz,C6),156.77(d,J(P,C)＝16.65Hz,C3),128.38-135.99(其它芳香碳),124.04(dt,J(P,C)＝93.58Hz,J(P,C)＝3.80Hz,C2),119.56(芳香碳),71.28(s,C9),69.01(s,C8)；HRMS(ESI):m/z理论值[C63H51ClOP3Ru]+,1053.1879；实测值1053.1894.
实施例3
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000197
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物I*-8的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例4制得的HC≡CCPh(OH)C≡CCH2C(COOMe)2CH2C≡CH。
获得红色固体状化合物I*-8，产率：70％(化合物I*-8的产率为化合物I*-8的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.07(s,1H,C7H),6.98-7.82(51H,苯基及C3H),3.65(s,6H,COOCH3),2.97(t,J(H,H)＝3.64,C10H),2.77(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝29.60(d,J(P,P)＝5.90Hz,RuPPh3),6.37(t,J(P,P)＝5.88Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝356.96(br,C1),251.88(t,J(P,C)＝11.97,C7),190.22(dt,J(P,C)＝25.66Hz,J(P,C)＝4.98Hz,C4),180.99(d,J(P,C)＝1.96Hz,C5),171.78(s,COOCH3),164.56(t,J(P,C)＝4.23Hz,C6),154.98(dt,J(P,C)＝14.45Hz,J(P,C)＝3.06Hz,C3),128.19-135.75(其它芳香碳),122.87(dt,J(P,C)＝92.98Hz,J(P,C)＝4.03Hz,C2),119.58(芳香碳),64.15(s,C9),53.64(s,COOCH3),39.07(s,C8),37.34(s,C10)；HRMS(ESI):m/z理论值[C74H61ClO4P3Ru]+,1243.2509；实测值1243.2505.
实施例4
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000198
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物I*-11的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例5制得的HC≡CCH(OH)C≡CCH2OCH2C≡CMe。
获得红色固体状化合物I*-11，产率：71％(化合物I*-11的产率为化合物I*-11的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝7.34(s,1H,C3H),7.00-7.82(46H,苯基及C3H),4.35(s,2H,C8H),4.14(d,J(H,H)＝5.81,C9H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝28.47(d,J(P,P)＝5.83Hz,RuPPh3),6.82(t,J(P,P)＝5.82Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝355.48(br,C1),246.20(t,J(P,C)＝12.94,C7),187.73(dt,J(P,C)＝25.68Hz,J(P,C)＝4.86Hz,C4),181.00(d,J(P,C)＝2.04Hz,C5),166.30(t,J(P,C)＝3.96Hz,C6),156.76(d,J(P,C)＝16.64Hz,C3),128.37-135.98(其它芳香碳),124.03(dt,J(P,C)＝93.57Hz,J(P,C)＝3.81Hz,C2),119.55(芳香碳),71.27(s,C9),69.00(s,C8),23.22(s,CH3)；HRMS(ESI):m/z理论值[C63H51ClOP3Ru]+,1053.1879；实测值1053.1894.
实施例5
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000199
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物I*-5的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中的反应温度由室温升高到60℃，时间由1小时延长到1天。
获得红色固体状化合物I*-5，产率：62％(化合物I*-5的产率为化合物I*-5的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.67(ddd,J(PH)＝18.35Hz,J(PH)＝4.98Hz,J(HH)＝2.64Hz,1H,C1H),8.26(dd,表现为t,J(PH)＝2.64Hz,J(HH)＝2.63Hz,1H,C3H),6.86-7.78(m,45H,Ph),3.62(s,6H,COOCH3),2.94(t,J(H,H)＝3.61,C10H),2.74(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝32.54(d,J(P,P)＝4.92Hz,RuPPh3),12.17(t,J(P,P)＝4.92Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝345.73(br,C7),249.97(br,J(P,C)＝12.92,C1),193.76(s,C5),187.72(dt,J(P,C)＝22.28Hz,J(P,C)＝5.84Hz,C4),157.57(s,C6),143.62(d,J(P,C)＝22.32Hz,C3),127.06-134.35(m,Ph),126.22(d,J(P,C)＝68.71Hz,C2),117.72(d,J(P,C)＝88.43Hz,Ph),64.12(s, C9),53.64(s,COOCH3),39.05(s,C8),37.34(s,C10)；HRMS(ESI):m/z理论值[C68H57ClO4P3Ru]+,1167.2212；实测值1167.2216.
实施例6
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000200
上式中，[Ir]2为IrCl(PPh3)2，[Ir]1为Ir(PPh3)2。
在氮气氛围下，在磁力搅拌下，将实施例9制得的化合物II*-10(300mg，0.25mmol)与Cs2CO3(414mg，1.25mmol)的二氯甲烷(二氯甲烷的用量为15mL)溶液室温下反应1h，溶液颜色为红色。将反应液过滤后获得的滤液用真空泵浓缩至2mL，然后用正己烷洗涤(洗涤三次，每次50mL)得红色固体化合物I*-7，产率：85％(化合物I*-7的产率为化合物I*-7的摩尔量/化合物II-10的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.31(s,1H,C7H),7.60(s,1H,C3H),7.01-7.78(m,45H,Ph),2.43(m,2H,C10H),2.02(tt,表现为五重峰,J(HH)＝7.26Hz,2H,C9H),1.78ppm(t,J(HH)＝7.28Hz,2H,C8H).31P{1H}NMR(121.5MHz,CD2Cl2):δ＝11.21(t,J(PP)＝5.73Hz,CPPh3),-3.24ppm(d,J(PP)＝5.73Hz,IrPPh3).13C{1H}NMR(75.5MHz,CD2Cl2):δ＝341.56(dt,apparent q,J(PC)＝13.34Hz,J(PC)＝13.34Hz,C1),226.58(t,J(PC)＝10.58Hz,C7),180.45(s,C5),176.50(t,J(PC)＝3.43Hz,C6),173.04(dt,J(PC)＝23.40Hz,J(PC)＝3.31Hz,C4),147.76(dt,J(PC)＝15.35Hz,J(PC)＝2.47Hz,C3),128.07-135.45(Ph),127.89(dt,J(PC)＝78.84Hz,J(PC)＝5.61Hz,C2),120.56(d,J(PC)＝70.83Hz,Ph),33.32(s,C8),28.57(s,C10),29.30ppm(s,C9).HRMS(ESI):m/z理论值[C63H54P3Ir]+,1096.3062；测量值,1096.3058.
实施例7
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000201
上式中，[Rh]2为RhCl(PPh3)2，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物I*-6的制备方法与实施例6中的化合物I*-7的制备方法相同：
将实施例6中使用的化合物II*-10换成等摩尔数的实施例11制得的化合物II*-2。
获得红色固体状化合物I*-6，产率：83％(化合物I*-6的产率为化合物I*-6的摩尔量/化合物II*-2的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.02(s,1H,C7H),7.68(s,1H,C3H),7.08-7.75(m,45H,Ph),2.47(m,2H,C10H),2.06(tt,表现为五重峰,J(HH)＝7.29Hz,2H,C9H),1.82ppm(t,J(HH)＝ 7.29Hz,2H,C8H).31P{1H}NMR(121.5MHz,CD2Cl2):δ＝35.63(dd,J(RhP)＝108.20Hz,J(PP)＝5.55Hz,RhPPh3),11.02(d,J(PP)＝5.55Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝347.32(dt,表现为四重峰,J(PC)＝13.02Hz,J(PC)＝13.02Hz,C1),226.10(t,J(PC)＝10.58Hz,C7),180.00(s,C5),176.30(t,J(PC)＝3.23Hz,C6),173.58(dt,J(PC)＝23.47Hz,J(PC)＝3.30Hz,C4),145.47(dt,J(PC)＝15.25Hz,J(PC)＝2.35Hz,C3),129.06-134.25(Ph),127.56(dt,J(PC)＝78.85Hz,J(PC)＝5.56Hz,C2),120.54(d,J(PC)＝70.88Hz,Ph),34.32(s,C8),26.57(s,C10),22.30ppm(s,C9).HRMS(ESI):m/z calcd for[C64H53P3Rh]+,1017.2410；found,1017.2406.
实施例8
本实施例用以说明式I*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000202
上式中，[Rh]2为RhCl(PPh3)2，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物I*-14的制备方法与实施例6中的化合物I*-7的制备方法相同：
将实施例6中使用的化合物II*-10换成等摩尔数的实施例12制得的化合物II*-13。
获得红色固体状化合物I*-14，产率：81％(化合物I*-14的产率为化合物I*-14的摩尔量/化合物II*-13的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.23(s,1H,C7H),7.85(s,1H,C3H),7.02-7.68(m,50H,Ph),2.52(m,2H,C10H),2.04(tt,表现为五重峰,J(HH)＝7.18Hz,2H,C9H),1.95ppm(t,J(HH)＝7.18Hz,2H,C8H).31P{1H}NMR(121.5MHz,CD2Cl2):δ＝35.72(dd,J(RhP)＝108.32Hz,J(PP)＝5.50Hz,RhPPh3),10.95(d,J(PP)＝5.50Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝348.24(dt,表现为四重峰,J(PC)＝13.22Hz,J(PC)＝13.22Hz,C1),225.21(t,J(PC)＝10.37Hz,C7),181.25(s,C5),175.36(t,J(PC)＝3.28Hz,C6),173.79(dt,J(PC)＝22.35Hz,J(PC)＝3.39Hz,C4),145.57(dt,J(PC)＝15.23Hz,J(PC)＝2.33Hz,C3),129.15-134.89(Ph),126.35(dt,J(PC)＝78.59Hz,J(PC)＝5.53Hz,C2),120.65(d,J(PC)＝71.22Hz,Ph),34.96(s,C8),29.65(s,C10),23.63ppm(s,C9).HRMS(ESI):m/z calcd for[C70H57P3Rh]+,1093.2723；found,1093.2718.
实施例9
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000203
上式中，[Ir]2为IrCl(PPh3)2，CDCl3为氘代氯仿。
除以下特征外，化合物II*-10的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例1制得的HC≡CCH(OH)C≡C(CH2)3C≡CH，将DCM换成CDCl3(氘代氯仿)，同时将RuCl2(PPh3)3换成IrHCl2(PPh3)3。
获得红色固体状化合物II*-10，产率：35％(化合物II*-10的产率为化合物II*-10的摩尔量/IrHCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CDCl3):δ＝14.34(s,1H,C7H),12.66(d,J(PH)＝20.03Hz,1H,C1H),8.67(t,J(PH)＝2.35Hz,1H,C3H),6.98-7.90(m,45H,Ph),2.56(m,2H,C10H),1.64(tt,表现为五重峰J(HH)＝7.44Hz,2H,C9H),1.15(t,J(HH)＝7.44Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝10.91(t,J(PP)＝5.97Hz,CPPh3),-5.77(d,J(PP)＝5.97Hz,IrPPh3)；13C{1H}NMR(150.9MHz,CDCl3):δ＝230.16(br,C7),215.13(br,C1),186.44(s,C5),184.96(s,C6),169.34(dt,J(PC)＝22.59Hz,J(PC)＝2.90Hz,C4),151.98(d,J(PC)＝24.44Hz,C3),137.51(dt,J(PC)＝62.94Hz,J(PC)＝3.21Hz,C2),119.36-135.16(Ph),31.75(s,C8),31.00(s,C10),28.75(s,C9)；HRMS(ESI):m/z理论值[C64H54ClP3Ir]+,1143.2748；实测值1143.2739.
实施例10
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000204
上式中，[Rh]2为RhCl(PPh3)2，HBF4·H2O为四氟硼酸水溶液。
在氮气氛围下，在磁力搅拌下，往RhCl(PPh3)3(1.46mmol)与PPh3(7.3mmol)的二氯甲烷(二氯甲烷的用量为40mL)溶液中逐滴加入制备例2制得的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH(2.19mmol)的二氯甲烷(二氯甲烷的用量为5mL)溶液，室温下反应1h，溶液颜色为红色。快速加入HBF4·H2O(0.33mL，2.68mmol)，溶液颜色立刻由黄色变为红色，室温下再反应10min，反应液用真空泵浓缩至5mL，接着用正己烷洗涤(洗涤三次，每次50mL)获得红色固体状化合物II*-1，产率：92％(化合物II*-1的产率为化合物II*-1的摩尔量/RhCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝12.83(s,1H,C7H),11.76(d,J(PH)＝21.49Hz,1H,C1H),6.89-7.82(45H,Ph),7.91(s,1H,C3H),3.64(s,6H,COOCH3),3.04(s,2H,C10H),2.33(s,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝26.82(d,J(RhP)＝105.77Hz,RhPPh3),9.72(s,CPPh3)；13C{1H}NMR(150.5MHz,CD2Cl2):δ＝265.29(br,C7),239.66(br,C1),188.77(s,C5),188.66(br,C4),172.54(s,C6),171.10(s,COOCH3),157.38(d,J(PC)＝25.91Hz,C3),134.14-135.39(Ph),131.86(dt,J(PC)＝55.99Hz,J(PC)＝4.31Hz,C2),128.40-131.03(Ph),119.19(d,J(PC)＝87.55Hz,Ph),63.73(s,C9),53.68(s,COOCH3),39.83(s,C8),38.60(s,C10)；HRMS(ESI):m/z理论值[C68H58ClO4P3Rh]+,1169.2286[M]+；实测值1169.2299.
其中，化合物HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH的制备方法参见实施例1。
实施例11
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000205
上式中，[Rh]2为RhCl(PPh3)2，HBF4·H2O为四氟硼酸水溶液。
除以下特征外，化合物II*-2的制备方法与实施例10中的化合物II*-1的制备方法相同：
将实施例10中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例1制得的HC≡CCH(OH)C≡C(CH2)3C≡CH。
获得红色固体状化合物II*-2，产率：89％(化合物II*-2的产率为化合物II*-1的摩尔量/RhCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝13.08(s,1H,C7H),11.50(d,J(PH)＝21.48Hz,1H,C1H),8.07(s,1H,C3H),6.88-7.80(45H,Ph),2.20(m,2H,C10H),1.47(tt,J(HH)＝7.31Hz,J(HH)＝7.31Hz,2H,C9H),1.36ppm(t,J(HH)＝7.31Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝28.70(dd,J(RhP)＝108.51Hz,J(PP)＝5.87Hz,RhPPh3),9.14ppm(d,J(PP)＝5.87Hz,CPPh3)；13C{1H}NMR(150.5MHz,CD2Cl2):δ＝261.20(br,C7),239.86(dt,J(RhC)＝35.44Hz,J(PC)＝10.37Hz,C1),1195.42(s,C5),187.62(ddt,J(RhC)＝29.21Hz,J(PC)＝25.20Hz,J(PC)＝4.83Hz,C4),178.70(s,C6),157.32(d,J(PC)＝26.58Hz,C3),130.20-134.95(Ph),129.41(ddt,J(PC)＝58.75Hz,J(RhC)＝8.59Hz,J(PC)＝4.48Hz,C2),127.80-128.45(Ph),119.00(d,J(PC)＝87.27Hz,Ph),32.50(s,C8),31.46(s,C9),28.42ppm(s,C10)；HRMS(ESI):m/z理论值[C64H55ClP3Rh]+,1053.2176[M]+；实测值1053.2170.
实施例12
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000206
上式中，[Rh]2为RhCl(PPh3)2，HBF4·H2O为四氟硼酸水溶液。
除以下特征外，化合物II*-13的制备方法与实施例10中的化合物II*-1的制备方法相同：
将实施例10中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例8制得的HC≡CCPh(OH)C≡C(CH2)3C≡CH。
获得红色固体状化合物II*-13，产率：86％(化合物II*-13的产率为化合物II*-13的摩尔量/RhCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝11.66(d,J(PH)＝21.25Hz,1H,C1H),8.13(s,1H,C3H),6.78-7.89(50H,Ph),2.25(m,2H,C10H),1.53(tt,J(HH)＝7.28Hz,J(HH)＝7.28Hz,2H,C9H),1.35ppm(t,J(HH)＝7.28Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝28.59(dd,J(RhP)＝108.48Hz,J(PP)＝5.85Hz,RhPPh3),9.19ppm(d,J(PP)＝5.85Hz,CPPh3)；13C{1H}NMR(150.5 MHz,CD2Cl2):δ＝258.23(br,C7),237.85(dt,J(RhC)＝35.43Hz,J(PC)＝10.34Hz,C1),193.42(s,C5),185.63(ddt,J(RhC)＝29.11Hz,J(PC)＝25.51Hz,J(PC)＝4.63Hz,C4),175.63(s,C6),157.96(d,J(PC)＝26.75Hz,C3),129.65-134.55(Ph),128.65(ddt,J(PC)＝58.55Hz,J(RhC)＝8.74Hz,J(PC)＝4.63Hz,C2),127.85-128.43(Ph),118.30(d,J(PC)＝87.25Hz,Ph),32.45(s,C8),31.23(s,C9),28.21ppm(s,C10)；HRMS(ESI):m/z理论值[C70H58ClP3Rh]+,1129.2489[M]+；实测值1129.2485.
实施例13
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000207
上式中，[Ir]2为IrCl(PPh3)2，HBF4·H2O为四氟硼酸水溶液。
除以下特征外，化合物II*-11的制备方法与实施例10中的化合物II*-1的制备方法相同：
将实施例10中的RhCl(PPh3)3换成等摩尔数的IrCl(PPh3)3。
获得红色固体状化合物II*-11，产率：55％(化合物II*-11的产率为化合物II*-11的摩尔量/IrCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝13.97(s,1H,C7H),12.90(d,J(PH)＝20.22Hz,1H,C1H),8.40(dd,J(PH)＝2.34Hz,J(HH)＝2.34Hz,1H,C3H),6.90-7.79(45H,Ph),3.61(s,6H,COOCH3),3.32(t,J(HH)＝3.25Hz,2H,C10H),1.91ppm(s,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝11.05(s,CPPh3),-7.59ppm(s,IrPPh3)；13C{1H}NMR(150.5MHz,CD2Cl2):δ＝232.46(br,C7),213.38(br,C1),178.81(s,C5),178.48(s,C6),170.54(s,C6),171.10(s,COOCH3),169.21(d,J(PC)＝22.17Hz,C4),151.03(d,J(PC)＝23.94Hz,C3),139.09(dt,J(PC)＝62.35Hz,J(PC)＝3.44Hz,C2),127.16-134.29(Ph),118.90(d,J(PC)＝87.37Hz,Ph),63.22(s,C9),52.65(s,COOCH3),38.293(s,C8),37.29ppm(s,C10)；HRMS(ESI):m/z理论值[C68H58ClO4P3Ir]+,1259.2860[M]+；实测值1259.2864.
实施例14
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000208
上式中，[Ir]2为IrCl(PPh3)2，HBF4·H2O为四氟硼酸水溶液。
除以下特征外，化合物II*-21的制备方法与实施例10中的化合物II*-1的制备方法相同：
将实施例10中的RhCl(PPh3)3换成等摩尔数的IrCl(PPh3)3。将实施例10中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例9制得的HC≡CCH(OH)C≡C(CH2)5C≡CH。
获得红色固体状化合物II*-21，产率：53％(化合物II*-21的产率为化合物II*-21的摩尔量/IrCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝14.02(s,1H,C7H),12.95(d,J(PH)＝19.22Hz,1H,C1H),8.35(dd,J(PH)＝2.32Hz,J(HH)＝2.10Hz,1H,C3H),6.95-7.71(45H,Ph),2.25(m,2H,C12H),1.53(m,2H,C11H),1.43(m,2H,C10H),1.40(m,2H,C9H),1.35ppm(t,J(HH)＝7.26Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝11.15(s,CPPh3),-7.35ppm(s,IrPPh3)；13C{1H}NMR(150.5MHz,CD2Cl2):δ＝230.43(br,C7),212.25(br,C1),177.32(s,C5),176.23(s,C6),171.53(s,C6),171.12(s,COOCH3),169.42(d,J(PC)＝22.16Hz,C4),151.42(d,J(PC)＝23.97Hz,C3),136.16(dt,J(PC)＝72.37Hz,J(PC)＝3.45Hz,C2),126.32-133.98(Ph),117.62(d,J(PC)＝87.25Hz,Ph),33.50(s,C12),35.61(s,C8),32.16(s,C10),28.54(s,C11),27.52ppm(s,C9)；HRMS(ESI):m/z理论值[C66H58ClP3Ir]+,1171.3064[M]+；实测值1171.3058.
实施例15
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000209
上式中，[Ru]1为RuCl(PPh3)2，[Ru]2为RuCO(PPh3)2。
在CO氛围下，在磁力搅拌下，将实施例1制得的化合物I*-1(0.25mmol)与苯硫酚钠(0.75mmol)混合，加入二氯甲烷(20mL)，室温下反应10min，得红色悬浊液。将悬浊液用砂芯漏斗过滤后，将滤液用真空泵抽干，过中性氧化铝柱(二氯甲烷/甲醇＝40/1体积比)，旋干得264mg红色固体状化合物II*-6，产率：81％(化合物II*-6的产率为化合物II*-6的摩尔量/化合物II*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(500.2MHz,CD2Cl2):δ＝10.88(s,1H,C7H),7.84(d,J(P,H)＝5.45Hz,1H,C3H),5.99-7.69(50H,其它芳香氢),3.54(s,6H,COOCH3),2.57(s,C10H),2.11(s,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝36.84(s,RuPPh3),7.28(s,CPPh3)；13C{1H}NMR(125.8MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝249.56(br,C1),238.51(t,J(P,C)＝18.01,C7),203.96(t,J(P,C)＝15.06Hz,RuCO),197.79(dt,J(P,C)＝27.45Hz,J(P,C)＝7.71Hz,C4),180.95(s,C5),171.71(s,COOCH3),169.85(s,C6),161.86(d,J(P,C)＝24.53Hz,C3),122.00-138.99(其它芳香碳),121.97(d,J(P,C)＝58.68Hz,C2),64.08(s,C9),53.32(s,COOCH3),38.38(s,C10),37.62(s,C8)；HRMS(ESI):m/z理论值[C75H62O5P3RuS]+,1269.2569；实测值1269.6588.
实施例16
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000210
上式中，[Ru]1为RuCl(PPh3)2，[Ru]2为RuCO(PPh3)2。
除以下特征外，化合物II*-7的制备方法与实施例14中的化合物II*-6的制备方法相同：
将实施例14中的化合物I*-1换成等摩尔数的实施例3制得的化合物I*-8，将苯硫酚钠换成等摩尔数的甲硫醇钠。
获得红色固体状化合物II*-7，产率：85％(化合物II*-7的产率为化合物II*-7的摩尔量/化合物I*-8的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(500.2MHz,CD2Cl2):δ＝10.85(s,1H,C7H),7.81(d,J(PH)＝5.35Hz,1H,C3H),5.96-7.56(50H,Ph),3.52(s,6H,COOCH3),2.55(s,C10H),2.45(s,SCH3),2.10ppm(s,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝36.92(s,RuPPh3),7.35(s,CPPh3)；13C{1H}NMR(125.8MHz,CD2Cl2):δ＝244.32(br,C1),236.52(t,J(P,C)＝18.21,C7),203.85(t,J(P,C)＝15.11Hz,RuCO),195.32(dt,J(P,C)＝27.21Hz,J(P,C)＝7.65Hz,C4),178.65(s,C5),171.31(s,COOCH3),169.64(s,C6),160.63(d,J(P,C)＝24.32Hz,C3),122.11-138.34(Ph),121.63(d,J(P,C)＝58.59Hz,C2),64.95(s,C9),54.32(s,COOCH3),38.65(s,C10),37.52(s,C8),14.63(s,SCH3)；HRMS(ESI):m/z理论值[C76H64O5P3RuS]+,1283.2725；实测值1283.2720.
实施例17
本实施例用以说明式II*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000211
上式中，[Ru]1为RuCl(PPh3)2，[Ru]2为RuCO(PPh3)2，Bu4N+Cl-为四正丁基氯化铵。
在氮气氛围下，冰浴中，往实施例2制得的化合物I*-3(0.46mmol)的二氯甲烷(二氯甲烷的用量为30mL)溶液中逐滴加入二氯乙酸(0.69mmol)，反应20min后，用真空泵把反应液抽干，加入四正丁基氯化铵(0.72mmol)，再把反应瓶置换成CO气氛，加入二氯甲烷，室温下反应1h，反应液为红色，反应液用真空泵浓缩至5mL，接着用正己烷洗涤(洗涤三次，每次50mL)，再过中性氧化铝柱(二氯甲烷/甲醇＝40/1体积比)，旋干得385mg红色固体状化合物II*-9，产率：75％(化合物II*-9的产率为化合物II*-9的摩尔量/化合物II*-3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(500.2MHz,CD2Cl2):δ＝11.80(d,J(P,H)＝20.78Hz,1H,C1H),8.18(s,1H,C3H),6.81-7.80(45H,Ph),3.89(s,1H,C8H),3.75(s,C9H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝41.36(s,RuPPh3),10.29(s,CPPh3)；13C{1H}NMR(125.8MHz,CD2Cl2):δ＝250.82(br,C7),244.05(br,C1),203.46(t,J(P,C)＝13.44Hz,CO),198.60(dt,J(P,C)＝27.91Hz,J(P,C)＝7.29Hz,C4),180.72(s,C5),175.75(s,C6),151.20(d,J(P,C)＝25.55Hz,C3),128.38-135.58(Ph),128.41(d,J(P,C)＝77.20Hz, C2),120.70(d,J(P,C)＝87.40Hz,Ph),72.76(s,C9),69.95(s,C8)；HRMS(ESI):m/z理论值[C64H51O2ClP3Ru]+,1081.1828；实测值1081.1822.
实施例18
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000212
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物III*-1的制备方法与实施例1中化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CHC(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例10制得的HC≡CCH(OH)C≡CCH2OCH2CH＝C＝CH。
获得红色固体状化合物III*-1，产率：61％(化合物III*-1的产率为化合物III*-1的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.92(d,J(P,H)＝17.35,1H,C1H),7.74(s,1H,C3H),6.89-7.83(46H,芳香氢和C3H),3.72(s,6H,COOCH3),3.68(s,2H,C8H),3.08(s,C11H),2.39(s,C9H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝21.70(d,J(P,P)＝4.23Hz,RuPPh3),9.87(t,J(P,P)＝4.23Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝269.25(br,C1),250.37(t,J(P,C)＝4.80Hz,C7),202.22(dt,J(P,C)＝26.68Hz,J(P,C)＝5.74Hz,C4),194.25(s,C5),171.09(s,COOCH3),153.55(s,C6),149.87(d,J(P,C)＝23.14Hz,C3),129.82(dt,J(P,C)＝66.67Hz,J(P,C)＝3.68Hz,C2),127.64-135.44(Ph和C2),119.51(d,J(P,C)＝88.14Hz,Ph),65.37(s,C10),53.78(s,COOCH3),45.64(s,C8),39.10(s,C9),34.93(s,C11)；HRMS(ESI):m/z理论值[C68H57ClO4P3Ru]+1216.2047，实测值1216.2041.
实施例19
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000213
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物III*-20的制备方法与实施例1中化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CHC(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例11制得的HC≡CCH(OH)C≡CCH2OCH2CH＝C＝CPh。
获得棕色固体状化合物III*-20，产率：64％(化合物III*-20的产率为化合物III*-20的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.81(d,J(P,H)＝17.24,1H,C1H),7.63(s,1H,C3H),6.78-7.72(51H,芳香氢和C3H),3.61(s,6H,COOCH3),3.57(s,1H,C8H),3.19(s,C11H),2.50(s,C9H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝21.81(d,J(P,P)＝4.34Hz,RuPPh3),9.76ppm(t,J(P,P)＝4.34Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝269.14(br,C1),250.26(t,J(P,C)＝4.71Hz,C7),202.11(dt,J(P,C)＝26.57Hz,J(P,C)＝5.85Hz,C4),194.14(s,C5),171.44(s,COOCH3),153.22(s,C6),149.75(d,J(P,C)＝23.12Hz,C3),129.71(dt,J(P,C)＝66.56Hz,J(P,C)＝3.57Hz,C2),127.43-135.55(Ph和C2),119.40(d,J(P,C)＝88.03Hz,Ph),65.26(s,C10),53.67(s,COOCH3),45.53(s,C8),39.02(s,C9),34.75(s,C11)；HRMS(ESI):m/z理论值[C74H61ClO4P3Ru]+1243.2509，实测值1243.2508.
实施例20
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000214
上式中，[Ru]1为RuCl(PPh3)2。
在二氯乙酸(22μL，0.28mmol)存在的条件下，在氮气氛围下，冰浴中，往实施例1制得的化合物I*-1(553mg，0.46mmol)的二氯甲烷(二氯甲烷的用量为20mL)溶液中加入环己基异氰(571μL，4.6mmol)(购自安耐吉化学)，室温下反应1.5h，反应液由红色变为绿色，反应液用真空泵浓缩至5mL，再过硅胶柱(100-200目，二氯甲烷/甲醇＝20/1)，旋干得129mg绿色固体状化合物III*-6，产率：72％(化合物III*-6的产率为化合物III*-6的摩尔量/化合物I*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.01(d,J(P,H)＝17.02,1H,C1H),7.41(s,1H,C3H),6.56-7.50(46H,芳香氢和C3H),3.67(s,6H,COOCH3),3.55(s,1H,C8H),3.32(s,C11H),3.08(m,1H,Cy),2.74(s,C9H),2.15(m,4H,Cy),1.63(m,4H,Cy),1.50(m,2H,Cy)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝30.75(s,RuPPh3),8.59ppm(s,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝267.26(br,C1),251.35(t,J(P,C)＝4.61Hz,C7),203.46(dt,J(P,C)＝26.31Hz,J(P,C)＝5.63Hz,C4),193.16(s,C5),174.43(s,COOCH3),160.34(s,C8),156.12(s,C6),149.75(d,J(P,C)＝23.12Hz,C3),128.13(dt,J(P,C)＝66.65Hz,J(P,C)＝3.65Hz,C2),126.43-135.13(Ph和C2),119.64(d,J(P,C)＝88.21Hz,Ph),68.32(s,Cy),65.64(s,C10),53.32(s,COOCH3),39.74(s,C9),34.85(s,C11),25.89(s,Cy),25.36(s,Cy),24.21(s,Cy)；HRMS(ESI):m/z理论值[C75H68ClNO4P3Ru]+1276.3088，实测值1276.3085.
实施例21
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000215
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物III*-8的制备方法与实施例20中化合物III*-6的制备方法相同：
将实施例20中使用的环己基异氰换成等摩尔数的水。
获得红色固体状化合物III*-8，产率：90％(化合物III*-8的产率为化合物III*-8的摩尔量/化合物I*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(600.1MHz,CD2Cl2):δ＝12.45(ddd,J(P,H)＝13.01Hz,J(P,H)＝4.12Hz,J(P,H)＝3.74Hz,J(P,H)＝2.09Hz,1H,C1H),6.85(1H,C3H,determined by1H-13C HSQC and1H-13C HMBC),6.84-7.81(46H,Ph and C3H mentioned above),3.67(s,6H,COOCH3),2.81(s,C8H),2.48ppm(s,C10H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝24.42(s,RuPPh3),8.60ppm(s,CPPh3)；13C{1H}NMR(150.9MHz,CD2Cl2):δ＝244.24(br,C7),230.85(t,J(P,C)＝6.38Hz,C1),193.06(dt,J(P,C)＝24.67Hz,J(P,C)＝6.59Hz,C4),192.80(s,C5),170.44(s,COOCH3),138.22(dd,J(P,C)＝18.73Hz,J(P,C)＝7.25Hz,C3),134.08-135.64(Ph),134.01(s,C6),128.54-130.98(Ph),120.86(d,J(P,C)＝82.02Hz,C2),119.27(d,J(P,C)＝89.95Hz,Ph),65.30(s,C9),54.00(s,COOCH3),37.16(t,J(P,C)＝20.17Hz,C10),31.54ppm(t,J(P,C)＝18.48Hz,C8)；HRMS(ESI):m/z理论值[C68H57ClO5P3Ru]+1183.2145，实测值1183.2141.
实施例22
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000216
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物III*-9的制备方法与实施例20中化合物III*-6的制备方法相同：
将实施例20中使用的环己基异氰换成等摩尔数的S8(购自安耐吉化学)。
获得红色固体状化合物III*-9，产率：90％(化合物III*-9的产率为化合物III*-9的摩尔量/化合物I*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(600.1MHz,CD2Cl2):δ＝12.44(ddd,J(P,H)＝13.56Hz,J(PH)＝4.36Hz,J(P,H)＝3.63Hz,J(P,H)＝2.22Hz,1H,C1H),6.85(s,1H,C3H),6.73-7.92(46H,Ph和C3H),3.78(s,6H,COOCH3),2.92(s,C8H),2.59ppm(s,C10H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝24.31(s,RuPPh3),8.49ppm(s,CPPh3)；13C{1H}NMR(150.9MHz,CD2Cl2):δ＝243.13(br,C7),231.96(t,J(P,C)＝6.27Hz,C1),193.17(dt,J(P,C)＝24.56Hz,J(P,C)＝6.48Hz,C4),192.69(s,C5),170.33(s,COOCH3),138.33(dd,J(P,C)＝18.62Hz,J(P,C)＝7.14Hz,C3),134.19-135.75(Ph),134.12(s,C6), 128.65-130.87(Ph),120.97(d,J(P,C)＝82.91Hz,C2),119.15(d,J(P,C)＝89.84Hz,Ph),65.19(s,C9),54.23(s,COOCH3),37.56(t,J(P,C)＝20.17Hz,C10),31.66ppm(t,J(P,C)＝18.59Hz,C8)；HRMS(ESI):m/z理论值[C68H57ClSO4P3Ru]+1199.1917，实测值1199.1916.
实施例23
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000217
上式中，[Ir]1为Ir(PPh3)2。
除以下特征外，化合物III*-10的制备方法与实施例10中化合物II*-1的制备方法相同：
将实施例10中的RhCl(PPh3)3换成等摩尔数的IrCl(PPh3)3。将实施例10中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例6制得的HC≡CCH(OH)C≡CCH2OCH2C＝C＝CH。
获得棕色固体状化合物III*-10，产率：41％(化合物III*-10的产率为化合物III*-10的摩尔量/IrCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(500.2MHz,CD2Cl2):δ＝14.23(d,J(PH)＝17.39Hz,1H,C1H),8.43(s,1H,C3H),6.90-7.92(m,45H,Ph),4.34(s,2H,C9H),3.43(s,2H,C10H),3.25ppm(s,2H,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝11.92(d,J(PP)＝4.95Hz,CPPh3),-13.39ppm(d,J(PP)＝4.96Hz,IrPPh3)；13C{1H}NMR(125.8MHz,CD2Cl2):δ＝239.39(br,C1),226.38(t,J(PC)＝4.59Hz,C7),183.68(s,C5),176.22(d,J(PC)＝25.42Hz,C4),163.34(s,C6),145.63(d,J(PC)＝21.85Hz,C3),134.88(dt,J(PC)＝70.95Hz,J(PC)＝3.96Hz,C2),118.68-134.39(Ph),69.96(s,C10),65.63(s,C9),23.30ppm(s,C8).HRMS(ESI):m/z理论值[C64H53OP3Ir]+1123.2933，实测值1123.2930.
实施例24
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000218
上式中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物III*-11的制备方法与实施例23中化合物III*-10的制备方法相同：
将实施例23中使用的IrCl(PPh3)3换成等摩尔数的RhCl(PPh3)3。
获得棕色固体状化合物III*-11，产率：75％(化合物III*-11的产率为化合物III*-11的摩尔量/IrCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(500.2MHz,CD2Cl2):δ＝13.44(d,J(PH)＝18.36Hz,1H,C1H),8.10(s,1H,C3H),6.79-7.83(m,45H,Ph),4.36(s,2H,C9H),3.76(s,2H,C10H),2.98ppm(s,2H,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝30.65(d,J(PP)＝108.36Hz,RhPPh3),10.32ppm(CPPh3)；13C{1H}NMR (125.8MHz,CD2Cl2):δ＝239.65(br,C1),229.34(t,J(PC)＝4.63Hz,C7),184.96(s,C5),173.21(d,J(PC)＝25.62Hz,C4),164.65(s,C6),145.94(d,J(PC)＝21.87Hz,C3),133.21(dt,J(PC)＝70.79Hz,J(PC)＝3.12Hz,C2),118.32-134.23(Ph),68.41(s,C10),64.14(s,C9),23.49ppm(s,C8).HRMS(ESI):m/z理论值[C64H53OP3Rh]+1033.2359，实测值1033.2358.
实施例25
本实施例用以说明式III*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000219
上式中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物III*-14的制备方法与实施例20中化合物III*-6的制备方法相同：
将实施例20中使用的环己基异氰换成等摩尔数的硒粉(购自安耐吉化学)；将式I*-1所示的化合物换成实施例7制得的式I*-6所示的化合物。
获得红色固体状化合物III*-14，产率：90％(化合物III*-14的产率为化合物III*-14的摩尔量/化合物I*-6的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(400.1MHz,CDCl3):δ＝13.6(d,J(PH)＝14.2Hz,1H,C1H),8.3(s,1H,C3H),7.8–6.8ppm(m,45H,Ph),2.57(m,2H,C10H),1.65(tt,J(HH)＝7.44Hz,2H,C9H),1.16(t,J(HH)＝7.44Hz,2H,C8H).31P-NMR(162.0MHz,CDCl3):δ＝12.2(s,CPPh3),–8.5ppm(s,OsPPh3).13C-NMR(100.6MHz,CDCl3):δ＝252.8(t,J(PC)＝6.1Hz,C7),241.7(br,C1),183.2(dt,J(PC)＝21.7Hz,J(PC)＝4.4Hz,C4),166.3(s,C5),153.7(d,J(PC)＝20.1Hz,C3),149.4(s,C6),128.7(d,J(PC)＝81.8Hz,C2),135.5–117.7ppm(m,Ph和C2),31.77(s,C8),31.22(s,C10),28.76(s,C9).HRMS(ESI):m/z理论值[C64H53SeP3Rh]+1097.1575，实测值1097.1573.
实施例26
本实施例用以说明式IV*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000220
上式中，[Ru]1为RuCl(PPh3)2。
在二氯乙酸(22μL，0.28mmol)存在条件下，在氮气氛围下，冰浴中，往实施例2制得的化合物I*-3(500mg，0.46mmol)的二氯甲烷(二氯甲烷的用量为10mL)溶液中逐滴加入乙氧基乙炔(178μL质量分数为50％的正己烷溶液，含乙氧基乙炔0.90mmol)，室温下反应1.5h，反应液由红色变为绿色，反应液用真空泵浓缩至5mL，再过硅胶柱(100-200目，二氯甲烷/甲醇＝20/1体积比)，旋干得129mg绿色固体状化合物IV*-1，产率：62％(化合物IV-1的产率为化合物IV-1的摩尔量/化合物I*-3的摩尔量×100％)。
所获得的金属桥位稠环化合物IV*-1的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.40(dd,J(P,H)＝18.71Hz,J(P,H)＝4.23Hz 1H,C1H),6.88-7.77(45H,Ph),6.16(br,1H,C3H),5.85(t,J(P,H)＝2.11Hz,1H,C8H),3.68(q,J(H,H)＝7.11Hz,OCH2CH3),3.52(s,C10H),3.43(s,C11H),1.23(t,J(H,H)＝7.11Hz,OCH2CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝19.84(d,J(P,P)＝2.83Hz,RuPPh3),6.45(t,J(P,P)＝2.83Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝253.15(br,C1),212.11(br,C9),204.92(t,J(P,C)＝8.92Hz,C7),191.02(dt,J(P,C)＝28.00Hz,J(P,C)＝9.16Hz,C4),188.04(s,C5),151.34(s,C6),147.14(d,J(P,C)＝24.94Hz,C3),126.77-133.90(Ph),125.87(t,J(P,C)＝3.73Hz,C8),121.36(d,J(P,C)＝71.91Hz,C2),118.69(d,J(P,C)＝88.44Hz,Ph),68.74(s,C11),68.23(s,OCH2CH3),65.11(s,C10),12.96(s,OCH2CH3)；HRMS(ESI):m/z理论值[C67H57ClO2P3Ru]+,1123.2298；实测值1123.2327.
实施例27
本实施例用以说明式IV*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000221
上式中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物IV*-5的制备方法与实施例26中化合物IV*-1的制备方法相同：
将实施例26中使用的乙氧基乙炔换成等摩尔数的
Figure PCTCN2016081392-appb-000222
(购自安耐吉化学)。
获得绿色固体状化合物IV*-5，产率：60％(化合物IV*-5的产率为化合物IV*-5的摩尔量/化合物I*-6的摩尔量×100％)。
所获得的金属桥位稠环化合物IV*-5的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.35(dd,J(P,H)＝18.56Hz,J(P,H)＝4.18Hz 1H,C1H),6.83-7.72(50H,Ph),6.11(br,1H,C3H),2.5(s,COCH3),3.52(s,C10H),3.43(s,C11H),；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝19.79(d,J(P,P)＝2.78Hz,RuPPh3),6.40(t,J(P,P)＝2.88Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝254.10(br,C1),213.06(br,C9),203.87(t,J(P,C)＝8.87Hz,C7),190.07(dt,J(P,C)＝28.15Hz,J(P,C)＝9.11Hz,C4),183.55(s,COCH3),181.09(s,C5),150.29(s,C6),146.09(d,J(P,C)＝24.89Hz,C3),126.72-133.85(Ph),125.82(t,J(P,C)＝3.68Hz,C8),121.31(d,J(P,C)＝70.86Hz,C2),118.64(d,J(P,C)＝88.39Hz,Ph),70.23(s,C11),68.06(s,C10)；31.64(s,COCH3)；HRMS(ESI):m/z理论值[C73H61ClO2P3Ru]+,1199.2611；实测值1199.2604.
实施例28
本实施例用以说明式IV*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000223
上式中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物IV*-8的制备方法与实施例26中化合物IV*-1的制备方法相同：
将实施例26中使用的化合物I*-3换成等摩尔数的实施例7制得的化合物I*-6。
获得绿色固体状化合物IV*-8，产率：60％(化合物IV*-8的产率为化合物IV*-8的摩尔量/化合物I*-6的摩尔量×100％)。
所获得的金属桥位稠环化合物IV*-8的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.17(dd,J(P,H)＝19.40Hz,J(P,H)＝3.73Hz 1H,C1H),7.88(s,1H,C3H),6.88-7.76(45H,Ph),3.45(q,J(H,H)＝7.24Hz,OCH2CH3),2.45(m,2H,C12H),2.05(tt,表现为五重峰,J(HH)＝7.28Hz,2H,C11H),1.81ppm(t,J(HH)＝7.28Hz,2H,C10H),1.12(t,J(H,H)＝7.24Hz,OCH2CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝23.59(d,J(RhP)＝103.22Hz,RhPPh3),7.93(s,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2):δ＝252.27(br,C1),214.80(br,C9),207.46(t,J(P,C)＝8.31Hz,C7),196.20(dt,J(P,C)＝28.05Hz,J(P,C)＝9.02Hz,C4),188.28(s,C5),171.21(s,COOCH3),151.68(s,C6),146.91(d,J(P,C)＝24.85Hz,C3),127.83-135.10(Ph),127.10(t,J(P,C)＝3.68Hz,C8),122.86(d,J(P,C)＝70.71Hz,C2),120.11(d,J(P,C)＝87.91Hz,Ph),69.33(s,OCH2CH3),34.21(s,C10),26.74(s,C12),22.21ppm(s,C11),13.88(s,OCH2CH3).
实施例29
本实施例用以说明式IV*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000224
上式中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物IV*-12的制备方法与实施例26中化合物IV*-1的制备方法相同：
将实施例26中使用的化合物I*-3换成等摩尔数的实施例6制得的化合物I*-7，将乙氧基乙炔换成等摩尔数的
Figure PCTCN2016081392-appb-000225
获得绿色固体状化合物IV*-12，产率：59％(化合物IV*-12的产率为化合物IV*-12的摩尔量/化合物I*-7的摩尔量×100％)。
所获得的金属桥位稠环化合物IV*-12的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.76(dd,J(P,H)＝18.32Hz,J(P,H)＝2.53Hz 1H,C1H),6.86-7.81(50H,Ph),6.53(s,1H,C3H),3.54(q,J(H,H)＝7.08Hz,OCH2CH3),2.52(m,2H,C12H),2.11(tt,表现为五重峰,J(HH)＝7.08Hz,2H,C11H),1.79ppm(t,J(HH)＝7.28Hz,2H,C10H),1.23(t,J(H,H)＝7.24Hz,OCH2CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝11.32(s,CPPh3),-7.93(s,IrPPh3).
实施例30
本实施例用以说明式V*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000226
上式中，[Ru]1为RuCl(PPh3)2，[Ru]3为Ru(PPh3)2。
氮气氛围下，往实施例18制得的化合物III*-1(300mg，0.25mmol)的二氯甲烷(二氯甲烷的用量为15mL)溶液中，加入三氟甲磺酸银(128mg，0.50mmol)，搅拌5min后加入丁炔酮(117μL，1.5mmol)，室温下反应30min后得绿色溶液，过滤、浓缩至2mL，然后加入30mL乙醚或正己烷作为沉淀剂，将获得的沉淀物经过滤、洗涤、柱色谱分离(洗脱剂为：二氯甲烷/丙酮＝8/1体积比)、旋干得187mg化合物V*-1，产率：55％(化合物V*-1的产率为化合物V*-1的摩尔量/化合物III*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物V*-1的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.45(d,J(P,H)＝21.21,1H,C1H),7.65(s,1H,C9H),6.90-7.81(46H,Ph和C9H),6.39(d,J(P,H)＝4.44,1H,C3H),5.91(s,1H,C8H),3.81(s,6H,COOCH3),2.97(s,4H,C13H and C15H),1.28(s,3H,C12H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝31.04(s,RuPPh3),9.28(s,CPPh3)；13C{1H}NMR(150.9MHz,CDCl3、):δ＝234.44(br,C1),224.27(t,J(P,C)＝8.61Hz,C7),195.35(s,C10),191.30(dt,J(P,C)＝30.23Hz,J(P,C)＝6.83Hz,C4),173.47(t,J(P,C)＝6.61Hz,C11),172.13(s,COOCH3),163.57(s,C5),159.08(s,C6),152.58(s,C9),131.00(s,C8),129.10(d,J(P,C)＝26.04Hz,C3),127.03-134.36(Ph和C8),121.94(d,J(P,C)＝62.97Hz,C2),120.51(d,J(P,C)＝87.61Hz,Ph),121.10(q,J(F,C)＝321.51Hz,CF3SO3)64.10(s,C14),53.03(s,COOCH3),37.00(s,C13),35.81(s,C15),25.34(s,C12)；HRMS(ESI):m/z理论值[C73H62O5P3Ru]+1213.2848，实测值1213.2857.
实施例31
本实施例用以说明式V*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000227
上式中，[Ru]1为RuCl(PPh3)2，[Ru]3为Ru(PPh3)2。
除以下特征外，化合物V*-3的制备方法与实施例30中的化合物V*-1的制备方法相同：
将实施例30中使用的丁炔酮换成等摩尔数的丁炔二酸二甲酯。
获得红色固体状化合物V*-3，产率：65％(化合物V*-3的产率为化合物V*-3的摩尔量/化合物III*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物V*-3的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.41(d,J(P,H)＝19.99,1H,C1H),6.90-7.85(45H,Ph),(d,J(P,H)＝3.50,1H,C3H),5.97(s,1H,C8H),3.82(s,6H,COOCH3),3.73(s,3H,C12H),3.43(s,C14H),2.96(s,2H,C17H),2.93(s,2H,C15H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝29.45(s,RuPPh3),9.47(s,CPPh3)；13C{1H}NMR(150.9MHz,CDCl3):δ＝228.93(br,C1),207.05(t,J(P,C)7.40Hz,C7),190.99(dt,J(P,C)＝30.72Hz,J(P,C)＝7.08Hz,C4),,175.10(t,J(P,C)＝7.05Hz,C10),172.16(s,COOCH3),168.08(s,C13),161.48(s,C11),160.92(s,C5),158.64(s,C6),152.53(s,C9),130.39(s,C8),127.10-134.54(Ph和C8),126.94(d,J(P,C)＝26.80Hz,C3),123.28(d,J(P,C)＝62.95Hz,C2),120.29(d,J(P,C)＝87.97Hz,Ph),121.14(q,J(F,C)＝321.21Hz,CF3SO3),64.08(s,C16), 52.99(s,COOCH3),51.55(s,C12),51.39(s,C14),36.85(s,C17),35.81(s,C15).HRMS(ESI):m/z理论值[C75H64O8P3Ru]+1287.2852,实测值1287.2857.
实施例32
本实施例用以说明式V*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000228
上式中，[Rh]1为Rh(PPh3)2，[Rh]3为RhClPPh3。
在氮气氛下，往实施例24制得的化合物III*-11(300mg，0.23mmol)和氯化钠(133mg，2.30mmol)的二氯甲烷(二氯甲烷的用量为15mL)溶液中，加入苯基丙炔酸甲酯(117μL，1.5mmol)，室温下反应1h后得绿色溶液，过滤、浓缩至2mL，然后加入30mL乙醚或正己烷作为沉淀剂，将获得的沉淀物经过滤、洗涤、柱色谱分离(洗脱剂为：二氯甲烷/丙酮＝8/1体积比)、旋干得化合物V*-22，产率：73％(化合物V*-22的产率为化合物V*-22的摩尔量/化合物III*-11的摩尔量×100％)。
所获得的金属桥位稠环化合物V*-22的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.46(d,J(P,H)＝19.87Hz,1H,C1H),6.96-7.79(35H,Ph),6.85(s,C3H),5.92(s,1H,C8H),4.34(s,2H,C13H),4.11(s,2H,C14H),3.78(s,3H,C12H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝32.12(d,J(Rh,P)＝105.32Hz,RhPPh3),7.21ppm(s,CPPh3).
实施例33
本实施例用以说明式V*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000229
上式中，[Ir]1为Ir(PPh3)2，[Ir]3为IrClPPh3。
除以下特征外，化合物V*-11的制备方法与实施例32中化合物V*-22的制备方法相同：
将实施例32中使用的化合物III*-11换成等摩尔数的实施例23制得的化合物III*-10，将苯基丙炔酸甲酯换成等摩尔数的丙炔酸甲酯。
获得绿色固体状化合物V*-11，产率：73％(化合物V*-11的产率为化合物V*-11的摩尔量/IrCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物V*-11的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.40(d,J(P,H)＝19.51,1H,C1H),7.57(s,1H,C9H),6.93-7.82(46H,Ph和C9H),6.15(s,1H,C3H),5.73(s,1H,C8H),4.12(s,2H,C13H),4.05(s,2H,C14H),3.44(s,3H,C12H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝15.63(s,CPPh3),-2.31(s,IrPPh3).
实施例34
本实施例用以说明式V*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000230
上式中，[Ru]1为Ru(PPh3)2，[Ru]3为Ru ClPPh3。
除以下特征外，化合物V*-7的制备方法与实施例32中化合物V*-22的制备方法相同：
将实施例32中使用的化合物III*-11换成等摩尔数的实施例18制得的化合物III*-1，将苯基丙炔酸甲酯换成等摩尔数的
Figure PCTCN2016081392-appb-000231
获得绿色固体状化合物V*-7，产率：69％(化合物V*-7的产率为化合物V*-7的摩尔量/化合物III*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物V*-7的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.91(d,J(P,H)＝19.84,1H,C1H),7.31(s,1H,C9H),6.91-7.81(55H,Ph和C9H),6.48(s,1H,C3H),5.53(s,1H,C8H),3.74(s,6H,COOCH3),2.65(s,4H,C12H和C13H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝28.35(s,IrPPh3),8.76(s,CPPh3)；13C{1H}NMR(150.9MHz,CDCl3):δ＝233.89(br,C1),212.65(br,C7),189.23(d,J(P,C)＝32.08Hz,C4),171.11(s,COOCH3),168.52(br,C10),161.36(s,C11),160.12(s,C5),155.21(s,C6),152.05(s,C9),129.32(s,C8),126.46(d,J(P,C)＝24.64Hz,C3),127.14-134.67(Ph和C8),121.74(d,J(P,C)＝63.44Hz,C2),121.02(q,J(F,C)＝321.45Hz,CF3SO3),119.35(d,J(P,C)＝87.31Hz,Ph),64.140(s,C13),52.16(s,COOCH3),36.36(s,C12),35.94(s,C14)；HRMS(ESI):m/z理论值[C84H69NO4P3Ru]+1350.3477,实测值1350.3471.
实施例35
本实施例用以说明式VI*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000232
上式中，[Ru]4为RuCl2PPh3。
除以下特征外，化合物VI*-1的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例7制得的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CC≡CPh。
获得红色固体状化合物VI*-1，产率：71％(化合物VI*-1的产率为化合物VI*-1的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CDCl3):δ＝14.44(ddd,J(PH)＝16.61Hz,J(PH)＝5.81Hz,J(HH)＝2.99Hz,1H,C1H),8.19(dd,J(HH)＝2.99Hz,J(PH)＝2.04Hz,1H,C3H),7.09-7.83(50H,Ph),3.74(s,3H,COOCH3),3.51(s,3H,COOCH3),2.90(d,J(HH)＝19.79Hz,1H,C12H),1.99(d,J(HH)＝18.06Hz,1H,C10H),1.92(d,J(HH)＝19.79Hz,1H,C12H),1.61(d,J(HH)＝18.06Hz,1H,C10H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝27.19(d,J(PP)＝4.66Hz,RuPPh3),19.32(s,C8PPh3),8.32(s,C2PPh3).13C{1H}NMR(150.5MHz,CDCl3):δ＝272.03(br,C1),209.49(dd,J(PC)＝27.40Hz,J(PC)＝5.64Hz,C7),205.96(s,C4),188.28(s,C5),170.52(s,COOCH3),170.36(s,COOCH3),166.17(s,C8),160.80(s,C6),150.76(d,J(PC)＝23.26Hz,C3),135.33(d,J(PC)＝64.64Hz,C9),127.76-135.05(m,Ph),119.38(d,J(PC)＝87.70Hz,Ph),105.64(d,J(PC)＝68.74Hz,C2),64.77(s,C11),53.45(s,COOCH3),53.35(s,COOCH3),37.27(s,C12),36.84(s,C10).HRMS(ESI):m/z理论值[C76H62Cl2O4P3Ru]+,1303.2291；实测值1303.2285.
实施例36
本实施例用以说明式VI*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000233
上式中，[Rh]4为RhClPPh3。
除以下特征外，化合物VI*-13的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例7制得的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CC≡CPh，将RuCl2(PPh3)3换成等摩尔数的RhCl(PPh3)3。
获得红色固体状化合物VI*-13，产率：71％(化合物VI*-13的产率为化合物VI*-13的摩尔量/RhCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝14.32(ddd,J(PH)＝16.44Hz,J(PH)＝5.78Hz,J(HH)＝3.01Hz,1H,C1H),7.84(dd,J(HH)＝3.18Hz,J(PH)＝2.11Hz,1H,C3H),7.04-7.76(50H,Ph),3.63(s,3H,COOCH3),3.44(s,3H,COOCH3),2.77(d,J(HH)＝19.86Hz,1H,C12H),1.82(d,J(HH)＝19.44Hz,1H,C10H),1.78(d,J(HH)＝19.93Hz,1H,C12H),1.56(d,J(HH)＝18.67Hz,1H,C10H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝25.63(d,J(PP)＝106.33Hz,RuPPh3),18.53(s,C8PPh3),93.37(s,C2PPh3).13C{1H}NMR(150.5MHz,CD2Cl2):δ＝273.12(br,C1),210.18(dd,J(PC)＝27.44Hz,J(PC)＝5.64Hz,C7),206.18(s,C4),188.84(s,C5),171.48(s,COOCH3),170.62(s,COOCH3),166.50(s,C8),161.43(s,C6),151.93(d,J(PC)＝23.35Hz,C3),136.47(d,J(PC)＝64.68Hz,C9),128.35-136.43(m,Ph),118.99(d,J(PC)＝87.71Hz,Ph),106.30(d,J(PC)＝68.73Hz,C2),66.10(s,C11),54.70(s,COOCH3),53.65(s,COOCH3),37.68(s,C12),37.55(s,C10).HRMS(ESI):m/z理论值[C76H62ClO4P3Rh]+,1269.2599；实测值1269.2594.
实施例37
本实施例用以说明式VI*所示的金属桥位稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000234
上式中，[Ir]4为IrClPPh3。
除以下特征外，化合物VI*-10的制备方法与实施例1中的化合物I*-1的制备方法相同：
将实施例1中使用的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH换成等摩尔数的制备例12制得的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CC≡CTh(Th为噻吩基)，将RuCl2(PPh3)3换成等摩尔的IrCl(PPh3)3。
获得红色固体状化合物VI*-10，产率：73％(化合物VI*-10的产率为化合物VI*-10的摩尔量/RhCl(PPh3)3的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝13.85(ddd,J(PH)＝16.89Hz,J(PH)＝4.43Hz,J(HH)＝2.42Hz,1H,C1H),8.09(dd,J(PH)＝2.65Hz,J(HH)＝2.65Hz,1H,C3H),6.79-7.85(49H,Ph),3.53(s,3H,COOCH3),3.30(s,3H,COOCH3),2.31(d,J(HH)＝19.53Hz,1H,C12H),1.79(d,J(HH)＝18.06Hz,1H,C10H),1.61(d,J(HH)＝18.01Hz,1H,C10H),1.19(d,J(HH)＝19.41Hz,1H,C12H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝18.88(s,C8PPh3),9.51(s,C2PPh3),-12.42(s,IrPPh3).13C{1H}NMR(150.5MHz,CD2Cl2):δ＝235.42(br,C1),188.33(d,J(PC)＝25.36Hz,C2),182.57(dd,J(PC)＝4.20Hz,J(PC)＝4.20Hz,C8),178.39(s,C5),170.42(s,COOCH3),169.82(s,COOCH3),163.10(s,C7),163.22(s,C6),142.18(d,J(PC)＝22.49Hz,C3),141.47（d,J(PC)＝70.68Hz,C9),126.71-134.11(m,Ph),119.17(d,J(PC)＝88.27Hz,Ph),98.24(d,J(PC)＝70.83Hz,C2),64.12(s,C11),52.56(s,COOCH3),52.23(s,COOCH3),36.26(s,C12),35.78(s,C10).HRMS(ESI):m/z理论值[C74H60ClO4P3Ir]+,1365.2737；实测值1365.2734.
实施例38
本实施例用以说明式I'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000235
其中，[Ru]1为RuCl(PPh3)2。
将实施例1制得的化合物I*-1(0.1mmol)溶入15mL氯仿中，然后加入氢氧化钠(NaOH0.50mmol)和水(0.1mL)的混合液，将获得的混合物在室温下搅拌1天后过滤，将滤液浓缩至2mL，加入30mL正己烷作为沉淀剂，将获得的沉淀物经过滤、洗涤和柱色谱分离(柱色谱填料为硅胶，洗脱剂为：二氯甲烷/丙酮＝10/1体积比)得红色固体I'*-1，产率：78％(化合物I'*-1的产率为化合物I'*-1的摩尔量/化合物I*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.15(s,1H,C7H),8.23(s,1H,C2H),7.45(s,1H,C3H),6.98-7.94(31H,Ph和C3H),3.72(s,6H,COOCH3),2.83(t,J(H,H)＝3.53,C10H),2.63(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝28.48(s,RuPPh3).
实施例39
本实施例用以说明式I'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000236
其中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物I'*-8的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例3制得的化合物I*-8。
获得红色固体状化合物I'*-8，产率：82％(化合物I'*-8的产率为化合物I'*-8的摩尔量/化合物I*-8的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.07(s,1H,C7H),8.12(s,1H,C2H),6.98-7.91(35H,Ph),3.71(s,6H,COOCH3),2.82(t,J(H,H)＝3.53,C10H),2.62(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝28.03(s,RuPPh3).
实施例40
本实施例用以说明式I'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000237
其中，[Ir]1为IrCl(PPh3)2。
除以下特征外，化合物I'*-7的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例6制得的化合物I*-7。
获得红色固体状化合物I'*-7，产率：81％(化合物I'*-7的产率为化合物I'*-7的摩尔量/化合物I*-7的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.28(s,1H,C7H),8.01(s,C2H),7.55(s,1H,C3H),6.59-7.73(m,30H,Ph),2.48(m,2H,C10H),2.07(tt,表现为五重峰,J(HH)＝7.27Hz,2H,C9H),1.73ppm(t,J(HH)＝7.27Hz,2H,C8H).31P{1H}NMR(121.5MHz,CD2Cl2):-4.01ppm(s,IrPPh3).
实施例41
本实施例用以说明式I'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000238
其中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物I'*-14的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例8制得的化合物I*-14。
获得红色固体状化合物I'*-14，产率：77％(化合物I'*-14的产率为化合物I'*-14的摩尔量/化合物I*-14的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.12(s,1H,C7H),8.03(s,C2H),7.74(s,1H,C3H),7.00-7.69(m，35H,Ph),2.61(m,2H,C10H),2.07(tt,表现为五重峰,J(HH)＝7.14Hz,2H,C9H),1.93ppm(t,J(HH)＝7.14Hz,2H,C8H).31P{1H}NMR(121.5MHz,CD2Cl2):δ＝35.02(dd,J(RhP)＝108.11Hz,J(PP)＝5.56Hz,RhPPh3).
实施例42
本实施例用以说明式II'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000239
其中，[Ru]2为RuCO(PPh3)2。
除以下特征外，化合物II'*-6的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例15制得的化合物II*-6。
获得红色固体状化合物II'*-6，产率：78％(化合物II'*-6的产率为化合物II'*-6的摩尔量/化合物II*-6的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(500.2MHz,CD2Cl2):δ＝10.73(s,1H,C7H),8.01(d,1H,J(HH)＝7.2Hz,C3H),7.92(d,1H,J(HH)＝7.2Hz,C2H),6.03-7.81(35H,Ph),3.45(s,6H,COOCH3),2.49(s,C10H),2.23(s,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝35.94ppm(s,RuPPh3).
实施例43
本实施例用以说明式II'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000240
其中，[Rh]2为RhCO(PPh3)2。
除以下特征外，化合物II'*-2的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例11制得的化合物II*-2。
获得红色固体状化合物II'*-2，产率：71％(化合物II'*-2的产率为化合物II'*-2的摩尔量/化合物II*-2的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝12.95(s,1H,C7H),11.60(d,J(HH)＝7.8Hz,1H,C1H),8.15(d,1H,J(HH)＝7.3Hz,C3H),7.93(dd,1H,J(HH)＝7.8Hz,J(HH)＝7.3Hz,C2H),6.69-7.78(30H,Ph),2.18(m,2H,C10H),1.44(tt,J(HH)＝7.28Hz,J(HH)＝7.28Hz,2H,C9H),1.37ppm(t,J(HH)＝7.28Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝26.50ppm(dd,J(RhP)＝109.11Hz,J(PP)＝4.97Hz,RhPPh3).
实施例44
本实施例用以说明式II'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000241
其中，[Ir]2为Ir CO(PPh3)2。
除以下特征外，化合物II'*-9的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例9制得的化合物II*-10。
获得红色固体状化合物II'*-9，产率：75％(化合物II'*-9的产率为化合物II'*-9的摩尔量/化合物II*-10的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝14.02(s,1H,C7H),12.43(d,J(HH)＝8.11Hz,1H,C1H),8.40(d,1H,J(HH)＝7.5Hz,C3H),8.12(dd,1H,J(HH)＝8.11Hz,J(HH)＝7.5Hz,C2H),6.79-7.82(30H,Ph),2.23(m,2H,C10H),1.41(tt,J(HH)＝7.32Hz,J(HH)＝7.32Hz,2H,C9H),1.33ppm(t,J(HH)＝7.32Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝-7.89ppm(s,IrPPh3).
实施例45
本实施例用以说明式III'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000242
其中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物III'*-1的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例19制得的化合物III*-20。
获得棕色固体状化合物III'*-1，产率：81％(化合物III'*-1的产率为化合物III'*-1的摩尔量/化合物III*-20的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.13(d,1H,J(HH)＝7.97Hz,C1H),7.58(d,1H,J(HH)＝7.39Hz,C3H),7.46(dd,1H,J(HH)＝7.97Hz,J(HH)＝7.39Hz,C2H),6.56-7.81(37H,Ph、C3H和 C2H),3.58(s,6H,COOCH3),3.52(s,1H,C8H),3.22(s,C11H),2.36(s,C9H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝22.06ppm(s,RuPPh3).
实施例46
本实施例用以说明式III'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000243
其中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物III'*-8的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例21制得的化合物III*-8。
获得红色固体状化合物III'*-8，产率：85％(化合物III'*-8的产率为化合物III'*-8的摩尔量/化合物III*-8的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(600.1MHz,CD2Cl2):δ＝12.01(d,J(HH)＝8.56Hz,1H,C1H),6.85(1H,C3H,determined by1H-13C HSQC and1H-13C HMBC),6.63(1H,C2H,determined by1H-13C HSQC and1H-13C HMBC),6.54-7.82(32H,Ph、C3H和C2H),3.75(s,6H,COOCH3),2.65(s,C8H),2.54ppm(s,C10H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝23.62ppm(s,RuPPh3).
实施例47
本实施例用以说明式III'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000244
其中，[Ir]1为Ir(PPh3)2。
除以下特征外，化合物III'*-10的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例23制得的化合物III*-10。
获得红色固体状化合物III'*-10，产率：81％(化合物III'*-10的产率为化合物III'*-10的摩尔量/化合物III*-10的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(500.2MHz,CD2Cl2):δ＝13.95(d,1H,J(HH)＝8.52Hz,C1H),8.43(d,J(HH)＝7.39Hz,1H,C3H),8.23(dd,1H,J(HH)＝8.52Hz,J(HH)＝7.39Hz,C2H),6.76-8.02(m,30H,Ph),4.50(s,2H,C9H),3.63(s,2H,C10H),3.17ppm(s,2H,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝-15.34ppm(s,IrPPh3).
实施例48
本实施例用以说明式III'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000245
其中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物III'*-14的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例25制得的化合物III*-14。
获得红色固体状化合物III'*-14，产率：81％(化合物III'*-14的产率为化合物III'*-14的摩尔量/化合物III*-10的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(400.1MHz,CDCl3):δ＝13.65(d,J(HH)＝8.76Hz,1H,C1H),8.54(d,1H,J(HH)＝7.26Hz,C3H),8.23(dd,1H,J(HH)＝8.76Hz,J(HH)＝7.26Hz,C2H),7.95–6.78ppm(m,30H,Ph),2.69(m,2H,C10H),1.75(tt,J(HH)＝7.61Hz,2H,C9H),1.36(t,J(HH)＝7.61Hz,2H,C8H).31P-NMR(162.0MHz,CDCl3):δ＝–9.3ppm(s,J(RhP)＝110.21Hz,RhPPh3).
实施例49
本实施例用以说明式IV'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000246
其中，[Rh]1为Rh(PPh3)2。
除以下特征外，化合物IV'*-9的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例28制得的化合物IV*-8。
获得绿色固体状化合物IV'*-9，产率：86％(化合物IV'*-9的产率为化合物IV'*-9的摩尔量/化合物IV*-8的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝12.59(d,1H,J(H,H)＝8.62Hz,C1H),6.88-7.76(35H,Ph),8.37(d,1H,J(H,H)＝8.62Hz,C2H),7.65(s,1H,C3H),5.54(s,1H,C8H),3.54(q,J(H,H)＝7.19Hz,OCH2CH3),2.43(m,2H,C12H),2.02(tt,表现为五重峰,J(HH)＝7.26Hz,2H,C11H),1.79ppm(t,J(HH)＝7.26Hz,2H,C10H),1.22(t,J(H,H)＝7.19Hz,OCH2CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝24.59ppm(d,J(RhP)＝102.72Hz,RhPPh3).
实施例50
本实施例用以说明式IV'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000247
其中，[Ru]1为RuCl(PPh3)2。
除以下特征外，化合物IV'*-5的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例27制得的化合物IV*-5。
获得绿色固体状化合物IV'*-5，产率：84％(化合物IV'*-5的产率为化合物IV'*-5的摩尔量/化合物IV*-5的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝11.95(d,1H,J(HH)＝8.57Hz,C1H),6.83-7.72(35H,Ph),6.11(d,1H,J(HH)＝7.12Hz,C3H),5.67(d,1H,J(HH)＝7.12Hz,C2H),2.74(s,COCH3),3.52(s,C10H),3.43(s,C11H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝20.36ppm(s,RuPPh3).
实施例51
本实施例用以说明式IV'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000248
其中，[Ir]1为Ir(PPh3)2。
除以下特征外，化合物IV'*-12的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例29制得的化合物IV*-12。
获得绿色固体状化合物IV'*-12，产率：87％(化合物IV'*-12的产率为化合物IV'*-12的摩尔量/化合物IV*-12的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝11.89(d,1H,J(HH)＝8.53Hz,C1H),6.75-7.66(35H,Ph),6.45(d,1H,J(HH)＝8.53Hz,C2H),3.53(s,6H,COOCH3),3.36(q,J(H,H)＝7.12Hz,OCH2CH3),2.48(s,C10H),2.26(s,C12H),1.29(t,J(H,H)＝7.12Hz,OCH2CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝-8.32ppm(s,IrPPh3).
1H NMR(300.1MHz,CD2Cl2):δ＝11.89(d,1H,J(HH)＝8.53Hz,C1H),6.75-7.66(35H,Ph),6.65(d，1H,J(HH)＝8.53Hz,C2H),6.53(s,1H,C3H),3.63(q,J(H,H)＝7.10Hz,OCH2CH3),2.41(m,2H,C12H),2.21(tt,表现为五重峰,J(HH)＝6.95Hz,2H,C11H),1.83ppm(t,J(HH)＝6.95Hz,2H,C10H),1.30(t,J(H,H)＝7.10Hz,OCH2CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝-8.32ppm(s,IrPPh3).
实施例52
本实施例用以说明式V'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000249
其中，[Ru]3为Ru(PPh3)2。
除以下特征外，化合物V'*-1的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例30制得的化合物V*-1。
获得绿色固体状化合物V'*-1，产率：80％(化合物V'-1的产率为化合物V'*-1的摩尔量/化合物V*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.23(d,J(HH)＝8.62Hz,1H,C1H),7.78(d,1H,J(HH)＝7.23Hz,C9H),6.90-7.81(31H,Ph和C9H),6.39(d,1H,J(HH)＝7.12,C3H),6.11(dd,1H,J(HH)＝8.62Hz,J(HH)＝7.12,C2H),5.85(d,1H,J(HH)＝7.23Hz,C8H),3.76(s,6H,COOCH3),2.94(s,4H,C13H and C15H),1.31(s,3H,C12H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝32.84(s,RuPPh3).
实施例53
本实施例用以说明式V'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000250
其中，[Ir]3为IrClPPh3。
除以下特征外，化合物V'*-11的制备方法与实施例38中的化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例33制得的化合物V*-11。
获得绿色固体状化合物V'*-11，产率：88％(化合物V'*-11的产率为化合物V'*-11的摩尔量/化合物V*-11的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝11.58(d,1H,J(HH)＝8.69Hz,C1H),7.63(d,1H,J(HH)＝7.31Hz,C9H),6.95-7.89(31H,Ph和C9H),6.45(d,1H,J(HH)＝7.15Hz,C3H),6.23(dd,1H,J(HH)＝8.69Hz,J(HH)＝7.15Hz,C2H),5.53(d,1H,J(HH)＝7.31Hz,C8H),4.12(s,2H,C13H),4.05(s,2H,C14H),3.54(s,3H,C12H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝-4.56ppm(s,IrPPh3).
实施例54
本实施例用以说明式V'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000251
其中，[Rh]3为RhClPPh3。
除以下特征外，化合物V'*-22的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例32制得的化合物V*-22。
获得绿色固体状化合物V'*-22，产率：88％(化合物V'*-22的产率为化合物V'*-22的摩尔 量/化合物V*-22的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H NMR(600.1MHz,CDCl3):δ＝12.57(d,1H,J(HH)＝8.92Hz,C1H),6.89-7.58(20H,Ph),6.81(s,C3H),6.54(d,1H,J(HH)＝8.92Hz,C2H),5.90(s,1H,C8H),4.31(s,2H,C13H),4.07(s,2H,C14H),3.72(s,3H,C12H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝35.93ppm(d,J(Rh,P)＝103.32Hz,RhPPh3).
实施例55
本实施例用以说明式VI'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000252
其中，[Ru]4为RuCl2PPh3。
除以下特征外，化合物VI'*-1的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例35制得的化合物VI*-1。
获得红色固体状化合物VI'*-1，产率：88％(化合物VI'*-1的产率为化合物VI'*-1的摩尔量/化合物VI*-1的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CDCl3):δ＝14.44(d,1H,J(HH)＝8.56Hz,C1H),8.19(d,J(HH)＝7.23Hz,1H,C3H),8.02(dd,J(HH)＝8.56Hz,J(HH)＝7.23Hz,C2H),6.89-7.93(35H,Ph),3.79(s,3H,COOCH3),3.46(s,3H,COOCH3),2.87(d,J(HH)＝20.03Hz,1H,C12H),1.99(d,J(HH)＝19.63Hz,1H,C10H),1.92(d,J(HH)＝20.03Hz,1H,C12H),1.61(d,J(HH)＝19.63Hz,1H,C10H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝32.58(s,RuPPh3),21.05ppm(s,C8PPh3).
实施例56
本实施例用以说明式VI'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000253
其中，[Ir]4为IrClPPh3。
除以下特征外，化合物VI'*-10的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例37制得的化合物VI*-10。
获得红色固体状化合物VI'*-10，产率：82％(化合物VI'*-10的产率为化合物VI'*-10的摩 尔量/化合物VI*-10的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝13.85(d,J(HH)＝8.96Hz,1H,C1H),9.35(d,J(HH)＝7.19Hz,1H,C3H),8.52(dd,1H,J(HH)＝8.96Hz,J(HH)＝7.19Hz,C2H),6.83-7.91(33H,Ph),3.65(s,3H,COOCH3),3.42(s,3H,COOCH3),2.36(d,J(HH)＝19.82Hz,1H,C12H),1.83(d,J(HH)＝18.26Hz,1H,C10H),1.74(d,J(HH)＝18.26Hz,1H,C10H),1.36(d,J(HH)＝19.82Hz,1H,C12H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝21.36(s,C8PPh3),-15.69ppm(s,IrPPh3).
实施例57
本实施例用以说明式VI'*所示的锇杂稠环化合物的制备方法。
Figure PCTCN2016081392-appb-000254
其中，[Rh]4为RhClPPh3。
除以下特征外，化合物VI'*-13的制备方法与实施例38中化合物I'*-1的制备方法相同：
将实施例38中使用的化合物I*-1换成等摩尔数的实施例36制得的化合物VI*-13。
获得红色固体状化合物VI'*-13，产率：83％(化合物VI'*-13的产率为化合物VI'*-13的摩尔量/化合物VI*-13的摩尔量×100％)。
所获得的金属桥位稠环化合物的波谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝13.21(d,J(HH)＝8.32Hz,1H,C1H),8.31(d,J(HH)＝7.60Hz,1H,C3H),8.01(dd,J(HH)＝8.32Hz,J(HH)＝7.60Hz,1H,C2H),6.78-7.96(35H,Ph),3.68(s,3H,COOCH3),3.48(s,3H,COOCH3),2.79(d,J(HH)＝19.89Hz,1H,C12H),1.84(d,J(HH)＝19.46Hz,1H,C10H),1.79(d,J(HH)＝19.89Hz,1H,C12H),1.57(d,J(HH)＝19.46Hz,1H,C10H)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝27.61(d,J(PP)＝106.33Hz,RuPPh3),13.51(s,C8PPh3).
实施例58
锇杂戊搭炔Os-1的合成。
Figure PCTCN2016081392-appb-000255
其中，DCM为二氯甲烷。
在氮气氛围下，将OsCl2(PPh3)3(500mg，0.48mmol，根据文献Inorg.Synth.,1989,26,184.合成)与PPh3(629mg，2.40mmol，购自国药集团化学试剂有限公司，商品牌号为80136926)溶于20mL二氯甲烷溶液中，并在磁力搅拌下，逐滴加入HC≡CCH(OH)C≡C(CH2)3C≡CH(105mg，0.72mmol，该化合物的合成见制备例1)的二氯甲烷溶液(将0.72mmol的 HC≡CCH(OH)C≡C(CH2)3C≡CH溶于2mL二氯甲烷中)，室温下反应1.5h，溶液颜色由绿色变成红色。将获得的反应混合物用真空泵浓缩至2mL，接着用Et2O(乙醚)洗涤三次，每次使用30mL乙醚，得450mg红色固体状Os-1。Os-1的产率：80％。(Os-1的产率为Os-1的摩尔量/OsCl2(PPh3)3的摩尔量×100％)。
Os-1的核磁和高分辨质谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.33(s,1H,C7H),7.61(s,1H,C3H),7.02-7.79(m,45H,Ph),2.44.(dt,J(HH)＝7.27Hz,J(HH)＝3.63Hz,2H,C10H),2.01(tt,apparent quint,J(HH)＝7.27Hz,2H,C9H),1.79(t,J(HH)＝7.27Hz,2H,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝5.76(t,J(PP)＝5.72Hz,CPPh3),3.23(d,J(PP)＝5.72Hz,OsPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ321.56(dt,apparent q,J(PC)＝13.33Hz,J(PC)＝13.33Hz,C1),216.58(t,J(PC)＝10.59Hz,C7),180.44(s,C5),175.50(t,J(PC)＝3.53Hz,C6),172.04(dt,J(PC)＝23.30Hz,J(PC)＝3.21Hz,C4),147.96(dt,J(PC)＝15.36Hz,J(PC)＝2.77Hz,C3),128.00-135.48(Ph),125.89(dt,J(PC)＝95.84Hz,J(PC)＝3.61Hz,C2),120.56(d,J(PC)＝90.83Hz,Ph),31.32(s,C8),29.57(s,C10),29.28(s,C9).HRMS(ESI):m/z计算值[C64H53ClP3Os]+,1141.2658；实际值,1141.2646.
实施例59
锇杂戊搭炔Os-2的合成。
Figure PCTCN2016081392-appb-000256
除以下特征外，Os-2的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的HC≡CCH(OH)C≡C(CH2)3C≡CH换成等摩尔数的HC≡CCH(OH)C≡CCH2OCH2C≡CH(该化合物的合成方法见制备例3)。
获得红色固体状Os-2，产率：82％。(Os-2的产率为Os-2的摩尔量/OsCl2(PPh3)3的摩尔量×100％)。
Os-2的核磁和高分辨质谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝13.27(s,1H,C7H),7.69(s,1H,C3H),7.01-7.79(Ph 46H,Ph and above-mentioned C3H),4.55(s,C9H),3.89(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝6.05(t,J(PP)＝4.67Hz,CPPh3),2.49(d,J(PP)＝4.67Hz,OsPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ302.51(dt,apparent q,J(PC)＝13.54Hz,J(PC)＝13.54Hz,C1),211.53(t,J(PC)＝11.06Hz,C7),172.79(s,C5),171.55(t,J(PC)＝4.96Hz,C6),169.26(dt,J(PC)＝23.95Hz,J(PC)＝2.97Hz,C4),150.34(d,J(PC)＝15.37Hz,C3),120.27-135.82(Ph),119.81(d,J(PC)＝90.43Hz,C2),71.39(s,C8),69.17(s,C9)；HRMS(ESI):m/z计算值[C63H51ClOP3Os]+,1143.2451；实际值,1143.2435.
实施例60
锇杂戊搭炔Os-3的合成。
Figure PCTCN2016081392-appb-000257
除以下特征外，Os-3的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的HC≡CCH(OH)C≡C(CH2)3C≡CH换成等摩尔数的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH(该化合物的合成方法见制备例2)。
获得红色固体状Os-3，产率：85％。(Os-3的产率为Os-3的摩尔量/OsCl2(PPh3)3的摩尔量×100％)。
Os-3的核磁和高分辨质谱数据如下：
1H-NMR(500.2MHz,CD2Cl2):δ＝13.16(s,1H,C7H),7.67(s,1H,C3H),7.02-7.80(m,46H,Ph and above-mentioned C3H),3.64(s,6H,COOCH3),3.12(s,C10H),2.44(s,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝5.79(t,J(P,P)＝5.00Hz,CPPh3),3.31(d,J(P,P)＝5.00Hz,OsPPh3)；13C{1H}NMR(125.8MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ321.57(dt,apparent q,J(P,C)＝13.33Hz,J(PC)＝13.33Hz,C1),217.23(q,J(P,C)＝9.78Hz,J(P,C)＝19.55Hz,C7),173.07(s,C5),172.16(s,COOCH3),171.81(d,J(P,C)＝23.02Hz,C4),170.12(s,C6),149.22(d,J(P,C)＝16.31Hz,C3),128.18-135.61(Ph),128.15(dt,J(P,C)＝81.30Hz,J(PC)＝3.64Hz,C2),120.30(d,J(PC)＝91.07Hz,Ph),64.38(s,C9),53.54(s,COOCH3),39.07(s,C8),37.62(s,C10)；HRMS(ESI):m/z计算值[C68H57ClO4P3Os]+,1257.2768；实际值,1257.2771.
实施例61
钌杂戊搭炔Ru-1的合成。
Figure PCTCN2016081392-appb-000258
除以下特征外，Ru-1的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的HC≡CCH(OH)C≡C(CH2)3C≡CH换成等摩尔数的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH(该化合物的合成方法见制备例2)，同时将OsCl2(PPh3)3换成RuCl2(PPh3)3。
获得红色固体状Ru-1，产率：70％。(Ru-1的产率为Ru-1的摩尔量/RuCl2(PPh3)3的摩尔量×100％)。
Ru-1的核磁和高分辨质谱数据如下：
1H NMR(300.1MHz,CD2Cl2):δ＝13.06(s,1H,C7H),7.33(1H,C3H,obtained by HSQC),6.99-7.81(46H,Ph and above-mentioned C3H),3.64(s,6H,COOCH3),2.96(t,J(H,H)＝3.63,C10H),2.76(s,C8H)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝29.59(d,J(P,P)＝5.89Hz,RuPPh3),6.38(t, J(P,P)＝5.89Hz,CPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝356.95(br,C1),251.89(t,J(P,C)＝11.96,C7),190.23(dt,J(P,C)＝25.65Hz,J(P,C)＝4.90Hz,C4),180.98(d,J(P,C)＝1.97Hz,C5),171.77(s,COOCH3),164.57(t,J(P,C)＝4.24Hz,C6),154.99(dt,J(P,C)＝14.44Hz,J(P,C)＝3.07Hz,C3),128.18-135.76(other aromatic carbons),122.86(dt,J(P,C)＝92.99Hz,J(P,C)＝4.02Hz,C2),119.57(other aromatic carbons),64.14(s,C9),53.63(s,COOCH3,obtained by13C-dept 135),39.06(s,C8),37.35(s,C10)；HRMS(ESI):m/z计算值[C68H57ClO4P3Ru]+,1167.2212；实际值,1167.2215.
实施例62
铑杂双五元环化合物Rh-2的合成。
Figure PCTCN2016081392-appb-000259
除以下特征外，Rh-2的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的HC≡CCH(OH)C≡C(CH2)3C≡CH换成等摩尔数的HC≡CCH(OH)C≡CCH2C(COOMe)2CH2C≡CH，同时将OsCl2(PPh3)3换成RhCl(PPh3)3。
获得黄色固体状Rh-2，产率：91％。(Rh-2的产率为Rh-2的摩尔量/RhCl(PPh3)3的摩尔量×100％)。
Rh-2的核磁和高分辨质谱数据如下：
1H-NMR(600.1MHz,CD2Cl2):δ＝10.27(d,J(PH)＝29.75Hz,,1H,C1H),6.87-8.20(45H,Ph),6.53(s,1H,C7H),3.57(s,3H,COOCH3),3.54(s,3H,COOCH3),3.45(d,J(HH)＝8.95Hz,1H,C3H),2.35(d,J(HH)＝16.47Hz,1H,C10H),2.27(d,J(HH)＝16.47Hz,1H,C10H),2.01(d,J(HH)＝17.02Hz,1H,C8H),1.78(d,J(HH)＝17.02Hz,1H,C8H),0.17(d,J(HH)＝8.95Hz,1H,OH)；31P{1H}NMR(242.9MHz,CD2Cl2):δ＝33.33(ddd,J(PP)＝431.55Hz,J(RhP)＝126.88Hz,J(PP)＝5.74Hz,RhPPh3),δ＝31.04(ddd,J(PP)＝431.55Hz,J(RhP)＝126.88Hz,J(PP)＝5.74Hz,RhPPh3),8.00(br,CPPh3)；13C{1H}NMR(150.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝221.27(br,C1),174.08(s,COOCH3),173.27(s,COOCH3),167.45(br,C4),154.85(s,C6),153.49(br,C7),145.57(s,C5),127.32-136.42(Ph),122.91(d,J(PC)＝46.59Hz,C2),122.89(d,J(PC)＝84.89Hz,Ph),80.32(d,J(PC)＝25.69Hz,C3),64.39(s,C9),52.90(s,COOCH3),52.70(s,COOCH3),39.06(s,C10),36.01(s,C10)；HRMS(ESI):m/z计算值[C68H60ClO5P3Rh]+,1187.2392[M+H]+；实际值,1187.2418.
实施例63
铱杂戊搭烯Ir-1的合成。
Figure PCTCN2016081392-appb-000260
除以下特征外，Ir-1的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的OsCl2(PPh3)3换成IrHCl2(PPh3)3(该化合物的合成见制备例1)。
Ir-1产率：35％。(Ir-1的产率为Ir-1的摩尔量/IrHCl2(PPh3)3的摩尔量×100％)。
Ir-1的核磁和高分辨质谱数据如下：
1H-NMR(600.1MHz,CDCl3):δ＝14.34(s,1H,C7H),12.66(d,J(PH)＝20.03Hz,1H,C1H),8.67(t,J(PH)＝2.35Hz,1H,C3H),6.98-7.90(m,45H,Ph),2.56(m,2H,C10H),1.64(tt,apparent quint,J(HH)＝7.44Hz,2H,C9H),1.15(t,J(HH)＝7.44Hz,2H,C8H)；31P{1H}NMR(242.9MHz,CDCl3):δ＝10.91(t,J(PP)＝5.97Hz,CPPh3),-5.77(d,J(PP)＝5.97Hz,IrPPh3)；13C{1H}NMR(150.9MHz,CDCl3,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝230.16(br,C7),215.13(br,C1),186.44(s,C5),184.96(s,C6),169.34(dt,J(PC)＝22.59Hz,J(PC)＝2.90Hz,C4),151.98(d,J(PC)＝24.44Hz,C3),137.51(dt,J(PC)＝62.94Hz,J(PC)＝3.21Hz,C2),119.36-135.16(Ph),31.75(s,C8),31.00(s,C10),28.75(s,C9)；HRMS(ESI):m/z计算值[C64H54ClP3Ir]+,1143.2748；实际值,1143.2739.
实施例64
锇杂戊搭烯衍生物Os-4的合成。
Figure PCTCN2016081392-appb-000261
除以下特征外，Os-4的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的HC≡CCH(OH)C≡C(CH2)3C≡CH换成等摩尔数的HC≡CCH(OH)C≡CCH2OCH2CH＝C＝CH(该化合物的合成方法见制备例6)。
获得红色固体状Os-4，产率：80％。(Os-4的产率为Os-4的摩尔量/OsCl2(PPh3)3的摩尔量×100％)。
Os-4的核磁和高分辨质谱数据如下：
1H-NMR(500.2MHz,CD2Cl2):δ＝14.01(d,J(P,H)＝17.17Hz,1H,C1H),8.21(s,1H,C3H),6.90-7.81(m,45H,Ph),4.12(s,2H,C9H),3.21(s,2H,C10H),3.03(s,2H,C8H)；31P{1H}NMR(202.5MHz,CD2Cl2):δ＝11.81(d,J(P,P)＝4.95Hz,CPPh3),-13.19(d,J(PP)＝4.95Hz,OsPPh3)；13C{1H}NMR(125.8MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ＝339.19(br,C1),226.16(t,J(P,C)＝4.37Hz,C7),183.46(s,C5),176.00(d,J(PC)＝25.20Hz,C4),163.13(s,C6),145.12(d,J(P,C)＝21.87Hz,C3),134.66(dt,J(P,C)＝70.73Hz,J(P,C)＝3.92Hz,C2),118.46-134.17(Ph),69.92(s,C10),65.41(s,C9),23.08(s,C8)；HRMS(ESI):m/z计算值[C64H53ClOP3Os]+,1157.2607；实际值,1157.2594.
实施例65
锇杂戊搭炔Os-5的合成。
Figure PCTCN2016081392-appb-000262
除以下特征外，Os-5的制备方法与实施例58中的Os-1的制备方法相同。
将实施例58中使用的HC≡CCH(OH)C≡C(CH2)3C≡CH换成等摩尔数的PhC≡CCMe(OH)C≡CCH2OCH2C≡CH(该化合物的合成方法与化合物5相同)。
获得红色固体状Os-5，产率：43％。(Os-5的产率为Os-5的摩尔量/OsCl2(PPh3)3的摩尔量×100％)。
Os-5的核磁和高分辨质谱数据如下：
1H-NMR(300.1MHz,CD2Cl2):δ＝7.05-7.72(m,50H,Ph),4.45(s,C9H),3.78(s,C8H),2.25(s,CH3)；31P{1H}NMR(121.5MHz,CD2Cl2):δ＝14.01(t,J(PP)＝4.72Hz,CPPh3),6.86(d,J(PP)＝4.72Hz,OsPPh3)；13C{1H}NMR(75.5MHz,CD2Cl2,plus13C-dept 135,1H-13C HSQC and1H-13C HMBC):δ330.11(br,C7),225.2(br,C1),171.79(s,C5),171.34(t,J(PC)＝4.94Hz,C6),168.11(dt,J(PC)＝23.45Hz,J(PC)＝2.85Hz,C4),148.33(d,J(PC)＝15.37Hz,C3),120.25-135.76(Ph),118.11(d,J(PC)＝90.21Hz,C2),71.35(s,C8),69.05(s,C9),25.12(s,CH3)；HRMS(ESI):m/z计算值[C70H57ClOP3Os]+,1233.2920；实际值,1233.2917.
测试例1
本测试例用来说明式I*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式I*的代表性化合物I*-1进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物I*-1稀释到1.0×10-5mol/L，在室温下进行测试。
图1为上述实施例1制备得到的金属桥位稠环化合物I*-1的紫外-可见吸收光谱图。
由图1可以看出，化合物I*-1在紫外-可见光区域具有宽的吸收(280nm～650nm)，在波长575nm处具有最大吸收，因此可用作太阳能电池的光敏化剂。
测试例2
本测试例用来说明式II*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例例中获得的式II*的代表性化合物II*-1和II*-11进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物II*-1和II*-11分别稀释到1.0×10-5mol/L，在室温下进行测试。
图2为金属桥位稠环化合物II*-1的紫外-可见吸收光谱图。
图3为金属桥位稠环化合物II*-11的紫外-可见吸收光谱图。
由图2和图3可以看出，化合物II*-1和II*-11在紫外-可见光区域都具有较宽的吸收(均为280nm～600nm)，化合物II*-1在波长530nm处具有最大吸收，化合物II*-11在波长490nm处具有最大吸收，因此可用作太阳能电池的光敏化剂。
测试例3
本测试例用来说明式II*所示的金属杂稠环化合物的循环-伏安曲线和应用。
(1)循环-伏安曲线
以玻碳电极为工作电极，铂电极为对电极，银/氯化银为参比电极，氮气氛、室温下，在0.1M的四丁基六氟磷酸铵的二氯甲烷溶液中对式II*的代表性化合物II*-2进行循环-伏安电化学性能进行测试。
如图4所示，化合物II*-2阳极正向扫描时，在+1.33V处有一准可逆的氧化峰，说明其氧化态较稳定；当阴极负向扫描时，在-0.79V处有一准可逆的还原峰，说明其还原态较稳定；其氧化和还原半波电位V1/2分别为+1.29V和-0.75V。而用于光解水产氢产氧的光敏剂，其理想的氧化还原半波电位在+1.3V和-0.9V之间，化合物II*-2的氧化还原半波电位位于该区间内，因此化合物II*-2可以用作光解水产氢产氧的光敏剂。
(2)作为催化剂在锂-空气电池中的应用
另外，基于化合物II*-2具有两对可逆的氧化还原峰，并且电位差在+2.0V以上，又对其在锂-空气电池中的应用进行了探究。以DMSO为电解液，测试了化合物II*-2对锂-空气电池充、放电电位的影响。
如图5所示，化合物II*-2可有效降低锂-空气电池的充电电位。因此，化合物II*-2可以作为储锂材料应用于锂-空气电池中。
测试例4
本测试例用来说明式IV*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
(1)化合物IV*-1的紫外-可见吸收光谱
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式IV*的代表性化合物IV*-1进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物IV*-1稀释到1.0×10-5mol/L，在室温下进行测试。
图6为金属桥位稠环化合物IV*-1的紫外-可见吸收光谱图。
由图6可以看出，化合物IV*-1在紫外-可见光区域具有宽的吸收(280nm～750nm)，在波长620nm处具有最大吸收。
(2)化合物IV*-1在肿瘤光动力学治疗中的用途测定
光动力学治疗原理：分子在光照射下由基态S0跃迁到单线激发态S1(步骤1)，S1辐射出荧光后回到基态S0(步骤2)或通过系间窜越生成三线态T1(步骤3)，T1与基态氧(三线态)作用生成单线态氧(步骤4)，1O2进而敏化杀死肿瘤细胞。
(1)S0(Sensor)+hν→S1；
(2)S1→S0+hν(Fluo)；
(3)S1→T1；
(4)T1+3O2→S0+1O2；
(5)1O2+基质→氧化。
利用荧光探针DCFH-DA进行活性氧检测。DCFH-DA本身没有荧光，可被碱水解生成DCFH。活性氧可以氧化无荧光的DCFH生成有荧光的DCF。检测DCF的荧光就能够得到体系中活性氧的水平。
利用化合物IV*-1在630nm附近有一强的吸收峰，与光动力学治疗所用激光光源的波长630nm匹配。依据文献(Li-Sen Lin,Zhong-Xiao Cong,Juan Li,Kai-Mei Ke,Shan-Shan Guo,Huang-Hao Yang,Guo-Nan Chen,Graphitic-phase C3N4nanosheets as efficient photosensitizers and pH-responsive drug nanocarriers for cancer imaging and therapy,J.Mater.Chem.B,2014,2,1031)报 道的体外活性氧测试实验条件，即配置等体积的DCFH荧光探针和样品溶液，630nm激光照射5分钟后，用488nm激光检测其在525nm处的荧光强度，测得结果如图7所示。
由图7可见，随着样品浓度的升高，探针DCFH的荧光强度随着增强，说明体系中因光敏化而产生的活性氧量增加。这说明化合物IV*-1可以用于光动力学治疗。
测试例5
本测试例用来说明式V*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式V*的代表性化合物V*-3进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物V*-3稀释到1.0×10-5mol/L，在室温下进行测试。
图8为金属桥位稠环化合物V*-3的紫外-可见吸收光谱图。
由图8可以看出，化合物V*-3在紫外-可见光区域具有宽的吸收(280nm～750nm)，在波长640nm处具有最大吸收，因此可用作太阳能电池的光敏化剂以及用于肿瘤光动力学治疗。
测试例6
本测试例用来说明式VI*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式VI*的代表性化合物VI*-1进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物VI*-1稀释到1.0×10-5mol/L，在室温下进行测试。
图9为金属桥位稠环化合物VI*-1的紫外-可见吸收光谱图。
由图9可以看出，化合物VI*-1在紫外-可见光区域具有宽的吸收(280nm～700nm)，在波长570nm处具有最大吸收，因此可用作太阳能电池的光敏化剂。
测试例7
本测试例用来说明式III*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式III*的代表性化合物III*-9进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物III*-9稀释到1.0×10-5mol/L，在室温下进行测试。
如图10所示，图10为金属桥位稠环化合物III*-9的紫外-可见吸收光谱图。
由图10可以看出，化合物III*-9在紫外-可见光区域具有宽的吸收(300nm～750nm)，在波长625nm处具有最大吸收，因此可用作太阳能电池的光敏化剂以及用于肿瘤光动力学治疗。
测试例8
本测试例用来说明式I'*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式I'*的代表性化合物I'*-6进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物I'*-6稀释到1.0×10-5mol/L，在室温下进行测试。
图11为金属桥位稠环化合物I'*-6的紫外-可见吸收光谱图。
由图11可以看出，化合物I'*-6在紫外-可见光区域具有宽的吸收(300nm～600nm)，在波长447nm处具有最大吸收，因此可用作太阳能电池的光敏化剂。
测试例9
本测试例用来说明式II'*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式II'*的代表性化合物II'*-9进 行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物II'*-9稀释到1.0×10-5mol/L，在室温下进行测试。
如图12所示，图12为金属桥位稠环化合物II'*-9的紫外-可见吸收光谱图。
由图12可以看出，化合物II'*-9在紫外-可见光区域具有宽的吸收(300nm～600nm)，在波长490nm处具有最大吸收，因此可用作太阳能电池的光敏化剂。
测试例10
本测试例用来说明式III'*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式III'*的代表性化合物III'*-4进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物III'*-4稀释到1.0×10-5mol/L，在室温下进行测试。
图13为金属桥位稠环化合物III'*-4的紫外-可见吸收光谱图。
由图13可以看出，化合物III'*-4在紫外-可见光区域具有宽的吸收(300nm～800nm)，在波长665nm处具有最大吸收，因此可用作太阳能电池的光敏化剂以及用于肿瘤光动力学治疗。
测试例11
本测试例用来说明式IV'*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式IV'*的代表性化合物IV'*-5进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物IV'*-5稀释到1.0×10-5mol/L，在室温下进行测试。
图14为金属桥位稠环化合物IV'*-5的紫外-可见吸收光谱图。
由图14可以看出，化合物IV'*-5在紫外-可见光区域具有宽的吸收(300nm～900nm)，在波长690nm处具有最大吸收，因此可用作太阳能电池的光敏化剂以及用于肿瘤光动力学治疗。
测试例12
本测试例用来说明式V'*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式V'*的代表性化合物V'*-1进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物V'*-1稀释到1.0×10-5mol/L，在室温下进行测试。
图15为金属桥位稠环化合物V'*-1的紫外-可见吸收光谱图。
由图15可以看出，化合物V'*-1在紫外-可见光区域具有宽的吸收(300nm～750nm)，在波长650nm处具有最大吸收，因此可用作太阳能电池的光敏化剂以及用于肿瘤光动力学治疗。
测试例13
本测试例用来说明式VI'*所示的金属杂稠环化合物的紫外-可见吸收光谱和应用。
使用SHIMADZU UV2550光谱仪对上述实施例中获得的式VI'*的代表性化合物VI'*-11进行紫外-可见吸收光谱测试。测试的条件为：使用二氯甲烷将化合物VI'*-11稀释到1.0×10-5mol/L，在室温下进行测试。
图16为金属桥位稠环化合物VI'*-11的紫外-可见吸收光谱图。
由图16可以看出，化合物VI'*-11在紫外-可见光区域具有宽的吸收(300nm～750nm)，在波长620nm处具有最大吸收，因此可用作太阳能电池的光敏化剂以及用于肿瘤光动力学治疗。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体 细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (19)

  1. 一种链状多炔化合物，其特征在于，该化合物具有以下式I所示的结构：
    Figure PCTCN2016081392-appb-100001
    其中，X为-O-、-S-、-CR4R5-、-SiR6R7-或-NR8-；R4、R5、R6、R7和R8各自独立地为氢、C1-20烷基、C1-20酯基、C1-20酰基、C3-20环烷基、C1-20卤代烷基、腈基、硝基、取代或未取代的芳基或者
    Figure PCTCN2016081392-appb-100002
    R9为C1-8烷基或者取代或未取代的芳基；
    R1为腈基、取代或未取代的C2-30炔基、取代或未取代的C4-30多炔基、取代或未取代的C3-30累积多烯基，且不含-C≡CCH(OH)C≡C-结构单元；
    R2和R3各自独立地为氢、取代或未取代的芳基、取代或未取代的C1-8烷基、取代或未取代的C1-8烷氧基、取代或未取代的C1-8烷硫基、取代或未取代的C3-8环烷基或者取代或未取代的C2-8炔基，且R2和R3中不含-C≡CCH(OH)C≡C-结构单元；
    m和n分别为1-6的整数，且m+n<8。
  2. 根据权利要求1所述的化合物，其中，X为-O-、-S-、-CH2-、-C(CH3)2-、-CHCH3-、-C(COOMe)2-、-C(COOEt)2-、-C(COCH3)(COOMe)-、-C(Cy)(COOMe)-、-C(CH2CH2Br)2-、-C(CN)2-、-C(NO2)2-、-SiH2-、-SiMe2-、-SiPh2-、-NH-、
    Figure PCTCN2016081392-appb-100003
    R1为腈基、乙炔基、
    Figure PCTCN2016081392-appb-100004
    Figure PCTCN2016081392-appb-100005
    Figure PCTCN2016081392-appb-100006
    R2和R3各自独立地为氢、甲基、乙基、正丙基、异丙基、甲氧基、乙氧基、正丙氧基、异丙氧基、甲硫基、乙硫基、环丙基、环己基、
    Figure PCTCN2016081392-appb-100007
    Figure PCTCN2016081392-appb-100008
    Figure PCTCN2016081392-appb-100009
    乙炔基、丙炔基、
    Figure PCTCN2016081392-appb-100010
    Figure PCTCN2016081392-appb-100011
    苯甲基或苯乙基。
  3. 根据权利要求1所述的化合物，其中，所述链状多炔化合物为如下化合物中的至少一种：
    Figure PCTCN2016081392-appb-100012
    Figure PCTCN2016081392-appb-100013
  4. 权利要求1-3中任意一项所述化合物的制备方法，其特征在于，该方法包括：将式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与式III所示的化合物接触反应，获得式IV所示的Y基团保护的链状多炔化合物；再将式IV所示的Y基团保护的链状多炔化合物进行脱保护基团处理，获得式I所示的链状多炔化合物：
    Figure PCTCN2016081392-appb-100014
    其中，Y为TMS、TES或TIPS；所述有机金属试剂RM1和RM2Z中的R为C1-8烷基、苯基或-NR10R11；R10和R11各自独立地为氢、C1-8烷基或三甲基硅基；M1为锂、钠或钾；M2为镁；Z为氯、溴或碘。
  5. 根据权利要求4所述的方法，其中，所述脱保护基团处理在脱保护剂存在下进行；所述脱保护剂为K2CO3、Na2CO3、Cs2CO3、KF、(n-Bu)4NF、(Et)4NF、(Me)4NF和(n-Pr)4NF中的至少一种。
  6. 权利要求1-3中任意一项所述化合物的制备方法，其特征在于，该方法包括：将式II所示的化 合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中进行金属交换反应，并将得到的反应混合物与式V所示的化合物进行接触反应，获得式I所示的链状多炔化合物：
    HC≡C-(CH2)m-X-(CH2)n-R1   式II，
    Figure PCTCN2016081392-appb-100015
    其中，所述有机金属试剂RM1和RM2Z中的R为C1-8烷基、苯基或-NR10R11；R10和R11各自独立地为氢、C1-8烷基或三甲基硅基；M1为锂、钠或钾；M2为镁；Z为氯、溴或碘。
  7. 根据权利要求4-6中任意一项所述的方法，其中，所述有机金属试剂RM1为甲基锂、乙基锂、正丁基锂、叔丁基锂、苯基锂、二异丙基胺基锂和双(三甲基硅基)胺基锂中的至少一种；
    有机金属试剂RM2Z为甲基溴化镁、乙基溴化镁、甲基氯化镁和乙基氯化镁中的至少一种。
  8. 根据权利要求4或6所述的方法，其中，所述式II所示的化合物与有机金属试剂RM1和RM2Z的总和的摩尔比为1:(0.5-1)；
    优选地，所述非质子性溶剂为苯、甲苯、正己烷、乙醚、乙二醇二甲醚、四氢呋喃和1,4-二氧六环、石油醚和汽油中的至少一种；
    优选地，所述式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中接触的条件包括温度为零下100℃至零上30℃；时间为0.5-10h；
    优选地，所述式II所示的化合物与有机金属试剂RM1和/或RM2Z在非质子性溶剂中进行金属交换反应得到的反应混合物与式III所示的化合物或式V所示的化合物接触反应的条件包括温度为零下100℃至零上30℃；时间为0.5-10h。
  9. 一种金属桥位稠环化合物，其特征在于，该化合物具有式I*-VI*和I'*-VI'*中的任意一个所示的结构：
    Figure PCTCN2016081392-appb-100016
    Figure PCTCN2016081392-appb-100017
    其中，式I*、III*、IV*、I'*、III'*和IV'*中，[M]1为RuAL2、RhL2或IrL2；
    式II*和II'*中，[M]2为RuL3、RhAL2或IrAL2；
    式V*和V'*中，[M]3为RuL2、RhAL或IrAL；
    式VI*和VI'*中，[M]4为RuA2L、RhAL或IrAL；
    A为-H、卤素、-SCN或-CN；
    L为膦配体、CO配体、吡啶类配体、氮杂环卡宾配体、腈类配体和异氰类双电子配体中的至少一种；
    R1*为位于式I*-VI*上标有数字1-6的位置中的任意一个上的阳离子取代基，且R1*为C3-30季鏻阳离子或C3-24季铵阳离子；
    R2*位于式I*-VI*上标有数字1-9的位置中的至少一个上，且R2*与R1*所在位置不同；
    R3*为位于式I'*-VI'*上标有数字1-9的位置中的至少一个上的取代基；
    R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-20烷基、C1-20烷氧基、C1-20烷硫基、C1-20酰基、C1-20酯基、C1-20胺基、C1-20酰胺基、C1-20羧基，C2-20酰胺基，C3-20环烷基，取代或未取代的芳基，取代或未取代的C2-20烯基，取代或未取代的C2-20炔基，取代或未取代的C6-20芳氧基、取代或未取代的C6-20芳硫基，以及能提高水溶性的取代基中的任意一种；
    式III*和III'*中，X1为
    Figure PCTCN2016081392-appb-100018
    -CR5*R6*-、-NR7*-、-O-、-S-和-Se-中的任意一种；R4*、R5*和R6*选择的取代基的范围与R2*或R3*相同，R7*为取代或未取代的芳基、取代或未取代的C1-20烷基或取代或未取代的C3-20环烷基；
    式V*和V'*中，Y1为-NR7*-、-O-或-S-；
    式I*-VI*中，Z1为Cl-、Br-、I-、BF4 -、CF3SO3 -、CH3COO-、(CF3SO2)2N-、NO3 -、ClO4 -、PF6 -或BPh4 -。
  10. 根据权利要求9所述的化合物，其中，L为三甲基膦、三乙基膦、三丙基膦、三异丙基膦、三叔丁基膦、三环己基膦、三苯基膦、三(对-甲基苯基)膦、三(间-甲基苯基)膦、二苯基膦、二苯 基甲基膦、二苯基乙基膦、甲基吡啶、乙基吡啶、1,4-联吡啶、1,2-二(4-吡啶基)乙烯、乙烯基吡啶、乙炔基吡啶、吡啶硼酸、氨基吡啶、氰基吡啶、巯基吡啶、二甲胺基吡啶、苯基吡啶、1,2-双(4-吡啶基)乙烷、咪唑型氮杂环卡宾、咪唑啉型氮杂环卡宾、噻唑型氮杂环卡宾、三唑型氮杂环卡宾、乙腈、丙腈、苯腈、环己基异氰、叔丁基异氰和苯基异氰中的至少一种；或者
    L2为一个整体，且L2为乙二胺、2,2'-联吡啶、1,10-菲罗啉、1,1-双(二苯基膦)甲烷、1,2-双(二苯基膦)乙烷、1,3-双(二苯基膦)丙烷、邻苯基吡啶或8-羟基喹啉；或者
    AL2为一个整体，且AL2为三联吡啶、PPP、PNP、PCP、NNN、NCN、NPN、ONO、OPO、OCO、SCS或CCC Pincer(钳形)配体；
    R1*为位于式I*-VI*上标有数字2-6的位置中的任意一个上的阳离子取代基，且R1*为C3-23季鏻阳离子或C3-20季铵阳离子；
    R2*位于式I*-VI*上标有数字1、2、3、4、5、6、8和9的位置中的至少一个上；
    R3*为位于式I'*-VI'*上标有数字1、2、3、4、5、6、8和9的位置中的至少一个上的取代基；
    R2*和R3*各自独立地选自-H，卤素，-SCN，-CN，C1-17烷基、C1-17烷氧基、C1-17烷硫基、C1-17酰基、C1-17酯基、C1-17胺基、C1-17酰胺基、C1-17羧基，C1-8烷基、C1-8烷氧基、C1-8烷硫基、C1-8酰基、C1-8酯基、C1-8胺基、C1-8酰胺基、C1-8羧基，取代的C2-17酰胺基，C3-17环烷基，取代或未取代的芳基，取代或未取代的C2-17烯基，取代或未取代的C2-17炔基，C6-17芳氧基、C6-17芳硫基，以及能提高水溶性的取代基中的至少一种；
    式III*和III'*中，X1为
    Figure PCTCN2016081392-appb-100019
    Figure PCTCN2016081392-appb-100020
    -NH-、
    Figure PCTCN2016081392-appb-100021
    Figure PCTCN2016081392-appb-100022
    式V*和V'*中，Y1为-NH-、
    Figure PCTCN2016081392-appb-100023
    Figure PCTCN2016081392-appb-100024
    -O-或-S-。
  11. 根据权利要求9或10所述的化合物，其中，R1*为三甲基鏻、三乙基鏻、三丙基鏻、三异丙基鏻、三叔丁基鏻、三环己基鏻、三苯基鏻、三(对-甲基苯基)鏻、三(间-甲基苯基)鏻、二苯基鏻、二苯基甲基鏻、二苯基乙基鏻、三甲基铵、三乙基铵、二甲基一乙基铵、三丙基铵、三异丙基铵或三叔丁基铵阳离子；
    R2*和R3*各自独立地选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基、叔辛基、正十二烷基、正十六烷基、正十八烷基、正二十烷基、
    Figure PCTCN2016081392-appb-100025
    Figure PCTCN2016081392-appb-100026
    甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、仲戊氧基、叔戊氧基、正己氧基、异己氧基、新己氧基、仲己氧基、叔己氧基、正庚氧基、异庚氧基、新庚氧基、仲庚氧基、叔庚氧基、正辛氧基、异辛氧基、新辛氧基、仲辛氧基、叔辛氧基、正十二烷氧基、正十六烷氧基、正十八烷氧基、正二十烷氧基、甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基、正戊硫基、异戊硫基、新戊硫基、仲戊硫基、叔戊硫基、正己硫基、异己硫基、新己硫基、仲己硫基、叔己硫基、正庚硫基、异庚硫基、新庚硫基、仲庚硫基、叔庚硫基、正辛硫基、异辛硫基、新辛硫基、仲辛硫基、叔辛硫基、正十二烷硫基、正十六烷硫基、正十八烷硫基、正二十烷硫基、
    Figure PCTCN2016081392-appb-100027
    Figure PCTCN2016081392-appb-100028
    Figure PCTCN2016081392-appb-100029
    Figure PCTCN2016081392-appb-100030
    甲胺基、乙胺基、丙胺基、丁胺基、戊胺基、己胺基、庚胺基、辛胺基、二甲胺基、二乙胺基、二丙胺基、二丁胺基、正十二胺基、正十六胺基、正十八胺基、正二十胺基、
    Figure PCTCN2016081392-appb-100031
    Figure PCTCN2016081392-appb-100033
    Figure PCTCN2016081392-appb-100034
    环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环十二烷基、环十六烷基、环十八烷基、环二十烷基、苯基、萘基、蒽基、菲基、芘基、噻吩基、呋喃基、吡啶基、吡咯基、
    Figure PCTCN2016081392-appb-100035
    Figure PCTCN2016081392-appb-100036
    Figure PCTCN2016081392-appb-100037
    苯氧基、萘氧基、蒽氧基、菲氧基、芘氧基、噻吩氧基、呋喃氧基、吡啶氧基、吡咯氧基、对-甲苯氧基、间-甲苯氧基、邻甲苯氧基、对-硝基苯氧基、对-甲氧基苯氧基、苯硫基、萘硫基、蒽硫基、菲硫基、芘硫基、噻吩硫基、呋喃硫基、吡啶硫基、吡咯硫基、对-甲苯硫基、间-甲苯硫基、邻甲苯硫基、对-硝基苯硫基、对-甲氧基苯硫基、聚乙二醇残基、透明质酸残基、聚丙烯酸和糖类衍生物残基中的至少一种。
  12. 根据权利要求9所述的化合物，其中，式I*-VI*和I'*-VI'*中，标有数字1-8的1,2-位置、2,3-位置、3,4-位置、4,5-位置、5,6-位置和7,8-位置中的至少一个上有取代或未取代的环状取代基；
    优选地，2,3-位置和/或4,5-位置处有取代或未取代的环状取代基；
    优选地，所述环状取代基为全部由碳原子组成的三元环、四元环、五元环、六元环、七元环或八元环取代基，或者由含有氧、硫、氮和硅中的至少一个杂原子组成的三元环、四元环、五元环、六元环、七元环或八元环取代基；
    优选地，所述取代的环状取代基的取代基为C1-20烷基、C1-20酯基、C1-20酰基、C1-20羧基、取代或未取代的芳基、C3-8环烷基、腈基、硝基和
    Figure PCTCN2016081392-appb-100038
    中的至少一种；R30*为C1-20烷基或者取代或未取代的芳基；
    进一步优选地，所述取代或未取代的环状取代基为
    Figure PCTCN2016081392-appb-100039
    Figure PCTCN2016081392-appb-100040
  13. 根据权利要求9所述的化合物，其中，
    A为氢、氟、氯、溴、碘或SCN；
    L为CO配体、三苯基膦配体、三甲基膦配体、三环己基膦、三(对-甲基苯基)膦、三(间-甲基苯基)膦、二苯基膦、二苯基甲基膦、二苯基乙基膦、和三乙基膦配体中的至少一种；
    式III*和III'*中，X1为-O-、-S-、-CH2-、
    Figure PCTCN2016081392-appb-100041
    Figure PCTCN2016081392-appb-100042
    式V*和V'*中，Y1为-O-、-S-或-NPh-；
    式I*-VI*中，Z1为Cl-、Br-、BF4 -、CF3SO3 -、PF6 -或BPh4 -；
    R1*为位于式I*-VI*上标有数字2或5的位置上的阳离子取代基，且R1*为三苯基鏻阳离子、三甲基鏻阳离子、三乙基鏻阳离子、三环己基鏻阳离子、三(对-甲基苯基)鏻阳离子、三(间-甲基苯基)鏻阳离子、二苯基鏻阳离子、二苯基甲基鏻阳离子、二苯基乙基鏻阳离子、三甲基胺阳离子或三乙基胺阳离子；
    R2*位于式I*-VI*上标有数字1、3、4、5、6、8和9的位置中的至少一个上；
    R3*为位于式I'*-VI'*上标有数字1、3、4、5、6、8和9的位置中的至少一个上的取代基；
    R2*和R3*各自独立地选自-H、-F、-Cl、-Br、-SCN、-CN、-OPh、-SPh、
    Figure PCTCN2016081392-appb-100043
    Figure PCTCN2016081392-appb-100044
    Figure PCTCN2016081392-appb-100045
    -OMe、-OEt、-SMe、-SEt、-NMe2、
    Figure PCTCN2016081392-appb-100046
    Figure PCTCN2016081392-appb-100047
    -Me、-Et、-CH2Ph、
    Figure PCTCN2016081392-appb-100048
    Figure PCTCN2016081392-appb-100049
    式I*-VI*和I'*-VI'*中的2,3-位置或4,5-位置处具有环状取代基，且所述环状取代基为
    Figure PCTCN2016081392-appb-100050
    Figure PCTCN2016081392-appb-100051
  14. 根据权利要求9所述的化合物，其中，所述金属桥位稠环化合物为如下化合物中的任意一种：
    Figure PCTCN2016081392-appb-100052
    Figure PCTCN2016081392-appb-100053
    Figure PCTCN2016081392-appb-100054
    Figure PCTCN2016081392-appb-100055
    Figure PCTCN2016081392-appb-100056
    Figure PCTCN2016081392-appb-100057
    Figure PCTCN2016081392-appb-100058
    Figure PCTCN2016081392-appb-100059
    Figure PCTCN2016081392-appb-100060
    Figure PCTCN2016081392-appb-100061
    Figure PCTCN2016081392-appb-100062
    Figure PCTCN2016081392-appb-100063
    Figure PCTCN2016081392-appb-100064
    Figure PCTCN2016081392-appb-100065
    以上化合物中，[Ru]1为RuA(PPh3)2，[Ru]2为RuCO(PPh3)2，[Ru]3为Ru(PPh3)2，[Ru]4为RuA2PPh3，[Rh]1为Rh(PPh3)2，[Rh]2为RhA(PPh3)2，[Rh]3为RhAPPh3，[Rh]4为RhAPPh3，[Ir]1为Ir(PPh3)2，[Ir]2为IrA(PPh3)2，[Ir]3为IrAPPh3，[Ir]4为IrAPPh3；
    A为H、Br、Cl或SCN。
  15. 权利要求9-14中任意一项所述化合物的制备方法，其特征在于，该方法包括：
    将式VII*所示的化合物与钌配合物进行环加成反应，得到式I*所示的化合物，且式I*所示的化合物中的[M]1为RuAL2；将式II*所示的化合物与碱1在有机溶剂中反应，得到式I*所示的化合物，且式I*所示的化合物中的[M]1为RhL2或IrL2；
    将式VII*所示的化合物分别与铑配合物和铱配合物进行环加成反应，得到式II*所示的化合物，且式II*所示的化合物中[M]2为RhAL2或IrAL2；或者，将式I*所示的化合物与亲核试剂进行亲核加成反应，得到式II*所示的化合物；
    将式I*所示的化合物与
    Figure PCTCN2016081392-appb-100066
    进行亲核加成反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为
    Figure PCTCN2016081392-appb-100067
    将式VIII*所示的化合物分别与钌配合物、铑配合物和铱配合物进行环加成反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-CR5R6-；将式I*所示的化合物与水或氧气反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-O-；将式I*所示的化合物与H2S、NaHS和S中的至少一种反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-S-；将式I*所示的化合物与Na2Se、NaHSe和Se的至少一种反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-Se-；将式I*所示的化合物与R7 *NH2反应，得到式III*所示的化合物，且式III*所示的化合物中的X1为-NR7 *-；
    将式X*所示的化合物与式I*所示的化合物进行环加成反应，得到式IV*所示的化合物；
    将式XI*所示的化合物与式III*所示的化合物进行扩环反应，得到式V*所示的化合物；
    将式IX*所示的化合物分别与钌配合物、铑配合物和铱配合物进行环加成反应，得到式VI*所示的化合物；
    将式I*所示的化合物在碱2的水溶液中水解，得到式I'*所示的化合物；
    将式I'*所示的化合物与亲核试剂进行亲核加成反应，得到式II'*所示的化合物；或者将式II*所示的化合物在碱2的水溶液中水解，得到式II'*所示的化合物；
    将式I'*所示的化合物与
    Figure PCTCN2016081392-appb-100068
    进行亲核加成反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为
    Figure PCTCN2016081392-appb-100069
    将式I'*所示的化合物与水或氧气反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-O-；将式I'*所示的化合物与H2S、NaHS和S中的至少一种反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-S-；将式I'*所示的化合物与Na2Se、NaHSe和Se的至少一种反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-Se-；将式I'*所示的化合物与R7*NH2反应，得到式III'*所示的化合物，且式III'*所示的化合物中的X1为-NR7*-；或者，将式III*所示的化合物在碱2的水溶液中水解，得到式III'*所示的化合物；
    将式X*所示的化合物与式I'*所示的化合物进行环加成反应，得到式IV'*所示的化合物；或者将式IV*所示的化合物在碱2的水溶液中水解，得到式IV'*所示的化合物；
    将式XI*所示的化合物与式III'*所示的化合物进行扩环反应，得到式V'*所示的化合物；或者将式V*所示的化合物在碱2的水溶液中水解，得到式V'*所示的化合物；
    将式VI*所示的化合物在碱2的水溶液中水解，得到式VI'*所示的化合物；
    Figure PCTCN2016081392-appb-100070
    式VII*-XI*中，G为-O-、-S-、-CR18*R19*-、-SiR20*R21*-或-NR22*-；
    R18*、R19*、R20*、R21*和R22*各自独立地为氢、C1-20烷基、C1-20酯基、C1-20酰基、C3-20环烷基、C1-20卤代烷基、腈基、硝基、取代或未取代的芳基或
    Figure PCTCN2016081392-appb-100071
    R23*为C1-8烷基或取代或未取代的芳基；
    R8*、R9*、R10*、R11*、R12*、R13*、R14*、R15*、R16*和R17*能选择的取代基的范围与R2*或R3*相同；
    m1和n1分别为1-6的整数，且m1+n1<8；
    所述钌配合物为RuCl2(PPh3)3、RuCl2(PMe3)3、RuCl2(PEt3)3和RuCl2(PCy3)3中的至少一种；
    所述铑配合物为RhCl(PPh3)3、RhHCl2(PPh3)3、RhCl(PMe3)3、RhCl(PEt3)3和RhCl(PCy3)3中的至少一种；
    所述铱配合物为IrHCl2(PPh3)3、IrCl(PPh3)3、IrCl(PMe3)3、IrCl(PEt3)3和IrCl(PCy3)3中的至少一种；
    所述碱1为碱金属的碳酸盐和/或氢化物；
    所述碱2为碱金属的氢氧化物；
    所述亲核试剂为卤化钠、卤化钾、卤化锂、C1-10醇、C1-10醇钠、C1-10醇钾、C1-10硫醇、C1-10硫醇钠、C1-10硫醇钾、C1-10酚、C1-10酚钠和C1-10酚钾中的至少一种。
  16. 根据权利要求15所述的方法，其中，
    所述环加成反应的条件包括反应温度为零下100℃至零上200℃；反应时间为1分钟至2天；
    所述亲核加成反应的条件包括反应温度为零下100℃至零上200℃；反应时间为1分钟至2天；
    所述扩环反应的条件包括反应温度为零下100℃至零上200℃；反应时间为1分钟至2天；
    所述反应均在有机溶剂存在下进行；所述有机溶剂为二氯甲烷、二氯乙烷、氯仿、甲醇、乙醇、丙酮、丁酮、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、甲苯、苯、二氧六环、乙醚和乙腈中的至少一种。
  17. 权利要求9-14中任意一项所述化合物在太阳能电池、光动力学治疗、光解水、锂-空气电池领域中的应用。
  18. 根据权利要求17所述的应用，其中，
    式I*、I'*、II*、II'*和VI*所示的化合物在太阳能电池领域中的应用；
    式II*所示的化合物在锂-空气电池领域中的应用；
    式III*、IV*、V*、III'*、IV'*、V'*和VI'*所示的化合物在光动力学治疗领域中的应用。
  19. 根据权利要求17所述的应用，其中，
    式I*所示的化合物中，R2*为标有数字1-6上的取代基，R2*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；进一步优选地，式I*所示的化合物用作太阳能电池的光敏化剂；
    式II*所示的化合物中，R2*为标有数字1-6上的取代基，R2*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；进一步地，式II*所示的化合物用作太阳能电池的光敏化剂或作为储锂材料应用于锂-空气电池中；
    式IV*所示的化合物中，R2*为标有数字1、2、3、7或8，优选标有数字8上的取代基，优选R2*为C1-20烷氧基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的四元环、五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的四元环、五元环或六元环取代基；
    式V*所示的化合物中，R2*为标有数字1、2、3、7、8和9中的至少一个上，优选为标有数字8和9上的取代基，R2*优选为C1-20烷氧基或C1-20酯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；Y1为-O-或-S-；进一步地，式 V*所示的化合物在肿瘤光动力学治疗中的应用；
    式VI*所示的化合物中，R2*为标有数字1、2、3、7或8上，优选标有数字8上的取代基，且R2*为芳基，优选为苯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；进一步地，式VI*所示的化合物用作太阳能电池的光敏化剂；
    式III*所示的化合物中，R2*为标有数字1-6上的取代基，R2*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；X1为-O-或-S-；进一步地，式III*所示的化合物在肿瘤光动力学治疗中的应用；
    式I'*所示的化合物中，R3*为标有数字1-6上的取代基，R3*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置和5,6-位置中的任意一个，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；进一步优选地，式I'*所示的化合物用作太阳能电池的光敏化剂；
    式II'*所示的化合物中，R3*为标有数字1-6上的取代基，R3*优选为H；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；进一步优选地，式II'*所示的化合物用作太阳能电池的光敏化剂；
    式III'*所示的化合物中，R3*为标有数字1-6上的取代基，R3*为芳基，优选为苯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；X1为
    Figure PCTCN2016081392-appb-100072
    进一步优选地，式III'*所示的化合物在肿瘤光动力学治疗中的应用；
    式IV'*所示的化合物中，R3*为标有数字1-8上的取代基，R3*为芳基，优选为苯基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；X1为
    Figure PCTCN2016081392-appb-100073
    进一步优选地，式IV'*所示的化合物在肿瘤光动力学治疗中的应用；
    式V'*所示的化合物中，R3*为标有数字1-9上的取代基，R3*为C1-20烷基；标有数字1-6的2,3- 位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；Y1为-O-或-S-；进一步优选地，式V'*所示的化合物在肿瘤光动力学治疗中的应用；
    式VI'*所示的化合物中，R3*为标有数字1-8上的取代基，R3*为C1-20烷氧基；标有数字1-6的2,3-位置、3,4-位置、4,5-位置或5,6-位置，优选4,5-位置处有取代或未取代的环状取代基；所述环状取代基优选为全部由碳原子组成的五元环或六元环取代基，或者由氧、氮和硅原子中的任意一个和碳原子一起组成的五元环或六元环取代基；所述取代的环状取代基上的取代基优选为C1-20酯基；进一步优选地，式VI'*所示的化合物在肿瘤光动力学治疗中的应用。
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