WO2004072082A1 - Superphthalocyanine compounds containing six isoindole subunits ini the porphyrazine cycle, the preparation processes and uses of them - Google Patents

Superphthalocyanine compounds containing six isoindole subunits ini the porphyrazine cycle, the preparation processes and uses of them Download PDF

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WO2004072082A1
WO2004072082A1 PCT/CN2004/000109 CN2004000109W WO2004072082A1 WO 2004072082 A1 WO2004072082 A1 WO 2004072082A1 CN 2004000109 W CN2004000109 W CN 2004000109W WO 2004072082 A1 WO2004072082 A1 WO 2004072082A1
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formula
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sulfonic acid
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Xi Guang Du
Guo Tong Du
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Dalian University of Technology
Jilin University
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0629—Heterocyclic compounds containing one hetero ring being five-membered containing one hetero atom
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
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    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
    • G03G5/0648—Heterocyclic compounds containing two or more hetero rings in the same ring system containing two relevant rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
    • G03G5/0651—Heterocyclic compounds containing two or more hetero rings in the same ring system containing four relevant rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
    • G03G5/0655—Heterocyclic compounds containing two or more hetero rings in the same ring system containing six relevant rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0696—Phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni

Definitions

  • the present invention relates to a superphthalocyanine compound having six isoindole subunits in a class of laver ring, a synthesis method and use thereof, and belongs to the technical field of synthesis of phthalocyanine compounds and preparation of related materials.
  • Phthalocyanine compounds are a class of widely used, very important functional molecules. At present, the application fields of phthalocyanine compounds have been involved in chemical sensor devices, electrophotographic materials, semiconductor devices, organic conductive materials, photodynamic therapy for cancer, solar cell materials, liquid crystal display materials, nonlinear optical materials, laser dyes, fuels. Battery, optical information storage and other fields. Since the first synthesis of Bumi and others in 1907, turnip has formed a family with a large number of derivatives.
  • the phthalocyanine group having four isoindole units, the superphthalocyanine group having five isoindole units, and the number of isoindole units contained in the porphyrin ring in the phthalocyanine molecule are classified.
  • a phthalocyanine family having three isoindole units except for the superphthalocyanine compound having five isoindole units, a phthalocyanine group having four isoindole units and a subphthalocyanine having three isoindole units due to poor stability and a small number of compounds The family has a large number of derivatives.
  • Superphthalocyanine compounds having six isoindole subunits in the pyromazine ring have not been reported.
  • the invention provides a super phthalocyanine compound having six isoindole subunits in a pyroxazine ring, a synthesis method and a use thereof, adding a new family to the phthalocyanine compound family and providing new materials for many fields. .
  • M includes an atom of the elements listed in the following table:
  • a 2 , A 3 , and A 4 are elements C and N atoms; R 2 and R 3 are hydrogen and various halogen atoms such as fluorine, chlorine, bromine, and iodine; or nitro, sulfonic acid groups, and aliphatic hydrocarbon groups are substituted.
  • a sulfonic acid group a substituted sulfonic acid group having a fluoro group substituted with fluorine, chlorine, bromine, iodine, a nitro group, a sulfonic acid group, an amino group, a hydroxyl group, a carbonyl group, and various alkoxy groups;
  • a carbonyl group, an alkoxycarbonyl group and an aryloxy group are aryloxy groups of a substituted phenyl group having a fluorine, chlorine, bromine, iodine, a nitro group, a sulfonic acid group, an amino group, a hydroxyl group, a carbonyl group, and various alkoxy groups bonded to a benzene ring.
  • a carbonyl group a hydroxy group and an alkoxy group
  • an aryloxy group is a substituted phenyl group having a fluorine, a chlorine, a bromine, an iodine, a nitro group, a sulfonic acid group, an amino group, a hydroxyl group, a carbonyl group, and various methoxy groups attached to the benzene ring.
  • An oxy group an amino group, an aliphatic group substituted with an aliphatic hydrocarbon group, a benzene ring substituted with an aryl group, a fluorine, a chlorine, a bromine, an iodine, a nitro group, a sulfonic acid group, an amino group, a hydroxyl group, a carbonyl group, and various alkoxy groups.
  • a substituted amine group; R 5 a group having the following structure:
  • the I, II, III moiety in the formula (1) may be the same structure or a different structure.
  • the compound of the following formula (2) has the following structure:
  • an atom of Mj, M 2 and an element represented by the formula (1) M The range is the same, IV ⁇ and can be atoms of the same element, or atoms of different elements; in the formula (2), ⁇ 2 , ⁇ 3 , ⁇ 4, ⁇ , ⁇ 2 ⁇ ⁇ 3 ⁇ ⁇ 4 ⁇
  • R 2 , R 3 , , R 2 , R 3 , , , and the range of the elemental atom represented by the formula (AA 2 , A 3 , and A 4 , and the range of the elemental atom and the group represented by R 2 , R 3 , and R 4 are the same;
  • the parts I, II, III, IV, V, VI in the formula (2) may be the same structure or different structures.
  • the compound of the formula (1) can be synthesized from the compound of the formula (3), the atom of the group A 2 , A 3 , A4 , the substituent of R 2 , R 3 , R 4 and the formula ( 1)
  • the range of element atoms represented by Aj, A 2 , A 3 , and A 4 in the compound is the same as the range of atoms and groups represented by R 2 , R 3 , and R4;
  • R represents a carboxyl group, a cyano group;
  • R represents a carboxylic anhydride group, a carboxylic acid imido group, a 1,3-isodecyl group;
  • the synthesis consists of the following steps:
  • the solvent used in the reaction includes quinoline, nitrobenzene, trichlorobenzene, 1-chloronaphthalene, isoamyl alcohol, and urea;
  • the elemental substance and compound include a halogenated salt (CuCl), a sulfate (NiS0 4 ), an acetate (HfAc 2 ), a nitrate (AgN0 3 );
  • the catalyst includes ammonium molybdate and sodium alkoxide.
  • the preparation method of the compound of the formula (2) comprises the following steps:
  • the compound of the formula (2) can be prepared by using the compound of the formula (1), and the compound of the formula (1) is charged into a thermal reaction apparatus with a vacuum and an addition, at 10 - 4 to 10 - 1 () Pa, 400 ⁇ The reaction is carried out at 600 ° C for 8 to 48 hours, and a bimolecular condensation occurs to obtain a compound of the formula (2).
  • the compound of the formula (1) is used as an intermediate compound of a synthetic phthalocyanine compound, and is mixed with a raw material compound of another synthetic phthalocyanine in a certain ratio, and under certain conditions, three or four of the laver ring can be synthesized.
  • the compound of the formula (2) provided by the present invention has a novel structure of a novel phthalocyanine compound and exhibits a new property which is not possessed by a series of existing phthalocyanine compounds.
  • These properties are: UY-VIS-MR absorption spectrum has three strong absorption peaks, the most characteristic of which is near-infrared absorption near 1428nm; surface photovoltaic characteristics; photoluminescence characteristics; electroluminescence characteristics; Thermal stability; good electrical conductivity, etc.
  • this class of molecules makes this class of compounds potentially useful in a number of important areas.
  • the compound can be used as a near-infrared optoelectronic material for the preparation of near-infrared optoelectronic devices, etc.; the ordered an ultrathin film exhibits good electrical anisotropy and can be used to prepare molecular device circuits.
  • Molecular wires; such compounds exhibit photoluminescence and electroluminescence properties and can be used in the preparation of organic display devices and the like.
  • the compound of formula (2) can possess a large population of derivatives.
  • the laverazine ring with four isoindole subunits can bind to more than seventy elements. If two different elements are taken out from more than seventy elements and combined to carry out the synthesis of the compound of the formula (2), only two hundred and five hundred kinds of derivatives of the compound of the formula (2) will be obtained only due to the change of the central ion. By introducing a substituent on the peripheral aromatic ring which is conjugated to the laverazine ring, the number of derivatives will be greatly increased. Such a compound of the formula (2) having a large number of derivatives will constitute an important family of phthalocyanine compounds. The invention has important significance for promoting the development of fields such as chemistry, materials science and information science.
  • Figure 7 A simulated image of compound i ai .
  • Figure 8. Molecular structure diagram of Compound 2.
  • Figure 9. Spectrum of Compound 2 1 .
  • Figure 22 is a structural diagram of the compound 2a 2 .
  • Figure 23 is a structural diagram of the compound la 3 .
  • Figure 24 is a structural diagram of the compound 2a 3 .
  • ⁇ ⁇ 4 in the general formula (1) represents a nitrogen atom
  • 2 and 3 represent a carbon atom
  • R4 does not represent any group and atom
  • ⁇ represents a hydrogen atom
  • R 5 ⁇ R6 representative NH
  • urea a compound of the formula (3) such as: Pyrazine-2,3-dicarboxylic acid 4.0008 g (0.0238 mol), CuCl 2 '2H 2 0 1.3683 g (0.0080 mol) ), (NH 4 ) 2 MoH N0 4 0.800 lg finely mixed and hooked into a steel bomb with a Teflon-lined seal, and the steel bomb was placed in an oven and heated to 240 ° C for 8 hours; The bomb was cooled to room temperature to open the lid, and the black solid was taken out; the black solid was placed in a vacuum purification apparatus, and purified at 10 to 4 Pa at 300 ° C for 24 hours.
  • a compound of the formula (3) such as: Pyrazine-2,3-dicarboxylic acid 4.0008 g (0.0238 mol), CuCl 2 '2H 2 0 1.3683 g (0.0080 mol) ), (NH 4 ) 2 MoH N0 4 0.800 lg finely mixed and hooked
  • ⁇ ⁇ 4 in the general formula (1) represents a nitrogen atom
  • ⁇ 2 and ⁇ 3 represent a carbon atom
  • R4 does not represent any group and atom
  • ⁇ represents a hydrogen atom
  • ⁇ represents a Cu(II) ion
  • I, II, III, IV, V, VI have the same structure and constitute compound 2 of formula (2).
  • the structural formula is Figure 8.
  • the obtained compound 1 of the general formula (1) is placed in a vacuum apparatus and reacted at 10 to 4 Pa at 500 ° C for 24 hours to produce a bimolecular condensation reaction of the compound 1 of the general formula (1), thereby obtaining a general formula.
  • (2) Compound 2 ai Compound 2 ai .
  • the molecular ion peak of the compound 2 ai of the general formula (2) was measured by a mass spectrometer ( FIG. 9 ) M+Na + : 931.9193 amu, which is close to the calculated value of 930.7240. Compliant with the calculated value of 93.31919 for M+H+Na+. This is due to hydrogen in the mass spectrometer the general formula (2) reacting compound 21 in the plasma environment.
  • Formula ⁇ spectrum (FIG.
  • UV-VIS-NIR absorption spectrum of compound 2 ai of formula (2) UV UV-VIS-NIR absorption spectrum of compound 2a x formic acid solution of formula (2) was investigated by UV-VIS-NIR spectrometer (Fig. 16) The results show that, in addition to the absorption peaks in the ultraviolet region and the visible region, which are common to phthalocyanines, there is an absorption in the near red region (1.428 U rn), and the absorption coefficient is large.
  • the UV-VIS-MR absorption spectrum of the compound 2 ai of the formula (2) observed by us is quite different from that of the general phthalocyanine.
  • a photovoltaic device particularly a near-infrared photovoltaic device, can be prepared using the compound of the formula (2).
  • Formula (2) photoactive compound 231 near-infrared region to the infrared photodynamic treatment of cancer by near infrared transmission properties of penetrating the human body, can be accomplished in vitro irradiation of light.
  • This property can also be used in the preparation of gas sensor materials for the determination of harmful substances in the environmental protection field.
  • Example 4 Photoluminescence spectrum of compound 2 (fluorescence spectrum) Using a fluorescence spectrometer at a temperature of 10 K The fluorescence spectrum of Compound 2 ai was measured by exciting the compound 2 ai with excitation light at 1200 nm and 350 nm (Figs. 17, 18). The results show that the compound is in the near infrared region of 1530 nm and the visible region of 450 nm. Fluorescence is emitted. Using this property, a compound 2 can be used to prepare a light-emitting device, particularly a near-infrared light-emitting device.
  • Photovoltaic properties of compound 2 ai of Example 5 (: surface photovoltage spectrum SPS)
  • the photovoltaic characteristic curve of the compound 2 1 was measured by a surface photovoltage spectrometer, that is, the surface photovoltage spectrum (Fig. 19). The results show that the photovoltaic properties of the compound 2 1 are very obvious, and the photovoltaic characteristics also appear in the near-infrared region at about llOOiim. Using this property, a device based on the photoelectric conversion principle can be prepared using Compound 2.
  • Compound 2 at 10- 4 ⁇ 10_ 1 ( ⁇ , 900 ⁇ vacuum deposition conditions, film material produced by mass spectrometry, NMR and XPS results revealed that the compound 2a x remains, which indicates that the compound having a heat ultrahigh Stability. Applying this property, compound 2 can be used to prepare photovoltaic devices that operate in high temperature environments for aerospace and other fields.
  • Example 6 Under the conditions of Example 6, the compound 2 ai was evaporated onto an ITO glass to obtain a ruthenium film having a thickness of about 100 nm (Fig. 20). Determination of the conductivity of the ruthenium film is 4 X 10 5 ⁇
  • compound 2 can be used to prepare conductive materials in molecular devices for use in the field of information engineering.
  • ⁇ ⁇ 4 in the general formula (1) represents a nitrogen atom
  • ⁇ 2 and ⁇ 3 represent a carbon atom
  • R4 does not represent any group and atom
  • ⁇ represents a hydrogen atom
  • ⁇ represents a Co(II) ion
  • urea a compound of the formula (1) such as: Pyrazine-2,3-dicarboxylic Acid 4.0008 g (0.0238 mol), CoCl 2 6H 2 0 1.8876 g (0.0080 mol) , (NH4) 2 MoO 4 0.8001g was finely mixed and filled into a steel bomb with a Teflon-lined seal.
  • the steel bomb was placed in an oven and heated to 240 ° C for 8 hours. After the steel bomb was cooled to room temperature, the lid was removed and the black solid was taken out. The black solid was placed in a vacuum purification apparatus and purified at 1 (T 4 Pa, 300 ° C for 24 hours. After the above operation, the molecular ion peak M+: 533.3452 amu was obtained by the compound la 1 ⁇ 5 mass spectrometer, and The calculated value of 533.3344 is consistent.
  • a 2 , A 3 and A 4 represent a carbon atom, and R 3 represents a hydrogen atom, which represents a nitro group, and M represents a Ni(II) ion, and ⁇ represents
  • A4 represents a nitrogen atom
  • a 2 and A 3 represent a carbon atom, and do not represent any group and atom
  • R 3 represents a hydrogen atom
  • Mi represents a Cu(II) ion
  • AA, 2 , A, 3 and A, 4 represent a carbon atom
  • R and R, 4 represents a hydrogen atom
  • R 2 represents a nitro group
  • M 2 represents a ruthenium (iridium) ion
  • the obtained compound 1 3 ⁇ 41 and the compound 1 were mixed at a molar ratio of 1/1, and placed in a vacuum apparatus, and reacted at 1 (T 4 Pa, 500 ° C for 8 hours to produce a double of the compound 1 and the compound la 3 After the molecular cross condensation reaction, the compound 2 was obtained.
  • the molecular ion peak M+Na+ 1054.9367 amu of the compound 2a 3 was measured by a mass spectrometer, which was in agreement with the calculated value of 1054.9356.

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Description

紫菜嗪环中具有六个异吲哚结构亚单元的
技术领域
本发明涉及一类紫菜嗪环中具有六个异吲哚结构亚单元的超酞 菁类化合物、合成方法及用途，属于酞菁类化合物的合成方法及相关 材料制备的技术领域。
背景技术
酞菁类化合物是一类应用广泛， 非常重要的功能分子。 目前， 酞 菁类化合物的应用领域已涉及到化学传感器件、电子照相材料、半导 体器件、有机导电材料、癌症的光动力治疗、太阳能电池材料、液晶 显示材料、非线性光学材料、激光染料、燃料电池、光信息存储等领 域。 酞菁自 1907年第一次由布鲁恩 (Bmmi)等人合成后， 已形成拥有 巨大数目衍生物的家族。在这酞菁化合物家族中，按酞菁分子中紫菜 嗪环含有的异吲哚单元数分类，具有四个异吲哚单元的酞菁族、具有 五个异吲哚单元的超酞菁族和具有三个异吲哚单元的亚酞菁族。除具 有五个异吲哚单元的超酞菁族化合物， 由于稳定性较差、化合物数目 较少以外，具有四个异吲哚单元的酞菁族和具有三个异吲哚单元的亚 酞菁族都有数目众多的衍生物。紫菜嗪环中具有六个异吲哚结构亚单 元的超酞菁类化合物未见报道。
1
确 认 本 发明的公开：
本发明提供一类紫菜嗪环中具有六个异吲哚结构亚单元的超酞 菁类化合物、合成方法及用途， 为酞菁类化合物家族中增添了新的一 族和为众多领域提供新的材料。
下述通式 (1)化合物， 具有以下结构：
Figure imgf000004_0001
(1)
通式 (1)化合物中， M包括下表所列元素的原子:
Figure imgf000004_0002
A2、 A3、 A4为元素 C、 N原子； 、 R2、 R3、 为氢 及各种卤原子如氟、 氯、 溴、 碘； 或硝基、 磺酸基、 带脂肪烃基 取代的磺酸基； 带有芳基取代的苯环上连有氟、 氯、 溴、 碘、 硝 基、磺酸基、氨基、羟基、羰基、及各种烷氧基的取代的磺酸基； 羰基、 烷氧羰基及芳氧基为苯环上连有氟、 氯、 溴、 碘、 硝基、 磺酸基、氨基、羟基、羰基、及各种烷氧基的取代苯基的芳氧基 羰基； 羟基及烷氧基； 芳氧基为苯环上连有氟、 氯、 溴、 碘、 硝 基、 磺酸基、 氨基、 羟基、羰基、及各种垸氧基的取代苯基的芳 氧基； 氨基、带脂肪烃基取代的胺基、带有芳基取代的苯环上连 有氟、 氯、 溴、 碘、 硝基、 磺酸基、 氨基、 羟基、 羰基、 及各种 烷氧基的取代的胺基； R5、 为具有下面结构的基团：
Figure imgf000005_0001
通式 （1 ) 中 I， II， III部分可以是相同结构， 也可以是不同结构 < 下述通式 (2)化合物， 具有以下结构：
Figure imgf000005_0002
(2)
通式 (2)化合物中， Mj, M2与通式 (1)M所代表的元素的原子 范围相同， IV^和 可以是同一种元素的原子， 也可以是不同种 元素的原子； 通式 (2)中 、 Α2、 Α3、 Α4、 Α 、 Α2\ Α3\ Α4\
R2、 R3、 、
Figure imgf000006_0001
R2、、 R3、、 、与通式 ( A A2、 A3、 A4 所代表的元素原子的范围和 、 R2、 R3、 R4所代表的元素原子 及基团的范围相同；
通式 (2)中 I、 II、 III、 IV、 V、 VI部分可以是相同结构， 也 可以是不同结构。
通式 (1)化合物的制备方法：
通式 (1)化合物可从用通式 (3)化合物来合成， 通式 (3)化合物中 、 A2、 A3、 A4的原子和 、 R2、 R3、 R4取代基与通式 (1)化合物中 Aj、 A2、 A3、 A4所代表的元素原子的范围和 、 R2、 R3、 R4所代表 的原子及基团的范围相同； R代表羧基、氰基； R… R、代表羧酸酐基、 羧酸亚胺基、 1 , 3-异吲哚基；
Figure imgf000006_0002
合成包括以下步骤：
反应所用的溶剂包括喹啉、 硝基苯、 三氯苯、 1-氯萘、 异戊醇、 尿素；
向某种如上提到的单一或混合溶剂中加入一定量的通式 (3)化 合物与通式（1 )化合物中 M所代表的元素的单质及化合物， 按摩尔 比： 通式 （3 )化合物 / M = 1.5~5.5/l相混合的原料， 加入一定量的 催化剂后，装入密闭的容器，在 180〜240 °C条件下反应 8至 48小时， 得到黑色固体， 在 10-4〜10-10 Pa， 200〜 300 °C条件下去除杂质后得 到通式 （2)化合物；
所述的单质和化合物包括卤化盐 (CuCl)、硫酸盐 (NiS04)、醋酸盐 (HfAc2)、 硝酸盐 (AgN03);
.所述的催化剂包括钼酸铵、 醇钠。
通式 (2)化合物的制备方法， 包括以下步骤：
通式 (2)化合物可用通式 （1 ) 化合物制备， 将通式 （1 ) 化合物 装入一个带有真空和可以加的热反应装置中， 在 10_4〜10—1() Pa， 400~600°C条件下反应 8〜48小时， 发生双分子缩合后得到通式 (2) 化合物。
以通式 （1 ) 化合物做为合成酞菁化合物的中间体化合物， 与另 一合成酞菁的原料化合物按一定比例混合，在一定条件下可合成出紫 菜嗪环中含有三个、四个、五个及六个异吲哚结构亚单元的酞菁化合 物。
本发明所提供的通式 （2) 化合物， 具有全新的酞菁类化合物的 基本结构， 表现出一系列已有的酞菁类化合物所不具备的新的性质。 这些性质是： UY— VIS— MR吸收光谱具有三个强吸收峰， 其中最有 特征的是 1428nm处时附近出现的近红外吸收； 表面光伏特性； 光致 发光特性； 电致发光特性；超高的热稳定性； 良好的导电性等。
这类分子所具有的一系列独特的性质，使得该类化合物在众多重 要领域中具有潜在的作用。例如，该类化合物表现出的近红外光电活 性，可使该类化合物成为一种近红外光电材料，用于制备近红外光电 器件等； 该类化合物有序超薄薄膜所表现出的良好的导电各向异性， 可用于制备分子器件线路的分子导线；该类化合物表现出的光致发光 和电致发光特性， 可用于制备有机显示器件等。另外， 由于该类化合 物在分子结构上所具有的特征，例如，在一个大的紫菜嗪环中有两个 金属离子， 使通式（2)化合物能拥有一个庞大的衍生物群体。 因为， 具有四个异吲哚亚单元的紫菜嗪环可以与七十余种元素结合。如果从 七十余种元素中取出二种不同元素进行组合进行通式 （2)化合物的 合成， 仅仅由于中心离子的改变， 将得到通式 (2)化合物二千五百 多种衍生物。通过在与紫菜嗪环并接的外围芳香环上引入取代基，将 使衍生物的数目剧增。 这种拥有数目众多衍生物的通式 （2)化合物 将构成酞菁类化合物家族中重要的一族。本发明对推动化学、材料科 学、 信息科学等领域的发展具有重要的意义。
附图说明
图 1、 化合物 1的结构通式 (1)。
图 2、 化合物 2的结构通式 (2)。
图 3、 化合物 3的结构通式 (3)。
图 4、 化合物 1¾的分子结构图。
图 5、 化合物 1¾的^^谱图。
图 6、 化合物 1 1的811^1图像。
图 7、 化合物 iai的模拟图像。
图 8、 化合物 2 的分子结构图。 图 9、 化合物 2 1的]^8谱图。
图 10、 化合物？^的！!1!^^谱图
图 11、 化合物 2a 的 I^C^NMR谱图。
图 12、 化合物 2a 的 XPS谱图。
图 13、 化合物 2a 的 STM图像。
图 14、 化合物 2a 的 STM 3D图像。
图 15、 化合物 2a 的模拟图。
图 16、 化合物 2a 的 UV-VIS-NIR吸收光谱。
图 17、 化合物 2a 的光致发光谱 (近红外区)。
图 18、 化合物 2a 的光致发光谱 (可见区)。
图 19、 化合物 2a 的表面光电压谱。
图 20、 化合物 2a在 ΠΌ玻璃上薄膜的三维 FAM图像 < 图 21、 化合物 la2的结构图。
图 22、 化合物 2a2的结构图。
图 23、 化合物 la3的结构图。
图 24、 化合物 2a3的结构图。
^佳实施例
实施例 1 化合物 1 的合成
选择通式 (1)中 Α^Π Α4代表氮原子， 2和 3代表碳原子， 和 R4不代表任何基团和原子， 和 代表氢原子， Μ代表 Cu(II)离子， R5〜R6代表 NH
HN
I， II， III部分的结构相同， 构成化合物 lai， 结构式为图 4。
称取尿素 8.0001g， 通式 （3 ) 化合物如： 2,3-吡嗪二甲酸 (Pyrazine-2,3 -dicarboxylic Acid) 4.0008g (0.0238mol)， CuCl2'2H20 1.3683g (0.0080mol), (NH4)2MoH N040.800 lg研细混合均勾后装入带有 聚四氟乙烯衬里的钢弹中密封，将钢弹放入烘箱中加热至 240°C 8小 时； 待钢弹冷却至室温开盖， 取出黑色固体； 将该黑色固体放入真空 提纯装置中， 在 10_4Pa， 300°C条件下提纯 24小时。 经过上述操作制 得了通式 ( 1 )化合物 la10质谱仪测得分子离子峰 (图 5)M+: 537.9452 amu, 与计算值 537.9472相吻合。 用超高真空的 STM获得了化合物 la,的单分子图像 (图 6)， 该图像与计算机模拟结果 (图 7)相符合。
实施例 2化合物 2ai的合成
选择通式 (1)中 Α^Π Α4代表氮原子， Α2和 Α3代表碳原子， 和 R4不代表任何基团和原子， 和 代表氢原子， Μ代表 Cu(II)离子， I、 II、 III、 IV、 V、 VI的结构相同， 构成通式（2)化合物 2 ， 结构 式为图 8
将制得的通式 （1 )化合物 1 放入真空装置中， 在 10_4 Pa， 500 °C条件下反应 24小时， 发生通式 （1 )化合物 1 的双分子缩合反应 后， 制得了通式 （2)化合物 2ai。 质谱仪测得通式 （2)化合物 2ai 的分子离子峰 (图 9) M+Na+ :931.9193 amu,与计算值 930.7240相接近， 与 M+H+Na+的计算值 931.7319相符合。这归结为在质谱仪中的氢气 与通式（2)化合物 2 1在等离子体的环境中发生反应。 通式 （2)化 合物 2 1的^ 谱 (图 10、 11)、 XPS (图 12)谱、 和 STM单分子图像 (图 13、 14、 15)进一步确定了通式（2)化合物 2ai的分子结构。 XPS 谱测得通式（2)化合物 2 1的元素有0、 N、 H、 Cu, NMR的 H1谱 确定了通式 （2)化合物 2ai中氢的种类和数量， NMR的 C13谱确定 了通式（2)化合物 2 1中（：的种类， STM分子图像确定了通式 （2) 化合物 2ai的分子构型。
实施例 3通式 （2)化合物 2ai的 UV-VIS-NIR吸收光谱 釆用 UV-VIS-NIR光谱仪研究通式（2)化合物 2ax甲酸溶液的 UV-VIS-NIR吸收光谱（图 16)、， 结果表明， 它除了具有一般酞菁所 共同具有的紫外区和可见区的吸收峰外，出现了一个在近红区（1.428 U rn)的吸收 ， 吸光系数很大。我们所观察到的通式（2)化合物 2ai 的 UV-VIS-MR吸收光谱与一般酞菁有很大的差别。应用这一性质可 用通式（2)化合物制备光电器件，特别是近红外光电器件。通式（2) 化合物 231近红外区的光活性用于癌症的红外光动力治疗时， 利用近 红外线对人体的穿透特性，在体外照射可完成光的传输过程。这一特 性还可以用于环保领域中有害物质测定所用气敏传感器材料的制备 实施例 4通式 （2) 化合物 2 的光致发光谱 (荧光光谱） 使用荧光光谱仪在 10 K的温度条件下分别用 1200nm和 350nm 波长的激发光激发化合物 2ai， 测量化合物 2ai的荧光光谱（图 17、 18)。 结果表明该化合物在 1530nm的近红外区和 450nm的可见光区 发射荧光。应用这一性质可用化合物 2制备发光器件，特别是近红外 发光器件。
实施例 5化合物 2ai的光伏特性 (：表面光电压谱 SPS)
用表面光电压谱仪测得化合物 2 1的光伏特性曲线， 即表面光电 压谱 （图 19)。 结果表明化合物 2 1的光伏特性非常明显， 并在近红 外区大约在 llOOiim左右也出现光伏特性。应用这一性质可用化合物 2制备基于光电转换原理的器件。
实施例 6化合物 2¾1的超高的热稳定性
将化合物 2 在10-4~10_1(^， 900Ό条件下进行真空镀膜， 对生 成的膜物质进行质谱、核磁和 XPS表征，发现该化合物 2ax仍然存在。 这表明该化合物具有超高的热稳性。应用这一性质可用化合物 2制备 在高温环境中工作的光电器件，用于航天航空等领域。 '
实施例 7化合物 2ai溥膜的导电性
在实施例 6的条件下， 将化合物 2ai蒸镀到 ITO玻璃上， 得到 lOOnm左右厚度的溥膜 (图 20)。 测定溥膜的电导率为 4 X 105 Ω
- m-l。应用这一性质可用化合物 2制备分子器件中的导电材料，用于 信息工程领域。
实施例 通式 （ 1 )化合物 la2的合成
选择通式 (1)中 Α^Π Α4代表氮原子， Α2和 Α3代表碳原子， 和 R4不代表任何基团和原子， 和 代表氢原子， Μ代表 Co(II)离子， 代表
Figure imgf000013_0001
I, II， III部分的结构相同， 构成化合物 la2， 结构式为图 21。
称取尿素 8.0001g， 通式 （1 ) 化合物如： 2,3-吡嗪二甲酸 (Pyrazine-2,3-dicarboxylic Acid) 4.0008g (0.0238mol) , CoCl26H20 1.8876g (0.0080mol), (NH4)2MoO40.8001g研细混合均匀后装入带有 聚四氟乙烯衬里的钢弹中密封。将钢弹放入烘箱中加热至 240°C 8小 时。待钢弹冷却至室温开盖， 取出黑色固体。将该黑色固体放入真空 提纯装置中， 在 l(T4Pa， 300°C条件下提纯 24小时。 经过上述操作制 得了化合物 la1 <5 质谱仪测得分子离子峰 M+: 533.3452 amu， 与计算 值 533.3344相吻合。
实施例 9通式 （2)化合物 la22a2的合成与表征
选择通式 (1)中 ^和 A4代表氮原子， A2和 A3代表碳原子， 和 不代表任何基团和原子， R2和 代表氢原子， IV^代表 Cu(II) 离子， 代表 Co(II)离子， I、 II、 III、 IV、 V、 VI的结构相同， 构 成化合物 2a1 结构式为图 22。
将制得的化合物 1 和化合物 la2按摩尔比为 1/1混合后放入真空 装置中， 在 10·4 Pa, 550°C条件下反应 28小时， 发生化合物 和化 合物 1 的双分子交叉缩合反应后， 制得了化合物 2 。 质谱仪测得 化合物 2a2的分子离子峰 M+Na+ :985.2193 amu,与计算值 985.1241相 符合。 实施例 10通式 （ 1 )化合物 la3的合成与表征
选择通式 (1)中 、 A2、 A3和 A4代表碳原子， 和 R3 代表氢原子， 代表硝基， M代表 Ni(II)离子， 〜 代表
Figure imgf000014_0001
I， II， ΙΠ部分的结构相同， 构成化合物 la3， 结构式为图 23。
称取尿素 8.0001g， 4-硝基邻苯二甲酸 (4-Nitro-phthalic acid)5.0460g (0.0239mol), NiS047H20 2.242g (0.0080mol), (NH4)2Mo040.800 lg研 细混合均勾后装入带有聚四氟乙烯衬里的钢弹中密封。将钢弹放入烘 箱中加热至 250Ό 18小时。待钢弹冷却至室温开盖，取出黑色固体。 将该黑色固体放入真空提纯装置中， 在 10—4Pa， 300°C条件下提纯 24 小时。 经过上述操作制得了化合物 la3。 质谱仪测得分子离子峰 M +: 662.1655 amu, 与计算值 662.1588相吻合。
实施例 11通式 （2)化合物 2 的合成与表征
选择通式 (1)中 和 A4代表氮原子， A2和 A3代表碳原子， 和 不代表任何基团和原子， 和 R3代表氢原子， Mi代表 Cu(II) 离子， A A、2、 A、3和 A、4代表碳原子， R 和 R、4代表氢原 子， R2代表硝基， M2代表 Μ(Π)离子， 结构式为图 24。
将制得的化合物 1¾1和化合物 1 按摩尔比为 1/1混合后放入真空 装置中， 在 1(T4 Pa， 500°C条件下反应 8小时， 发生化合物 1 和化合 物 la3的双分子交叉缩合反应后， 制得了化合物 2 。 质谱仪测得化 合物 2a3的分子离子峰 M+Na+ 1054.9367 amu,与计算值 1054.9356相 符合。

Claims

权 利 要 求
1.下述通式 (1)化合物， 具有以下结构 -
Figure imgf000015_0001
通式 (1)化合物中， M包括下表所列元素的原子:
Figure imgf000015_0002
Aj、 A2、 A3、 A4为元素 C、 N原子； 、 R2、 R3、 为氢 及各种卤原子如氟、 氯、 溴、 碘； 或硝基、 磺酸基、 带脂肪烃基 取代的磺酸基； 带有芳基取代的苯环上连有氟、 氯、 溴、碘、 硝 基、磺酸基、氨基、羟基、羰基、及各种烷氧基的取代的磺酸基； 羰基、 垸氧羰基及芳氧基为苯环上连有氟、 氯、 溴、 碘、 硝基、 磺酸基、 氨基、羟基、羰基、 及各种垸氧基的取代苯基的芳氧基 羰基； 羟基及烷氧基； 芳氧基为苯环上连有氟、 氯、 溴、 碘、 硝 基、 磺酸基、 氨基、 羟基、羰基、 及各种垸氧基的取代苯基的芳 氧基； 氨基、带脂肪烃基取代的胺基、 带有芳基取代的苯环上连 有氟、 氯、 溴、 碘、 硝基、 磺酸基、 氨基、 羟基、 羰基、 及各种 垸氧基的取代的胺基； R5、 为具有下面结构的基团：
Figure imgf000016_0001
通式（1 ) 中 I， II， III部分可以是相同结构， 也可以是不同结构。
2、 下述通式 (2)化合物， 具有以下结构：
Figure imgf000016_0002
(2)
通式 (2)化合物中， M2与通式 (1)M所代表的元素的原子 范围相同， Μ^Π Μ2可以是同一种元素的原子， 也可以是不同种 元素的原子； 通式 (2)中 、 Α2、 Α3、 Α4、
Figure imgf000016_0003
、 R2、 R3、 、 Rr、 R2、、 R3、、 、与通式 (1) 、 A2、 A3、 A4 所代表的元素原子的范围和 、 R2、 R3、 R4所代表的元素原子 及基团的范围相同；
通式 (2)中 I、 II、 III、 IV、 V、 VI部分可以是相同结构， 也 可以是不同结构。
3、 通式 (1)化合物的制备方法：
通式 (1)化合物可从用通式 (3)化合物来合成， 通式 (3)化合物中 A2、 A3、 A4的原子和 、 R2、 R3、 R4取代基与通式 (1)化合物中 、 A2、 A3、 A4所代表的元素原子的范围和 、 R2、 R3、 所代表 的原子及基团的范围相同； R代表羧基、氰基； R、〜R、代表羧酸酐基、 羧酸亚胺基、 1， 3-异吲哚基；
Figure imgf000017_0001
合成包括以下步骤：
反应所用的溶剂包括喹啉、 硝基苯、 三氯苯、 1-氯萘、 异戊醇、 尿素；
向某种如上提到的单一或混合溶剂中加入一定量的通式 (3)化 合物与通式 ( 1 )化合物中 M所代表的元素的单质及化合物， 按摩尔 比： 通式（3 )化合物 / M = 1.5~5.5/l相混合的原料， 加入一定量的 催化剂后，装入密闭的容器，在 180~240 °C条件下反应 8至 48小时， 得到黑色固体， 在 10-4〜10-10 Pa， 200〜 300Ό条件下去除杂质后得 到通式 （2)化合物；
所述的单质和化合物包括卤化盐 (CuCl)、硫酸盐 (NiS04)、醋酸盐 (HfAc2)、 硝酸盐 (AgN03);
所述的催化剂包括钼酸铵、 醇钠。
4、 通式2)化合物的制备方法， 包括以下步骤：
通式 (2)化合物可用通式 （1 ) 化合物制备， 将通式 （1 ) 化合物 装入一个带有真空和可以加的热反应装置中， 在 10_4 ~10_1Q Pa， 400~600°C条件下反应 8〜48小时， 发生双分子缩合后得到通式 （2) 化合物。
5、 以通式（1 )化合物做为合成酞菁化合物的中间体化合物， 与 另一合成酞菁的原料化合物按一定比例混合，在一定条件下可合成出 紫菜嗪环中含有三个、四个、五个及六个异吲哚结构亚单元的酞菁化 合物。
6、 通式 （2)化合物的应用：
航空航天领域中耐热电子器件材料的制备；信息材料的制备和能源材 料的制备；环境监测中传感器件材料的制备及在与生命科学有关的材
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JPH05163440A (ja) * 1991-12-16 1993-06-29 Japan Carlit Co Ltd:The フタロシアニン化合物
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