WO2022218399A1 - 中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用 - Google Patents

中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用 Download PDF

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WO2022218399A1
WO2022218399A1 PCT/CN2022/086993 CN2022086993W WO2022218399A1 WO 2022218399 A1 WO2022218399 A1 WO 2022218399A1 CN 2022086993 W CN2022086993 W CN 2022086993W WO 2022218399 A1 WO2022218399 A1 WO 2022218399A1
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mmol
equiv
nitrogen
room temperature
synthesis
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李贵杰
佘远斌
郭华
许克伟
刘顺
湛丰
文剑锋
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浙江工业大学
浙江华显光电科技有限公司
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Priority to KR1020237039317A priority patent/KR20240016952A/ko
Priority to EP22787621.6A priority patent/EP4306521A1/en
Publication of WO2022218399A1 publication Critical patent/WO2022218399A1/zh
Priority to US18/484,200 priority patent/US20240059962A1/en

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Definitions

  • the present invention relates to a circularly polarized luminescent material and application thereof, in particular to a circularly polarized luminescent material of central chirality-induced spiro chiral tetradentate ring metal platinum (II) and palladium (II) complexes and its application.
  • Circularly polarized luminescence is a phenomenon in which chiral luminescent substances emit left- or right-handed circularly polarized light after being excited. Therefore, the design and development of chiral luminescent materials is the key to this field. With the in-depth research of researchers, so far, circularly polarized luminescent materials have important applications in 3D display, data storage, quantum computing, optical anti-counterfeiting, biological imaging and asymmetric synthesis.
  • Cyclometallic platinum(II) and palladium(II) complex phosphorescent materials can make full use of all singlet and triplet excitons generated by electrical excitation due to their heavy atom effect, so that their maximum theoretical quantum efficiency can be as high as 100%. Complexes are an ideal class of luminescent materials.
  • the bidentate ring metal platinum(II) and palladium(II) complexes have low rigidity, because the two bidentate ligands are easily distorted and vibrated, so that the energy of the excited state material molecules is consumed in a non-radiative manner, resulting in a decrease in the luminescence quantum efficiency.
  • the central metal ions of the divalent cyclic metal platinum(II) and palladium(II) complexes are both dsp 2 hybridized, which are easy to coordinate with tetradentate ligands to form stable and rigid planar quadrilateral configuration molecules; high molecular rigidity can inhibit the Due to the non-radiative relaxation caused by molecular vibration and rotation, the energy loss of the excited state material molecules is reduced, which is beneficial to the improvement of the luminescence quantum efficiency of the material molecules.
  • the material molecule Due to the steric hindrance of the two aryl groups at the end of the tetradentate ligand of the cyclometallic platinum(II) and palladium(II) complexes, the material molecule exhibits a twisted tetragonal configuration (Chem.Mater.2020, 32, 537), which theoretically has The nature of spirochirality, but the molecule is easily racemized by the up-and-down vibration of the two aryl groups at the end of the ligand in solution or in the process of heating sublimation, so it is impossible to separate its enantiomers, and it is extremely difficult to obtain optically pure cyclometallic Molecules of platinum(II) and palladium(II) complex materials, so that they do not have the property of circularly polarized light emission.
  • the purpose of the present invention is to provide a central chirality-induced spiro-chiral tetradentate ring metal platinum(II) and palladium(II) complex circularly polarized luminescent material and application in view of the deficiencies in the prior art.
  • the spiro chiral metal complex molecule can autonomously induce the entire tetradentate ligand to coordinate with the metal ion in a way of small steric hindrance through the central chiral fragment L a in the tetradentate ligand to form an optically pure spiro.
  • the chiral metal complex circularly polarized light emitting material does not need chiral separation, and the material has high chemical stability and thermal stability, and has important applications in circularly polarized light emitting elements.
  • a central chirality induced spiro chiral tetradentate ring metal platinum (II) and palladium (II) complex circularly polarized light-emitting material characterized in that its chemical formula is such as general formula (I), (I'), (II) , (II'), (III) and (III'), wherein (I) and (I'), (II) and (II'), (III) and (III') are enantiomers of each other body:
  • V 1 , V 2 , V 3 and V 4 are each independently N or C;
  • L 1 , L 2 and L 3 are each independently a five- or six-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring;
  • La and L b are each independently a five-membered central chiral carbocyclic or heterocyclic ring ring; due to the steric hindrance between L a and L 1 , L a and L b , the whole metal complex is in a non-planar configuration, and the central chirality L a can autonomously induce the metal complex with a small steric hindrance Formation of centered spirochiral tetradentate ring metal platinum(II) and palladium(II) complexes;
  • R 1 , R 2 and R 3 each independently represent mono-, di-, tri-, or tetra-substituted or unsubstituted, while R 1 , R 2 , R 3 , R a , R b , R c , R d , R e , Rf , Rg , Rh , Rx, Ry , and Rz are each independently hydrogen, deuterium , halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl , haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, mono or dialkyl Amino, mono or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido
  • the above-mentioned central chirality-induced spiro-chiral tetradentate ring metal platinum(II) and palladium(II) complex circularly polarized light-emitting materials having general formulae (I), (I'), (II) and (II') can be of the following general formulae (I-A), (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H), (I-I), (II-A) and Its enantiomers (I'-A), (I'-A), (I'-B), (I'-C), (I'-D), (I'-E), (I '-F), (I'-G), (I'-H), (I'-I), (II'-A), but not limited to:
  • V 1 , V 2 , V 3 and V 4 are each independently N or C;
  • L 1 , L 2 and L 3 are each independently a five- or six-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring;
  • L a is a five-membered central chiral carbocyclic or heterocyclic ring; since L a and L The steric hindrance between 1 makes the whole metal complex a non-planar configuration, and the spirochiral tetradentate ring metal platinum ( II) and the formation of palladium(II) complexes;
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent mono-, di-, tri-, or tetra-substituted or unsubstituted, while R 1 , R 2 , R 3 , R 3 , R 4 , R 5 , Ra , Rb , Rc , Rd , Rx, Ry , and Rz are each independently hydrogen, deuterium , halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, Heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono or Dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido,
  • La and L b in the general structure of the above-mentioned central chirality-induced spiro chiral tetradentate ring metal platinum (II) and palladium (II) complex circularly polarized light-emitting material can be the following structures, but are not limited thereto:
  • R a1 , R a2 and R a3 each independently represent hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, Ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl
  • R b1 , R c1 and R c2 are each independently mono-, di-, tri-, or tetra-substituted or unsubstituted, and R b1 , R c1 and R c2 are each independently hydrogen, deuterium, halogen, alkyl, cyclic Alkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl , hydroxyl, mercapto, nitro, cyano, amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkane Oxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfam
  • L a and L b can be further specified as the following structures, but are not limited thereto:
  • R d1 , R e1 , R e2 , R e3 and R e4 are each independently mono-, di-, tri-, tetra-substituted or unsubstituted
  • R b1 , R c1 and R c2 are each independently hydrogen, deuterium, halogen , alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, ring Alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl , amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfony
  • central chirality induced spiro chiral tetradentate ring metal platinum(II) and palladium(II) complex circularly polarized light-emitting materials are preferably selected from:
  • central chirality induced spiro chiral tetradentate ring metal complex circularly polarized luminescent material can be selected from the following platinum (II) metal complexes and their corresponding isomers and their corresponding metal palladium (II) Complex:
  • the central chirality induces the application of the spirochiral tetradentate ring metal platinum(II) and palladium(II) complex circularly polarized light-emitting materials in organic light-emitting devices.
  • the organic light-emitting element is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.
  • the light-emitting element includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, and the organic layer includes a central chirality-induced spirochiral tetradentate ring metal Platinum(II) and palladium(II) complex circularly polarized light-emitting materials.
  • the central chirality induces the application of the spirochiral tetradentate ring metal platinum(II) and palladium(II) complex circularly polarized light-emitting materials in organic light-emitting devices.
  • the organic light-emitting element is a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, a biological imaging device, and the like.
  • Central chirality autonomously induces the generation of spiro chirality: by designing and developing a tetradentate ligand with central chirality L a , utilizing the steric hindrance effect between it and the other end ligand L 1 or L b , making the whole tetradentate ring metal ring metal platinum (II) and palladium (II) complex molecules into a twisted tetragonal configuration; at the same time, the central chirality La can autonomously induce the whole tetradentate ligand to be sterically hindered. Coordinate with metal ions to form optically pure metal ion-centered spirochiral tetradentate ring metal platinum(II) and palladium(II) complex circularly polarized light emitting materials. As shown in Figure 1.
  • Circularly polarized light-emitting materials do not require chiral resolution: two chiral tetradentate ring metal platinum(II) and palladium(II) complexes can be conveniently prepared from the above two chiral optically pure tetradentate ligands A chiral optically pure enantiomer circularly polarized light emitting material does not need to be separated and purified by a chiral column, which greatly reduces the preparation cost of the material.
  • the designed and developed tetradentate ligands can coordinate well with dsp 2 hybridized platinum(II) and palladium(II) metal ions to form stable and rigid quadrilaterals
  • the configuration molecule has high chemical stability; at the same time, due to the large steric hindrance effect between the designed central chiral ligand L a and the other end ligand L 1 or L b , the entire metal complex molecule can be used.
  • a stable spirochiral tetradentate ring metal complex is formed, so that it will not lose its circularly polarized luminescence property due to racemization during solution or high temperature sublimation.
  • Fig. 1 is the design idea of optically pure metal ion-centered spirochiral tetradentate ring metal complex circularly polarized light emitting material
  • Figure (A) is the front view of the X-diffraction single crystal structure of the optically pure spiro chiral material (R,S)-M-PtLA1
  • Figure (B) is the optically pure spirochiral material (R,S) - Top view of the X-diffraction single crystal structure of M-PtLA1
  • Figure (C) is the front view of the (R,S)-M-PtLA1 molecular structure optimized by density functional theory (DFT) calculation
  • Figure (D) is obtained by The top view of the (R,S)-M-PtLA1 molecular structure optimized by density functional theory (DFT) calculation
  • Figure (E) is the front view of the molecular structure of (S,R)-P-PtLA1 optimized by DFT calculation
  • Figure (F) The top view of the molecular structure of (S,R)-P-PtLA1 optimized by DFT calculation;
  • Figure (A) is a front view of the molecular structure of (R,S)-M-PtLB3 optimized by DFT calculation
  • Figure (B) is (R,S)-M-PtLB3 optimized by DFT calculation
  • the top view of the molecular structure of is the molecular formula of (R,S)-M-PtLB3
  • Figure (D) is the front view of the molecular structure of (S,R)-P-PtLB3 optimized by DFT calculation
  • Figure (E) is the top view of the molecular structure of (S,R)-P-PtLB3 optimized by DFT calculation
  • Figure (F) is the molecular structure of (S,R)-P-PtLB3;
  • Figure (A) is a front view of the molecular structure of (R,S)-M-PtLH1 optimized by DFT calculation
  • Figure (B) is (R,S)-M-PtLH1 optimized by DFT calculation.
  • the top view of the molecular structure of Figure (C) is the molecular formula of (R,S)-M-PtLH1
  • Figure (D) is the front view of the molecular structure of (S,R)-P-PtL H1 optimized by DFT calculation
  • Figure (E) is a top view of the molecular structure of (S,R)-P-PtL H1 optimized by DFT calculation
  • Figure (F) is the molecular structural formula of (S,R)-P-PtL H1;
  • Figure (A) is the front view of the molecular structure of M-PtLIII-1 after optimization by DFT calculation
  • Figure (B) is the molecular structure formula of M-PtLIII-1
  • Figure (C) is after optimization by DFT calculation
  • Figure (D) is the molecular structure of P-PtLIII-1;
  • Figure 6 shows the emission spectra of optically pure (R,S)-M-PtLA1 and (S,R)-P-PtLA1 in dichloromethane solution at room temperature;
  • Figure 7 shows the emission spectra of optically pure (R,S)-M-PtLA2 and (S,R)-P-PtLA2 in dichloromethane solution at room temperature;
  • Figure 8 is the emission spectra of optically pure (R,S)-M-PtLA3 and (S,R)-P-PtLA3 in dichloromethane solution at room temperature;
  • Figure 9 shows the emission spectra of optically pure (R,S)-M-PtLAN and (S,R)-P-PtLAN in dichloromethane solution at room temperature;
  • Figure 10 shows the emission spectra of optically pure (R,S)-M-PtLH1 and (S,R)-P-PtLH1 in dichloromethane solution at room temperature;
  • Figure 11 shows the emission spectra of optically pure (S,R)-P-PtLC3 and P-PtLIII-1 in dichloromethane solution at room temperature;
  • Figure 12 is the emission spectra of optically pure M-PdLA1 and P-PdLA1 in dichloromethane solution at room temperature;
  • Figure 13 is the emission spectra of optically pure M-PtLB1 and P-PtLB1 in dichloromethane solution at room temperature;
  • Figure 14 shows the emission spectra of optically pure M-PtLC1 and P-PtLC1 in dichloromethane solution at room temperature
  • Figure 15 shows the emission spectra of optically pure M-PtLD1 and P-PtL1 in dichloromethane solution at room temperature
  • Figure 16 shows the emission spectra of optically pure M-PtLE1 and P-PtLE1 in dichloromethane solution at room temperature
  • Figure 17 is the emission spectra of optically pure M-PtLF1 and P-PtLF1 in dichloromethane solution at room temperature;
  • Figure 18 shows the emission spectra of optically pure (R,S)-M-PtLK1 and (S,R)-P-PtLK1 in dichloromethane solution at room temperature;
  • Figure 19 shows the emission spectra of optically pure M-PtL1 and P-PtL1 in dichloromethane solution at room temperature
  • Figure 20 shows the emission spectra of optically pure M-PtL3 and P-PtL3 in dichloromethane solution at room temperature
  • Figure 21 is the circular dichroism spectrum (CD) of (S,R)-P-PtLA1 and (R,S)-M-PtLA1 in dichloromethane solution;
  • Figure 22 is the circular dichroism spectrum (CD) of P-PtOO and M-PtLOO in dichloromethane solution
  • Figure 23 is the circular dichroism spectrum (CD) of (S,R)-P-PtLA3 and (R,S)-M-PtLA3 in dichloromethane solution;
  • Figure 24 is the circular dichroism spectrum (CD) of (S,R)-P-PtLJ1 and (R,S)-M-PtLJ1 in dichloromethane solution;
  • Figure 25 is the circular dichroism spectrum (CD) of P-PtLB3 and M-PtL B3 in dichloromethane solution;
  • Figure 26 is the circularly polarized luminescence spectrum (CPPL) of P-PtOO, M-PtLOO and their equivalent mixtures in dichloromethane solution;
  • Figure 27 is the circularly polarized light emission spectrum (CPPL) of (S,R)-P-PtLA1 and (R,S)-M-PtLA1 in dichloromethane solution;
  • Figure 28 is the circularly polarized light emission spectrum (CPPL) of (S,R)-P-PtLA3 and (R,S)-M-PtLA3 in dichloromethane solution;
  • Figure 29 is the circularly polarized luminescence spectrum (CPPL) of optically pure M-PtL1 and P-PtL1 in dichloromethane solution at room temperature;
  • Figure 30 is the circularly polarized light emission spectrum (CPPL) of (S,R)-P-PtLA3 and (R,S)-M-PtLA3 in dichloromethane solution;
  • Figure 31 is the circularly polarized light emission spectrum (CPPL) of (S,R)-P-PtLJ1 and (R,S)-M-PtLJ1 in dichloromethane solution;
  • Figure 32 is the circularly polarized luminescence spectrum (CPPL) of P-PtLB3 and M-PtL B3 in dichloromethane solution;
  • Figure 33 is the circularly polarized luminescence spectrum (CPPL) of P-PtLB9 and M-PtL B9 in dichloromethane solution;
  • Figure 34 shows the high-performance liquid chromatogram (HPLC), optically pure (R,S)-M-PtLA1 of the mixture of (R,S)-M-PtLA1 and (S,R)-P-PtLA1 from top to bottom, respectively High performance liquid chromatography, optically pure (S,R)-P-PtLA1 high performance liquid chromatography and sublimed (R,S)-M-PtLA1 high performance liquid chromatography;
  • HPLC high-performance liquid chromatogram
  • Figure 35 is the thermogravimetric analysis curve of (R,S)-M-PtLA1;
  • 36 is a schematic structural diagram of an organic light-emitting element
  • Figure 37 shows the propagation mode of sunlight rays
  • Fig. 38 shows the propagation mode of circularly polarized light emitting light.
  • the terms "optional” or “optionally” mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • compositions described herein are disclosed, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that combinations, subsets, interactions, groups, etc. of these materials are disclosed, although specific references to each different individual and collective combination and permutation of these compounds are not specifically disclosed. , but each has its own specific assumptions and descriptions. For example, if a specific compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then every combination and permutation of the compound and possible modifications are specifically contemplated unless specifically stated to the contrary possible modifications.
  • Linking atoms used in the present invention are capable of linking two groups, eg, linking N and C.
  • the linking atom can optionally (if the valence allows) attach other chemical groups.
  • an oxygen atom would not have any other chemical group attached, as a valence bond is already satisfied once two atoms (eg, N or C) are bonded.
  • carbon is the linking atom
  • two additional chemical groups can be attached to the carbon atom.
  • cyclic structure refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclyl Ring Carbine.
  • substituted or similar terms as used herein includes all permissible substituents of organic compounds.
  • the permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds.
  • exemplary substituents include those described below.
  • the permissible substituents may be one or more, the same or different.
  • a heteroatom eg, nitrogen
  • the present invention is not intended to be limited in any way by the permissible substituents of organic compounds.
  • substituted or “substituted with” include the implied condition that the substitution complies with the substituted atom and the permissible valency of the substituent, and that the substitution results in a stable compound (e.g., that does not spontaneously undergo transformation ( Compounds such as by rearrangement, cyclization, elimination, etc.).
  • individual substituents can be further optionally substituted (ie, further substituted or unsubstituted).
  • R 1 ", “R 2 ", “R 3 " and “R 4 " are used in the present invention as general symbols to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed in the present invention, when they are defined as some substituents in one instance, they may also be defined as some other substituents in another instance.
  • alkyl as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl alkyl, eicosyl, tetracosyl, etc.
  • the alkyl group can be cyclic or acyclic.
  • the alkyl group can be branched or unbranched.
  • the alkyl group can also be substituted or unsubstituted.
  • the alkyl group can replace one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, methyl, etc. described herein.
  • a "lower alkyl” group is an alkyl group containing from 1 to 6 (eg, 1 to 4) carbon atoms.
  • alkyl generally refers to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the particular substituent on the alkyl group.
  • halogenated alkyl or “haloalkyl” specifically refers to an alkyl group substituted with one or more halogens (eg, fluorine, chlorine, bromine, or iodine).
  • alkoxyalkyl specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below.
  • alkylamino specifically refers to an alkyl group substituted with one or more amino groups, as described below and the like.
  • alkyl is used in one instance and a specific term such as “alkyl alcohol” is used in another, it is not meant to imply that the term “alkyl” does not simultaneously refer to a specific term such as “alkyl alcohol” Alcohol” etc.
  • cycloalkyl as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms composed of at least three carbon atoms.
  • examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like.
  • heterocycloalkyl is a class of cycloalkyl groups as defined above and is included within the meaning of the term “cycloalkyl” wherein at least one ring carbon atom is replaced by a heteroatom such as but not limited to nitrogen, oxygen, sulfur or phosphorus replace.
  • the cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted.
  • the cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro as described in the present invention , silyl groups, sulfur-oxo groups and mercapto groups.
  • polyolefin group refers to a group containing two or more CH2 groups attached to each other.
  • a “polyolefin group” can be represented as -( CH2 ) a- , where "a” is an integer between 2 and 500.
  • alkoxy and “alkoxy group” as used herein refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through an ether linkage; that is, “alkoxy” can be defined as— OR 1 , wherein R 1 is alkyl or cycloalkyl as defined above.
  • Alkoxy also includes the alkoxy polymers just described; that is, the alkoxy group can be a polyether, such as -OR 1 -OR 2 or -OR 1 -(OR 2 ) a -OR 3 , where "a” is an integer from 1 to 500, and R 1 , R 2 and R 3 are each independently alkyl, cycloalkyl, or a combination thereof.
  • alkenyl as used herein is a hydrocarbon group of 2 to 30 carbon atoms whose structural formula contains at least one carbon-carbon double bond.
  • the alkenyl can be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo or mercapto.
  • groups including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo or mercapto.
  • Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, and the like.
  • heterocycloalkenyl is a class of cycloalkenyl groups as defined above and is included within the meaning of the term “cycloalkenyl” wherein at least one carbon atom of the ring is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus substitution. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted.
  • the cycloalkenyl and heterocycloalkenyl may be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkenyl, and cycloalkenyl groups described in the present invention.
  • alkynyl as used in the present invention is a hydrocarbon group having 2 to 30 carbon atoms whose structural formula contains at least one carbon-carbon triple bond.
  • Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups, cycloalkenyl groups, alkynyl groups described herein. , cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo or mercapto.
  • cycloalkynyl as used herein is a non-aromatic carbon-based ring containing at least 7 carbon atoms and containing at least one carbon-carbon triple bond.
  • cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like.
  • heterocycloalkynyl is a cycloalkenyl group as defined above and is included within the meaning of the term “cycloalkynyl” wherein at least one of the carbon atoms of the ring is replaced by a heteroatom, the heteroatom Atoms such as but not limited to nitrogen, oxygen, sulfur or phosphorus.
  • Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkyne described in the present invention group, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo group, or mercapto.
  • groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkyne described in the present invention group, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester
  • aryl refers to any carbon-based aromatic group of 60 carbon atoms or less, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like.
  • aryl also includes "heteroaryl,” which is defined as an aromatic-containing group containing at least one heteroatom in the ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, or phosphorus.
  • non-heteroaryl (which is also included in the term “aryl”) defines an aromatic-containing group that does not contain heteroatoms.
  • Aryl groups can be substituted or unsubstituted.
  • Aryl can be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, Aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo or mercapto.
  • the term "biaryl” is a specific type of aryl group and is included in the definition of "aryl”. Biaryl refers to two aryl groups joined together through a fused ring structure, as in naphthalene, or two aryl groups joined through one or more carbon-carbon bonds, as in biphenyl.
  • amine or “amino” as used herein is represented by the formula —NR1R2 , wherein R1 and R2 can be independently selected from hydrogen , alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, selected from cycloalkynyl, aryl or heteroaryl.
  • alkylamino as used herein is represented by the formula -NH(-alkyl), wherein the alkyl group is as described herein.
  • Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, isopentyl Amino, tert-amylamino, hexylamino, etc.
  • dialkylamino as used in the present invention is represented by the formula -N(-alkyl) 2 , wherein the alkyl group is as described in the present invention.
  • Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino , Diamylamino, Diisoamylamino, Di-tert-amylamino, Dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N -propylamino, etc.
  • carboxylic acid as used in the present invention is represented by the formula -C(O)OH.
  • esters used in the present invention is represented by the formula -OC(O)R 1 or -C(O)OR 1 , wherein R 1 can be the alkyl, cycloalkyl, alkenyl, cycloalkenyl described in the present invention , alkynyl, cycloalkynyl, aryl or heteroaryl.
  • polyester as used in the present invention is represented by the formula -(R 1 O(O)CR 2 -C(O)O) a - or -(R 1 O(O)CR 2 -OC(O)) a - , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein and "a” is 1 to An integer of 500.
  • the term “polyester” is used to describe groups produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.
  • ether as used in the present invention is represented by the formula R 1 OR 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkyne as described herein aryl, aryl or heteroaryl.
  • polyether used in the present invention is represented by the formula —(R 1 OR 2 O) a —, wherein R 1 and R 2 can be independently alkyl, cycloalkyl, alkenyl, cycloalkene as described in the present invention alkynyl, alkynyl, cycloalkynyl, aryl or heteroaryl and "a" is an integer from 1 to 500.
  • Examples of polyether groups include polyethylene oxide, polypropylene oxide and polybutylene oxide.
  • halogen refers to the halogens fluorine, chlorine, bromine and iodine.
  • heterocyclyl refers to monocyclic and polycyclic non-aromatic ring systems
  • heteroaryl refers to monocyclic and polycyclic no more than 60 carbon atoms
  • An aromatic ring system wherein at least one of the ring members is not carbon.
  • the term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl and oxazolyl of 1,3,4-oxadiazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, Pyrimidyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, including 1,2,3,4-tetrazolyl and 1 , tetrazolyl of 2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadia
  • hydroxyl as used in the present invention is represented by the formula -OH.
  • ketone used in the present invention is represented by the formula R 1 C(O)R 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkyne as described in the present invention alkynyl, cycloalkynyl, aryl or heteroaryl.
  • azido used in the present invention is represented by the formula -N 3 .
  • nitro used in the present invention is represented by the formula -NO 2 .
  • nitrile as used in the present invention is represented by the formula -CN.
  • sil used in the present invention is represented by the formula —SiR 1 R 2 R 3 , wherein R 1 , R 2 and R 3 can be independently hydrogen or alkyl, cycloalkyl, alkoxy as described in the present invention alkenyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.
  • thio-oxo group as used herein is represented by the formula -S(O)R 1 , -S(O) 2 R 1 , -OS(O) 2 R 1 or -OS(O) 2 OR 1 , wherein R 1 can be hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described in the present invention.
  • R 1 can be hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described in the present invention.
  • sulfonyl refers to a thio-oxo group represented by the formula -S(O) 2 R 1 , wherein R 1 can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkyne alkynyl, cycloalkynyl, aryl or heteroaryl.
  • sulfone used in the present invention is represented by the formula R 1 S(O) 2 R 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl.
  • sulfoxide used in the present invention is represented by the formula R 1 S(O)R 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl.
  • mercapto used in the present invention is represented by the formula -SH.
  • R1", R2", R3 ", " Rn " (where n is an integer ) as used herein may independently have one or more of the above-listed groups.
  • R1 is a straight chain alkyl group
  • one hydrogen atom of the alkyl group may be optionally substituted with a hydroxy, alkoxy, alkyl, halo, and the like.
  • the first group may be incorporated within the second group, or the first group may be pendant (ie, attached) to the second group.
  • the amino group may be incorporated within the backbone of the alkyl group.
  • the amino group can be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is embedded or attached to the second group.
  • the compounds of the present invention may contain "optionally substituted” moieties.
  • substituted means that one or more hydrogens of the specified moiety are replaced with a suitable substituent.
  • an "optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be selected from one of the specified groups When the above substituents are substituted, the substituents may be the same or different at each position.
  • Combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. It is also contemplated that, in certain aspects, unless expressly stated to the contrary, each substituent may be further optionally substituted (ie, further substituted or unsubstituted).
  • R n is usually an integer. That is, R n is understood to represent the five individual substituents R n(a) , R n(b) , R n(c) , R n(d) , R n(e) . "Individual substituents" means that each R substituent may be independently defined. For example, if in one instance Rn(a) is halogen, then Rn(b) in that instance is not necessarily halogen.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. are mentioned several times in the chemical structures and units disclosed and described herein. Any description of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. in the specification applies to any structure or units, unless otherwise stated.
  • fused ring used in the present invention means that two adjacent substituents can be fused into a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a meta-diaza ring etc., and saturated six- or seven-membered carbocyclic or carboheterocycles, etc.
  • a heteroaromatic ring such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a meta-diaza ring etc.
  • High-resolution mass spectra were measured on an ESI-QTOF mass spectrometer of Applied Biosystems, and the sample ionization mode was electrospray ionization.
  • Example 1 The synthetic route of tetradentate ring metal platinum (II) complex (S,R)-P-PtLA1 is as follows:
  • the sealed tube was stirred in an oil bath at 110 °C, reacted for 2 days, cooled to room temperature, washed with water, adjusted to neutral or weakly acidic by adding dilute hydrochloric acid, and then adjusted to weakly alkaline by adding sodium bicarbonate, and ethyl acetate was added. Extraction, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 90°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the reaction solution was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 2 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (114 mg, 0.6 mmol, 2.0 equivalents), Dichloromethane (30 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 100°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 100°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the reaction liquid was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 120 ° C for 2 days, cooled to room temperature, evaporated under reduced pressure to remove the solvent, and added stannous chloride (140 mg, 0.74 mmol, 2.0 equivalents), Dichloromethane (30 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 90°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the reaction liquid was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 110 ° C for 2 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (140 mg, 0.74 mmol, 2.0 equivalents), Dichloromethane (30 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 100°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 100°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • P-PtLC1 (200 mg, 0.37 mmol, 1.0 equiv), potassium chloroplatinite (162 mg, 0.39 mmol, 1.05 equiv) and tetra-n-butyl bromide were sequentially added to a 50 mL three-necked flask with magnetrons Ammonium chloride (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • Ammonium chloride (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • M-PtLC1 (200 mg, 0.37 mmol, 1.0 equiv), potassium chloroplatinite (162 mg, 0.39 mmol, 1.05 equiv) and tetra-n-butyl bromide were added to a 50 mL three-necked flask with magnetrons in turn Ammonium chloride (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • Ammonium chloride (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • the sealed tube was stirred in an oil bath at 90°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • M-PtLIII-1 (200 mg, 0.41 mmol, 1.0 equiv.) and potassium chloroplatinite (178 mg, 0.43 mmol, 1.05 equiv.) were sequentially added to a 50 mL three-necked flask with magnetic particles. ) and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol%), purged nitrogen three times, added acetic acid (25 mL), bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then warmed to 120 ° C and reacted for 2 days .
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • P-PtLB1 (200 mg, 0.41 mmol, 1.0 equiv.), potassium chloroplatinite (178 mg, 0.43 mmol, 1.05 equiv.) and tetranormal Butylammonium bromide (13 mg, 0.041 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (25 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • P-LD1 200 mg, 0.37 mmol, 1.0 equiv.
  • potassium chloroplatinite 162 mg, 0.39 mmol, 1.05 equiv.
  • tetranormal Butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • M-LD1 Synthesis of M-LD1: LD-OH (500 mg, 1.65 mmol, 1.0 equiv.), 2-Br (572 mg, 1.82 mmol, 1.1 equiv.), iodine (572 mg, 1.82 mmol, 1.1 equiv.) and Cuprous (32 mg, 0.17 mmol, 10 mol %), ligand 2 (59 mg, 0.17 mmol, 10 mol %) and potassium phosphate (700 g, 3.30 mmol, 2.0 equiv), purge nitrogen 3 times, add dimethyl sulfoxide ( 10 mL), placed in a 90°C oil bath, and reacted for 2 days.
  • LD-OH 500 mg, 1.65 mmol, 1.0 equiv.
  • 2-Br 572 mg, 1.82 mmol, 1.1 equiv.
  • iodine 572 mg, 1.82 mmol, 1.1 equiv.
  • Cuprous 32 mg, 0.17
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • P-PtLE1 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinite (162 mg, 0.39 mmol, 1.05 equiv.) and tetranormal Butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • P-LF1 200 mg, 0.37 mmol, 1.0 equiv.
  • potassium chloroplatinite 162 mg, 0.39 mmol, 1.05 equiv.
  • tetranormal Butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) was purged with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled for 30 minutes, stirred at room temperature for 12 hours, then heated to 120° C. and reacted for 2 days.
  • reaction solution was washed with water, extracted with ethyl acetate three times, the organic phases were combined, washed with water once, dried over anhydrous sodium sulfate, filtered, mixed with silica gel, sampled by dry method, separated and purified by column chromatography, washed
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • P-PtB1 (243 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinite (262 mg, 0.63 mmol, 1.05 mol. equiv), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv), then nitrogen purged three times and acetic acid (36 mL) pre-sparged with nitrogen was added.
  • the reaction solution was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 3 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (228 mg, 1.2 mmol, 2.0 equiv), Dichloromethane (60 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • M-PtB1 (243 mg, 0.60 mmol, 1.0 equiv), potassium chloroplatinite (262 mg, 0.63 mmol, 1.05 equiv), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv), then nitrogen purged three times and acetic acid (36 mL) pre-sparged with nitrogen was added.
  • the reaction solution was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 3 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (228 mg, 1.2 mmol, 2.0 equiv), Dichloromethane (60 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • P-PtB2 (2) Synthesis of P-PtB2: P-B1 (182 mg, 0.40 mmol, 1.0 equiv), potassium chloroplatinite (174 mg, 0.42 mmol, 1.05 equiv), tetra-n-butylammonium bromide (13 mg, 0.040 mmol, 0.1 equiv), then nitrogen purged three times and acetic acid (24 mL) pre-sparged with nitrogen was added.
  • the reaction liquid was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 3 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (152 mg, 0.8 mmol, 2.0 equivalents), Dichloromethane (40 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • M-PtB2 (273 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinite (262 mg, 0.63 mmol, 1.05 mol. equiv), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv), then nitrogen purged three times and acetic acid (36 mL) pre-sparged with nitrogen was added.
  • the reaction solution was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 3 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (228 mg, 1.2 mmol, 2.0 equiv), Dichloromethane (60 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • P-PtB3 (22 mg, 0.40 mmol, 1.0 equiv.), potassium chloroplatinite (174 mg, 0.42 mmol, 1.05 mol. equiv), tetra-n-butylammonium bromide (13 mg, 0.040 mmol, 0.1 equiv), then nitrogen purged three times and acetic acid (24 mL) pre-sparged with nitrogen was added.
  • the reaction liquid was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 3 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (152 mg, 0.8 mmol, 2.0 equivalents), Dichloromethane (40 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • M-PtB3 (273 mg, 0.60 mmol, 1.0 equiv), potassium chloroplatinite (262 mg, 0.63 mmol, 1.05 equiv), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv), then nitrogen purged three times and acetic acid (36 mL) pre-sparged with nitrogen was added.
  • the reaction solution was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 100 ° C for 3 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, and added with stannous chloride (228 mg, 1.2 mmol, 2.0 equiv), Dichloromethane (60 mL) was stirred at room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 80°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • M-B8 (1.0 g, 2.25 mmol, 1.0 equiv.) was sequentially added to a dry sealed tube with a magnetic rotor, nitrogen was pumped three times, and toluene was added under nitrogen protection (30 mL) and iodomethane (384 mg, 2.71 mmol, 1.2 equiv).
  • the sealed tube was stirred in an oil bath at 100 °C, reacted for 2 days, cooled to room temperature, filtered after adding water, the solid was transferred to the sealed tube, methanol (30 mL) was added, and ammonium hexafluorophosphate (550 mg, 3.38 g) was added after dissolving.
  • M-PtB8 M-B8-Me (237 mg, 0.39 mmol, 1.0 equiv.) and (1,5-cyclooctadiene) were sequentially added to a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • P-PtB9 (200 mg, 0.48 mmol, 1.0 equiv.), potassium chloroplatinite (208 mg, 0.50 mmol, 1.05 mol. equiv), tetra-n-butylammonium bromide (15mg, 0.048mmol, 0.1 equiv), purged nitrogen three times, added acetic acid (30mL), the reaction liquid was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then heated at 110°C The reaction was continued for 48 hours, cooled to room temperature, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • M-PtB9 (200 mg, 0.48 mmol, 1.0 equiv), potassium chloroplatinite (208 mg, 0.50 mmol, 1.05 equiv), tetra-n-butylammonium bromide (15mg, 0.048mmol, 0.1 equiv), purged nitrogen three times, added acetic acid (30mL), the reaction liquid was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then heated at 110°C The reaction was continued for 48 hours, cooled to room temperature, and the solvent was distilled off under reduced pressure.
  • M-PdLA1 (200 mg, 0.41 mmol, 1.0 equiv), palladium acetate (101 mg, 0.45 mmol, 1.1 equiv) and tetra-n-butylammonium bromide ( 13 mg, 0.041 mmol, 10 mol%), nitrogen was purged three times, acetic acid (25 mL) was added, nitrogen was bubbled for 30 minutes, the temperature was raised to 120° C., and the reaction was carried out for 2 days. After cooling to room temperature, the solvent was removed by rotary evaporation under reduced pressure, washed with water, and extracted three times.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 100°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 100°C, reacted for 2 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the reaction solution was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, then stirred at 120°C for 2 days, cooled to room temperature, distilled under reduced pressure to remove the solvent, dissolved in dichloromethane, washed with water, and the aqueous layer was extracted with dichloromethane Three times, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • reaction solution was bubbled with nitrogen for 30 minutes, the reaction solution was stirred at room temperature for 12 hours, then stirred at 120 ° C for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure, adding stannous chloride dihydrate (1.10 g, 5.00 mmol, 10.0 equiv), dichloromethane (15 mL), and stirred at 40 °C for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • reaction liquid was bubbled with nitrogen for 30 minutes, it was first stirred at 40 °C for 12 hours, then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure, and stannous chloride dihydrate (790 mg, 3.50 mmol, 10.0 equiv), dichloromethane (15 mL), stirred at 40 °C for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the sealed tube was stirred in an oil bath at 85°C, reacted for 3 days, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, and the organic phase was washed once with brine, Dry over anhydrous sodium sulfate, filter, and evaporate the solvent under reduced pressure.
  • reaction liquid was bubbled with nitrogen for 30 minutes, it was first stirred at 30 °C for 12 hours, then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure, and stannous chloride dihydrate (734 mg, 3.25 mmol, 5.0 equiv), dichloromethane (15 mL), stirred at 40 °C for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined, and the solvent was distilled off under reduced pressure.
  • the N atom uses the 6-31G(d) basis set, and the Pt atom uses the LANL2DZ basis set.
  • the enantiomeric purity (ee value) was tested on a chiral chromatographic column EnantiopakR-C (size: 4.6 ⁇ 250 mm, 5um).
  • the cyclometallic complex can be controlled by the regulation of the tetradentate ligand structure. Efficient adjustment of the luminescence color proximity of the tetradentate can be achieved from the ultraviolet region of about 360nm to the red light region of 650nm; it is believed that through the further regulation of the tetradentate ligand structure, infrared luminescence can also be achieved.
  • the emission spectra in Fig. 6 to Fig. 20 are basically completely overlapped, which further proves that the corresponding material molecules in the drawings are enantiomers.
  • CD is the circular dichroism spectrum, and the sample concentration is 5 ⁇ 10 -5 M; its spectrum has high mirror symmetry and a strong Cotton effect at about 248, 275, 300 and 248 nm, indicating that the enantiomer (S,R)- P-PtLA1 and (R,S)-M-PtLA1 have strong deflection ability to linearly polarized light.
  • the spiro chiral material molecules in this application all exhibit strong circularly polarized luminescence, and the absolute value of the asymmetry factor (g PL ) can be as high as 4.0 ⁇ 10 -3 , and Fig. 26 to Fig. 33 are partial Circularly polarized luminescence spectra of material molecules.
  • the contrast material molecules PtON1, PtON3 and PtOO3 have no circularly polarized luminescence.
  • the material has high chemical and thermal stability.
  • the designed and developed tetradentate ligands can coordinate well with dsp 2 -hybridized platinum(II) and palladium(II) metal ions to form stable and rigid tetragonal configuration molecules with high chemical stability;
  • the designed central chiral ligand L a and the other end ligand L 1 or L b have a large steric hindrance effect, so that the entire metal complex molecule can form a stable spirochiral tetradentate ring metal complex, It will not lose its circularly polarized luminescence properties in the process of solution or high temperature sublimation.
  • the optical rotations also differ greatly, such as (S,R)-P-PtLA1(+477.2) and (S,R)-P-PtLA1(+784.6), indicating that the ligand structure has a great influence on its optical rotation.
  • the excited radiative emission of metal complexes mainly involves the metal-to-ligand charge transfer state (MLCT) and the charge transfer state within the ligand (ILCT), the spiro chirality of metal complexes and the ligand structure are circularly polarized to them. Light properties can also have a significant impact.
  • the dihedral angle refers to the angle formed between the two terminal heterocycles that coordinate with the central metal ion.
  • organic light-emitting element carriers are injected into the light-emitting material from the positive and negative electrodes, and the light-emitting material in the excited state is generated and made to emit light.
  • the complex of the present invention represented by the general formula (1) can be applied to an excellent organic light-emitting element such as an organic photoluminescent element or an organic electroluminescent element as a phosphorescent light-emitting material.
  • the organic photoluminescence element has a structure in which at least a light-emitting layer is formed on a substrate.
  • the organic electroluminescence element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed.
  • the organic layer includes at least a light-emitting layer, and may be composed of only the light-emitting layer, or may have one or more organic layers in addition to the light-emitting layer.
  • a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer and the like can be mentioned.
  • the hole transport layer may be a hole injection transport layer having a hole injection function
  • the electron transport layer may also be an electron injection transport layer having an electron injection function.
  • FIG. 35 A schematic diagram of the structure of a specific organic light-emitting element is shown in FIG. 35 .
  • FIG 35 there are 7 layers from bottom to top, representing the substrate, anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer and cathode in sequence, wherein the light-emitting layer is a guest material doped into a host material mixed layer.
  • ITO/HATCN(10nm)/TAPC(65nm)/host material luminescent material(10wt.%,20nm)/TmPyPB(55nm)/LiF/Al
  • ITO is the transparent anode
  • HATCN is the hole injection layer
  • TAPC is the hole transport layer
  • the host materials are mCBP and 26mCPy
  • TmPyPB is the electron transport layer
  • LiF is the electron injection layer
  • Al is the cathode. Numbers in nanometers (nm) in parentheses are the thickness of the films.
  • the molecular formula of the material applied in the device is as follows:
  • an organic light-emitting device carriers are injected into the light-emitting material from the positive and negative electrodes to generate an excited state of the light-emitting material and make it emit light.
  • the complex of the present invention can be used as a phosphorescent light-emitting material to be applied to excellent organic light-emitting devices such as organic photoluminescent devices or organic electroluminescent devices.
  • the organic photoluminescence device has a structure in which at least a light-emitting layer is formed on a substrate.
  • the organic electroluminescence element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed.
  • the organic layer includes at least a light-emitting layer, and may be composed of only the light-emitting layer, or may have one or more organic layers in addition to the light-emitting layer.
  • a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer and the like can be mentioned.
  • the hole transport layer may be a hole injection transport layer having a hole injection function
  • the electron transport layer may also be an electron injection transport layer having an electron injection function.
  • FIG. 6 A schematic diagram of the structure of a specific organic light-emitting element is shown in FIG. 6 . In Fig.
  • Each layer of the organic light-emitting device of the present invention can be formed by vacuum evaporation, sputtering, ion plating, etc., or wet film formation such as spin coating, printing, printing, etc.
  • the solvent used is not particularly limited.
  • the OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, particularly preferably selected from the following structures, but does not represent the present invention Limited to the following structures:
  • the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants.
  • the preferred p-type dopant of the present invention has the following structure, but it does not mean that the present invention is limited to the following structure:
  • the electron transport layer can be selected from at least one of compounds ET-1 to ET-13, but does not mean that the present invention is limited to the following structures:
  • the electron transport layer may be formed of an organic material together with one or more n-type dopants such as LiQ.
  • the compound shown in Example 1 is used as a circularly polarized light-emitting material in an OLED device, and its structure can also be expressed as: on the glass containing ITO, the hole injection layer (HIL) is HT-1:P-3 ( 95:5v/v%) with a thickness of 10 nm; the hole transport layer (HTL) is HT-1 with a thickness of 90 nm; the electron blocking layer (EBL) is HT-10 with a thickness of 10 nm, and the emissive layer (EML) ) is the host material (H-1 or H-2 or H-3 or H-4 or H-5 or H-6): the platinum metal complex of the present invention (95:5v/v%), the thickness is 35 nanometers, The electron transport layer (ETL) was ET-13:LiQ (50:50 v/v%) with a thickness of 35 nm, and then the cathode Al was evaporated to 70 nm.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron
  • the fabricated organic light-emitting device was tested under the current condition of 10 mA/cm 2 using a standard method known in the art, wherein a device using (S,R)-P-PtLA1 as the light-emitting material had a significant circularly polarized electroluminescence signal, and no The symmetry factor (g EL ) reaches 1.4 ⁇ 10 -3 , and its maximum external quantum efficiency (EQE) reaches 18%.
  • the structure is an example of an application of the circularly polarized light emitting material of the present invention, and does not constitute a limitation of the specific OLED device structure of the circularly polarized light emitting material shown in the present invention, and the circularly polarized light emitting material is not limited to the implementation of compounds shown in the examples.
  • the structure is an example of an application of the phosphorescent material of the present invention, and does not constitute a limitation of the specific OLED device structure of the phosphorescent material shown in the present invention, and the phosphorescent light-emitting material is not limited to the compounds shown in the examples.

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Abstract

本发明公开了一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用。所述螺手性金属配合物分子可通过四齿配体中的中心手性片段La可自主诱导整个四齿配体以空间位阻小的方式和金属离子配位，形成光学纯的的螺手性金属配合物圆偏振光发光材料，无需手性拆分，且材料具有高的化学稳定性和热稳定性，在圆偏振发光元件中具有重要应用。

Description

中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用 技术领域
本发明涉及一种圆偏振发光材料及其应用，尤其涉及一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用。
背景技术
圆偏振发光(CPL)是由手性发光物质受到激发后发射出左旋或右旋的圆偏振光的现象，因此，手性发光材料的设计发展是此领域的关键。随着科研人员的深入研究，到目前为止，圆偏振发光材料在3D显示、数据存储、量子计算、光学防伪、生物成像及不对称合成等领域具有重要应用。
环金属铂(II)和钯(II)配合物磷光材料由于其重原子效应可以充分利用电致激发产生的所有单线态和三线态激子，使其最大理论量子效率可高达100％，所以此类配合物是一类理想的发光材料。双齿环金属铂(II)和钯(II)配合物刚性较低，由于两个双齿配体易扭曲、振动从而使激发态材料分子的能量以非辐射方式消耗，致使其发光量子效率降低(Inorg.Chem.2002,41,3055)；虽然基于三齿配体的环金属铂(II)和钯(II)配合物由于其分子刚性增强可以提高发光量子效率(Inorg.Chem.2010,49,11276)，但是所含有的第二个单齿配体(如Cl -、苯氧基负离子、炔负离子、卡宾等)会使配合物的化学稳定性和热稳定性大大降低，难以升华提纯用于OLED器件的制备；所以基于双齿和三齿配体环金属配合物发光材料均不利于其在稳定高效OLED器件方面是应用。二价环金属铂(II)和钯(II)配合物中心金属离子均为dsp 2杂化，易于和四齿配体配位形成稳定而刚性的平面四边形构型分子；高的分子刚性可抑制由于分子振动和转动所引起的非辐射弛豫，减少激发态材料分子的能量损失，因此利于材料分子发光量子效率的提高。由于环金属铂(II)和钯(II)配合物四齿配体末端两个芳基的位阻，使材料分子呈现出扭曲的四边形构型(Chem.Mater.2020,32,537)，理论上具有螺手性的性质，但是分子在溶液中或加热升华过程中极易通过配体末端两个芳基的上下振动而消旋，无法分离其对映异构体，极难得到光学纯的环金属铂(II)和钯(II)配合物材料分子，使其不具有圆偏振发光的性质。因此，如何设计和发展具有高化学稳定性和热稳定性，且兼具圆偏振发光性质的光学纯环金属铂(II)和钯(II)配合物材料分子对于其在圆偏振发光OLED器件(CP-OLED)中的应用具有重要意义和巨大实用价值，也是CP-OLED领域急需解决的问题。
发明内容
本发明的目的是针对现有技术不足，提供了一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用。所述螺手性金属配合物分子可通过四齿配体中的中心手性片段L a可自主诱导整个四齿配体以空间位阻小的方式和金属离子配位，形成光学纯的的螺手性金属配合物圆偏振光发光材料，无需手性拆分，且材料具有高的化学稳定性和热稳定性，在圆偏振发光元件中具有重要应用。
本发明的目的是通过以下技术方案来实现的：
一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料，其特征在于，其化学式如通式(I)、(I')、(II)、(II')、(III)和(III')所示，其中(I)和(I')、(II)和(II')、(III)和(III')互为对映异构体：
Figure PCTCN2022086993-appb-000001
其中M为Pt或Pd；V 1、V 2、V 3和V 4各自独立的为N或C；
L 1、L 2和L 3是各自独立的为五元或六元碳环、杂环、芳环或者杂芳环；L a和L b是各自独立的为五元中心手性碳环或者杂环；由于L a和L 1、L a和L b之间的空间位阻，使整个金属配合物为非平面构型，且中心手性L a可自主以空间位阻小的方式诱导以金属为中心的螺手性四齿环金属铂(II)和钯(II)配合物的形成；
A 1、A 2、X和X 1各自独立地为O、S、CR xR y、C＝O、SiR xR y、GeR xR y、NR z、PR z、R zP＝O、AsR z、R zAs＝O、S＝O、SO 2、Se、Se＝O、SeO 2、BH、BR z、R zBi＝O或BiR z；
R 1、R 2和R 3各自独立地表示单、双、三、或四-取代或者无取代，同时R 1、R 2、R 3、R a、R b、R c、R d、R e、R f、R g、R h、R x、R y和R z各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R 1、R 2和R 3可以选择性连接形成稠环；R a、R b、R c和R d中的任意两个基团可连接形成环状体系，R e、R f、R g和R h中的任意两个基团可连接形成环状体系。
上述具有通式(I)、(I')、(II)和(II')的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料，可为如下通式(I-A)、(I-A)、(I-B)、(I-C)、(I-D)、(I-E)、(I-F)、(I-G)、(I-H)、(I-I)、(II-A)和其对映异构体(I'-A)、(I'-A)、(I'-B)、(I'-C)、(I'-D)、(I'-E)、(I'-F)、(I'-G)、(I'-H)、(I'-I)、(II'-A)之一，但不局限于此：
Figure PCTCN2022086993-appb-000002
Figure PCTCN2022086993-appb-000003
其中M为Pt或Pd；V 1、V 2、V 3和V 4各自独立的为N或C；
L 1、L 2和L 3是各自独立的为五元或六元碳环、杂环、芳环或者杂芳环；L a为五元中心手性碳环或者杂环；由于L a和L 1之间的空间位阻，使整个金属配合物为非平面构型，且由中心手性L a可自主以空间位阻小的方式诱导以金属为中心的螺手性四齿环金属铂(II)和钯(II)配合物的形成；
A 1、X、Z和Z 1各自独立地为O、S、CR xR y、C＝O、SiR xR y、GeR xR y、NR z、PR z、R zP＝O、AsR z、R zAs＝O、S＝O、SO 2、Se、Se＝O、SeO 2、BH、BR z、R zBi＝O或BiR z；
R 1、R 2、R 3、R 4和R 5各自独立地表示单、双、三、或四-取代或者无取代，同时R 1、R 2、R 3、R 3、R 4、R 5、R a、R b、R c、R d、R x、R y和R z各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷 酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R 1、R 2、R 3、R 4和R 5可以选择性连接形成稠环；R a、R b、R c和R d中的任意两个基团可连接形成环状体系。
上述中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料通式结构中的L a和L b可为如下结构，但不局限于此：
Figure PCTCN2022086993-appb-000004
其中R a1、R a2和R a3各自独立地表示氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；
其中R b1、R c1和R c2各自独立地表示单、双、三、或四-取代或者无取代，同时R b1、R c1和R c2各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R b1、R c1和R c2可以选择性连接形成稠环。
上述的L a和L b可进一步具体为如下结构，但不局限于此：
Figure PCTCN2022086993-appb-000005
Figure PCTCN2022086993-appb-000006
Figure PCTCN2022086993-appb-000007
其中R d1、R e1、R e2、R e3和R e4各自独立地表示单、双、三、四-取代或者无取代，同时R b1、R c1和R c2各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R b1、R c1和R c2可以选择性连接形成稠环。
进一步地，所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料优选自：
Figure PCTCN2022086993-appb-000008
Figure PCTCN2022086993-appb-000009
Figure PCTCN2022086993-appb-000010
进一步地，所述的中心手性诱导螺手性四齿环金属配合物圆偏振发光材料可选自如下的铂(II)金属配合物及其对应异构体和其对应的金属钯(II)配合物：
Figure PCTCN2022086993-appb-000011
Figure PCTCN2022086993-appb-000012
Figure PCTCN2022086993-appb-000013
Figure PCTCN2022086993-appb-000014
Figure PCTCN2022086993-appb-000015
Figure PCTCN2022086993-appb-000016
Figure PCTCN2022086993-appb-000017
Figure PCTCN2022086993-appb-000018
Figure PCTCN2022086993-appb-000019
Figure PCTCN2022086993-appb-000020
Figure PCTCN2022086993-appb-000021
Figure PCTCN2022086993-appb-000022
Figure PCTCN2022086993-appb-000023
Figure PCTCN2022086993-appb-000024
Figure PCTCN2022086993-appb-000025
Figure PCTCN2022086993-appb-000026
Figure PCTCN2022086993-appb-000027
Figure PCTCN2022086993-appb-000028
Figure PCTCN2022086993-appb-000029
Figure PCTCN2022086993-appb-000030
Figure PCTCN2022086993-appb-000031
Figure PCTCN2022086993-appb-000032
Figure PCTCN2022086993-appb-000033
Figure PCTCN2022086993-appb-000034
Figure PCTCN2022086993-appb-000035
Figure PCTCN2022086993-appb-000036
Figure PCTCN2022086993-appb-000037
Figure PCTCN2022086993-appb-000038
Figure PCTCN2022086993-appb-000039
Figure PCTCN2022086993-appb-000040
Figure PCTCN2022086993-appb-000041
Figure PCTCN2022086993-appb-000042
Figure PCTCN2022086993-appb-000043
Figure PCTCN2022086993-appb-000044
Figure PCTCN2022086993-appb-000045
Figure PCTCN2022086993-appb-000046
Figure PCTCN2022086993-appb-000047
Figure PCTCN2022086993-appb-000048
Figure PCTCN2022086993-appb-000049
Figure PCTCN2022086993-appb-000050
Figure PCTCN2022086993-appb-000051
Figure PCTCN2022086993-appb-000052
Figure PCTCN2022086993-appb-000053
Figure PCTCN2022086993-appb-000054
Figure PCTCN2022086993-appb-000055
Figure PCTCN2022086993-appb-000056
进一步地，中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料在有机发光元件中的应用。所述有机发光元件，其为有机发光二极管、发光二极管或发光电化学电池。
所述发光元件包括第一电极、第二电极及设置于所述第一电极和所述第二电极之间的至少一个有机层，所述有机层包括中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料。
进一步地，中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料在有机发光元件中的应用。所述有机发光元件，其为3D显示器件、三维成像器件、光学信息加密器件、信息存储器件、生物成像器件等。
本发明的有益效果是：
(1)中心手性自主诱导螺手性的产生：通过设计和发展具有中心手性L a的四齿配体，利用其和另一末端配体L 1或L b之间的空间位阻效应，使整个四齿环金属环金属铂(II)和钯(II)配合物分子为扭曲的四边形构型；同时，中心手性L a可自主诱导整个四齿配体以空间位阻小的方式和金属离子配位，形成光学纯的以金属离子为中心的螺手性四齿环金属铂(II)和钯(II)配合物圆偏振光发光材料。如附图1所示。
(2)光学纯原料经济易得：制备含有中心手性L a四齿配体所需要的两个手性光学纯对应异构体均为商业化经济易得的化合物，便于大量制备两个手性光学纯的四齿配体。
(3)圆偏振光发光材料无需手性拆分：由上述两个手性光学纯的四齿配体可以方便制备螺手性四齿环金属铂(II)和钯(II)配合物的两个手性光学纯的对应异构体圆偏振光发光材料，无需通过手性柱分离纯化，大大降低材料的制备成本。
(4)材料化学稳定性和热稳定性高：所设计发展的四齿配体可以和dsp 2杂化的铂(II)和钯(II)金属离子很好的配位形成稳定而刚性的四边形构型分子，化学稳定性高；同时，由于所设计的中心手性配体L a和另一末端配体L 1或L b之间具有较大空间位阻效应，使整个金属配合物分子可形成稳定的螺手性四齿环金属配合物，使其在溶液或高温升华过程中均不会发生消旋而丧失圆偏振发光性质。
附图说明
图1为光学纯的以金属离子为中心的螺手性四齿环金属配合物圆偏振光发光材料设计思路图；
图2中，图(A)为光学纯螺手性材料(R,S)-M-PtLA1的X-衍射单晶结构正视图，图(B)为光学纯螺手性材料(R,S)-M-PtLA1的X-衍射单晶结构俯视图，图(C)为通过密度泛函理论(DFT)计算优化后的(R,S)-M-PtLA1分子结构正视图，图(D)为通过密度泛函理论(DFT)计算优化后的(R,S)-M-PtLA1分子结构俯视图，图(E)为DFT计算优化后的(S,R)-P-PtLA1的分子结构正视图，图(F)为DFT计算优化后的(S,R)-P-PtLA1的分子结构俯视图；
图3中，图(A)为通过DFT计算优化后的(R,S)-M-PtLB3的分子结构正视图，图(B)为通过DFT计算优化后的(R,S)-M-PtLB3的分子结构俯视图，图(C)为(R,S)-M-PtLB3的分子结构式，图(D)为通过DFT计算优化后的(S,R)-P-PtLB3的分子结构正视图，图(E)为通过DFT计算优化后的(S,R)-P-PtLB3的分子结构俯视图，图(F)为(S,R)-P-PtLB3的分子结构式；
图4中，图(A)为通过DFT计算优化后的(R,S)-M-PtLH1的分子结构正视图，图(B)为通过DFT计算优化后的(R,S)-M-PtLH1的分子结构俯视图，图(C)为(R,S)-M-PtLH1的分子结构式，图(D)为通过DFT计算优化后的(S,R)-P-PtL H1的分子结构正视图，图(E)为通过DFT计算优化后的(S,R)-P-PtL H1的分子结构俯视图，图(F)为(S,R)-P-PtL H1的分子结构式；
图5中，图(A)为通过DFT计算优化后的M-PtLIII-1的分子结构正视图，图(B)为M-PtLIII-1的分子结构式，图(C)为通过DFT计算优化后的P-PtLIII-1的分子结构正视图，图(D)为P-PtLIII-1的分子结构式；
图6为光学纯(R,S)-M-PtLA1和(S,R)-P-PtLA1在二氯甲烷溶液中室温下的发射光谱图；
图7为光学纯(R,S)-M-PtLA2和(S,R)-P-PtLA2在二氯甲烷溶液中室温下的发射光谱图；
图8为光学纯(R,S)-M-PtLA3和(S,R)-P-PtLA3在二氯甲烷溶液中室温下的发射光谱图；
图9为光学纯(R,S)-M-PtLAN和(S,R)-P-PtLAN在二氯甲烷溶液中室温下的发射光谱图；
图10为光学纯(R,S)-M-PtLH1和(S,R)-P-PtLH1在二氯甲烷溶液中室温下的发射光谱图；
图11为光学纯(S,R)-P-PtLC3和P-PtLIII-1在二氯甲烷溶液中室温下的发射光谱图；
图12为光学纯M-PdLA1和P-PdLA1在二氯甲烷溶液中室温下的发射光谱图；
图13为光学纯M-PtLB1和P-PtLB1在二氯甲烷溶液中室温下的发射光谱图；
图14为光学纯M-PtLC1和P-PtLC1在二氯甲烷溶液中室温下的发射光谱图；
图15为光学纯M-PtLD1和P-PtL1在二氯甲烷溶液中室温下的发射光谱图；
图16为光学纯M-PtLE1和P-PtLE1在二氯甲烷溶液中室温下的发射光谱图；
图17为光学纯M-PtLF1和P-PtLF1在二氯甲烷溶液中室温下的发射光谱图；
图18为光学纯(R,S)-M-PtLK1和(S,R)-P-PtL K1在二氯甲烷溶液中室温下的发射光谱图；
图19为光学纯M-PtL1和P-PtL1在二氯甲烷溶液中室温下的发射光谱图；
图20为光学纯M-PtL3和P-PtL3在二氯甲烷溶液中室温下的发射光谱图；
图21为(S,R)-P-PtLA1和(R,S)-M-PtLA1在二氯甲烷溶液中的圆二色光谱图(CD)；
图22为P-PtOO和M-PtLOO在二氯甲烷溶液中的圆二色光谱图(CD)；
图23为(S,R)-P-PtLA3和(R,S)-M-PtLA3在二氯甲烷溶液中的圆二色光谱图(CD)；
图24为(S,R)-P-PtLJ1和(R,S)-M-PtLJ1在二氯甲烷溶液中的圆二色光谱图(CD)；
图25为P-PtLB3和M-PtL B3在二氯甲烷溶液中的圆二色光谱图(CD)；
图26为P-PtOO、M-PtLOO及其等量混合物在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图27为(S,R)-P-PtLA1和(R,S)-M-PtLA1在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图28为(S,R)-P-PtLA3和(R,S)-M-PtLA3在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图29为光学纯M-PtL1和P-PtL1在二氯甲烷溶液中室温下的圆偏振发光谱图(CPPL)；
图30为(S,R)-P-PtLA3和(R,S)-M-PtLA3在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图31为(S,R)-P-PtLJ1和(R,S)-M-PtLJ1在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图32为P-PtLB3和M-PtL B3在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图33为P-PtLB9和M-PtL B9在二氯甲烷溶液中的圆偏振发光谱图(CPPL)；
图34自上而下分别为(R,S)-M-PtLA1和(S,R)-P-PtLA1混合物的高效液相色谱谱图(HPLC)、光学纯(R,S)-M-PtLA1高效液相色谱谱图、光学纯(S,R)-P-PtLA1高效液相色谱谱图以及升华后的(R,S)-M-PtLA1高效液相色谱谱图；
图35为(R,S)-M-PtLA1的热重分析曲线；
图36为有机发光元件的结构示意图；
图37为太阳光光线的传播方式；
图38为圆偏振发光光线的传播方式。
具体实施方式
以下对本发明的内容进行详细说明。以下所记载的构成要件的说明有时是基于本发明的代表性实施方式或具体例而成，但本发明并不限定于此种实施方式或具体例。
下面举例说明上述通式中所代表的本发明的圆偏振光发光材料的具体实例，然而，不解释为限制本发明。
通过参考以下具体实施方式和其中包含的实施例，可以更容易地理解本公开。在公开和描述本发明的化合物、器件和/或方法之前，应当明白，除非另有说明，否则他们不限于具体的合成方法或者具体的试剂，因为这是可以变化的。也应当明白本发明中使用的术语仅是用于描述特定方面，并不旨在限制。尽管本发明描述的那些类似或者等价的任何方法和材料都可用于该实践或者试验，但现在描述了示例方法和材料。
在说明书和所附权利要求中所用的术语单数形式“一种”、“一个”和“所述”包含复数指代，否则上下文中会另有明确指出。因此，例如提及“组分”时包含两种或多种组分的混合物。
本发明所使用的术语“任选的”或“任选地”意味着随后描述的事件或情况可以或不发生，并且该描述包括所述事件或情况发生的实例及它未发生的实例。
公开了可用于制备本发明所述的组合物的组分，以及要用于本发明中公开的方法中的组合物本身。本发明公开了这些和其它材料，并且应当理解公开了这些物质的组合、子集、相互作用、组等，虽然不能具体地公开这些化合物的每个不同的单独和总的组合以及排列的具体参考，但各自有专门的设想和描述。例如，如果公开和讨论了具体的化合物，并且讨论了能够对许多包含该化合物的分子进行的许多修饰，那么具体地考虑了该化合物的每种组合和排列以及可能进行的修饰，除非特别指出相反的可能修饰。因此，如果公开了一类分子A、B和C以及一类分子D、E和F，和组合分子A-D的实例，那么即使没有单独地记载每一个，但也考虑公开了每个单独地和总的含义组合，A-E、A-F、B-D、B-E、B-F、C-D、C-E和C-F。同样地，也公开了任何子集或这些的组合。例如，A-E、B-F和C-E的子组也是公开的。这一概念适用于本发明的所有方面，包括但不限于制备和使用该组合物的方法中的步骤。因此，如果存在各种另外的步骤能够进行，应当理解，这些另外的步骤各自能够以该方法的具体实施方式或者实施方式的组合进行。
本发明使用的连接原子能够连接两个基团，例如，连接N和C。该连接原子能够任选地(如果价键允许)附接其他的化学基团。例如，氧原子不会具有任何其它的化学基团附接，因为一旦键合两个原子(例如，N或C)价键则已经满足。相反，当碳是连接原子时，两个另外的化学基团能够附接至该碳原子。合适的化学基团包括但不限于氢、羟基、烷基、烷氧基、＝O、卤素、硝基、胺、酰胺、巯基、芳基、杂芳基、环烷基和杂环基。
本发明使用的术语“环状结构”或类似术语是指任何环状化学结构，其包括但不限于芳基、杂芳基、环烷基、环烯基、杂环基、卡宾和N-杂环卡宾。
本发明使用的术语“取代的”或类似术语包含有机化合物的所有允许的取代基。广义上，允许的取代基包括有机化合物的环状和非环状、支链和非支链、碳环和杂环、芳香族和非芳香族取代基。例如，示例性取代基包括以下所述。对于合适的有机化合物来说，允许的取代基可为一个或多个，相同或不同。对于本发明的目的而言，杂原子(例如氮)能够具有氢取代基和/或本发明所述满足该杂原子价键的有机化合物的任何允许取代基。本发明不意图以任何方式用有机化合物允许的取代基来进行任何限制。同样，术语“取代”或“取代有”包含隐含条件是这种取代符合取代的原子和该取代基的允许的价键，和该取代导致稳定的化合物 (例如，不会自发地进行转化(例如通过重排、环化、消去等)的化合物)。在某些方面，除非明确指出相反，否则，单独的取代基能够进一步任选地取代(即，进一步取代或未取代的)。
在定义各种术语时，“R 1”、“R 2”、“R 3”和“R 4”在本发明中作为通用符号来表示各种特定的取代基。这些符号能够是任何取代基，不限于本发明公开的那些，当它们在一个实例中被定义为某些取代基时，在另一个实例中也可以被定义为一些其他取代基。
本发明使用的术语“烷基”是1至30个碳原子的支链或非支链的饱和烃基，例如甲基、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、仲戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十四烷基、十六烷基、二十烷基、二十四烷基等。该烷基可为环状或非环状。该烷基可为支链或非支链的。该烷基也可为取代或未取代的。例如，该烷基可取代一个或多个基团，包括但不限于本发明所述的任选取代的烷基、环烷基、烷氧基、氨基、醚、卤素、羟基、硝基、甲硅烷基、硫-氧代基团和巯基。“低级烷基”基团是含有1至6个(例如1至4个)碳原子的烷基。
在整个说明书中，“烷基”通常同时指未取代烷基和取代烷基；但是，取代烷基也在本发明中通过确定烷基上的特定取代基来具体地提及。例如，术语“卤化的烷基”或者“卤代烷基”具体是指取代有一个或多个卤素(例如，氟、氯、溴或碘)的烷基。术语“烷氧基烷基”具体是指取代有一个或多个烷氧基的烷基，如下所述。术语“烷基氨基”具体是指取代有一个或多个氨基的烷基，如下所述等。当在一种情况中使用“烷基”而在另一情况中使用具体的术语如“烷基醇”时，不意味着暗示该术语“烷基”不同时指代具体的术语如“烷基醇”等。
这种做法也用于本发明所述的其它基团。也即，当术语如“环烷基”同时指代未取代的和取代的环烷基部分时，该取代的部分可另外具体地在本发明中确定；例如，具体取代的环烷基可称为例如“烷基环烷基”。类似的，取代的烷氧基可具体地称为例如“卤代烷氧基”，具体的取代烯基可为例如“烯醇”等。同样地，使用通用术语如“环烷基”和具体术语如“烷基环烷基”的不意味着该通用术语不同时包含该具体术语。
本发明使用的术语“环烷基”是由至少三个碳原子构成的3至30个碳原子的非芳香族的碳基环。环烷基的例子包括但不限于环丙基、环丁基、环戊基、环己基、环壬基等。术语“杂环烷基”是一类如上定义的环烷基，并且包含在术语“环烷基”的含义中，其中至少一个环碳原子被杂原子例如但不限于氮、氧、硫或磷取代。该环烷基和杂环烷基可为取代或未取代的。该环烷基和杂环烷基可取代有一个或多个基团，包括但不限于如本发明所述的烷基、环烷基、烷氧基、氨基、醚、卤素、羟基、硝基、甲硅烷基、硫-氧代基团和巯基。
本发明使用的术语“聚烯烃基团”是指含有两个或多个彼此相连的CH 2基团的基团。“聚烯烃基团”可以表示为—(CH 2) a—,其中“a”是2到500之间整数。
本发明使用的术语“烷氧基”和“烷氧基基团”是指通过醚键键合的1至30个碳原子的烷基或环烷基；即“烷氧基”可定义为—OR 1，其中R 1是如上定义的烷基或环烷基。“烷氧基”也包含刚刚描述的烷氧基聚合物；即烷氧基可为聚醚，如—OR 1-OR 2或—OR 1-(OR 2) a-OR 3，其中“a”是整数1至500，而R 1、R 2和R 3各自独立地为烷基、环烷基或其组合。
本发明使用的术语“烯基”是2至30个碳原子的烃基，其结构式含有至少一个碳-碳双键。不对称结构如(R 1R 2)C＝C(R 3R 4)包含E和Z异构体。这可推定在本发明的结构式中，其中存在不对称烯烃，或者它可通过键符号C＝C明确表示。该烯基可取代有一个或多个基团，包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“环烯基”是非芳香族的3至30个碳原子的碳基环，其由至少3个碳原子构成，并且含有至少一个碳碳双键，即C＝C。环烯基的实例包括但不限于环丙烯基、环丁烯基、环戊烯基、环戊二烯基、环己烯基、环己二烯基、环庚烯基等。术语“杂环烯基”是一类如上定义的环烯基，并且包含在术语“环 烯基”的含义中，其中该环的至少一个碳原子用杂原子例如但不限于氮、氧、硫或磷取代。环烯基和杂环烯基可为取代或未取代的。该环烯基和杂环烯基可取代有一个或多个基团，包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“炔基”是具有2至30个碳原子的烃基，其结构式至少含有一个碳-碳三键。炔基可为未取代的或者取代有一个或多个基团，所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“环炔基”是非芳香族的碳基环，其包含至少7个碳原子并含有至少一个碳-碳三键。环炔基的实例包括但不限于环庚炔基、环辛炔基、环壬炔基等。术语“杂环炔基”是如上所定义的一种环烯基，并且包含在术语“环炔基”的含义内，其中所述环的碳原子中的至少一个被杂原子替代，所述杂原子例如但不限于氮、氧、硫或磷。环炔基和杂环炔基可为取代或未取代的。环炔基和杂环炔基可取代有一个或多个基团，所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“芳基”是指含有任何碳基芳香族的60个碳原子及以内的基团，包括但不限于苯、萘、苯基、联苯、苯氧基苯等。术语“芳基”也包括“杂芳基”，其被定义为含有芳香族的基团，所述芳香族基团环内至少含有一个杂原子。杂原子的实例包括但不限于氮、氧、硫或磷。同样，术语“非杂芳基”(其也包括在术语“芳基”中)定义了含有芳香族的基团，所述芳香族基团不含杂原子。芳基可为取代或未取代的。芳基可取代有一个或多个基团，所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。术语“联芳基”是特定类型的芳基并且包含在“芳基”的定义中。联芳基是指经稠合的环结构结合在一起的两个芳基，如在萘中一样，或者经一个或多个碳-碳键连接的两个芳基，如在联苯中一样。
本发明使用的术语“醛”通过式—C(O)H表示。在整个说明书中，“C(O)”是羰基(即，C＝O)的简写形式。
本发明使用的术语“胺”或“氨基”通过式—NR 1R 2表示，其中R 1和R 2可以独立的从氢、烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基中选择。
本发明使用的术语“烷基氨基”通过式—NH(-烷基)表示，其中烷基如本发明所述。代表性实例包括但不限于甲基氨基、乙基氨基、丙基氨基、异丙基氨基、丁基氨基、异丁基氨基、仲丁基氨基、叔丁基氨基、戊基氨基、异戊基氨基、叔戊基氨基、己基氨基等。
本发明使用的术语“二烷基氨基”通过式—N(-烷基) 2表示，其中烷基如本发明所述。代表性实例包括但不限于二甲基氨基、二乙基氨基、二丙基氨基、二异丙基氨基、二丁基氨基、二异丁基氨基、二仲丁基氨基、二叔丁基氨基、二戊基氨基、二异戊基氨基、二叔戊基氨基、二己基氨基、N-乙基-N-甲基氨基、N-甲基-N-丙基氨基、N-乙基-N-丙基氨基等。
本发明使用的术语“羧酸”通过式—C(O)OH表示。
本发明使用的术语“酯”通过式—OC(O)R 1或者—C(O)OR 1表示，其中R 1可为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“聚酯”通过式—(R 1O(O)C-R 2-C(O)O) a—或者—(R 1O(O)C-R 2-OC(O)) a—表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基并且“a”为1至500的整数。术语“聚酯”用于描述通过具有至少两个羧基的化合物与具有至少两个羟基的化合物之间的反应产生的基团。
本发明使用的术语“醚”通过式R 1OR 2表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、 环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“聚醚”通过式—(R 1O-R 2O) a—表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基并且“a”为1至500的整数。聚醚基团的实例包括聚氧化乙烯、聚氧化丙烯和聚氧化丁烯。
本发明使用的术语“卤素”是指卤素氟、氯、溴和碘。
本发明使用的术语“杂环基”是指单环的和多环的非芳香族环系，并且本发明使用的“杂芳基”是指单环和多环的不多于60个碳原子的芳香族环系：其中环成员中的至少一个不为碳。该术语包括氮杂环丁烷基、二噁烷基、呋喃基、咪唑基、异噻唑基、异噁唑基、吗啉基、噁唑基(包括1,2,3-噁二唑基、1,2,5-噁二唑基和1,3,4-噁二唑基的噁唑基)、哌嗪基、哌啶基、吡嗪基、吡唑基、哒嗪基、吡啶基、嘧啶基、吡咯基、吡咯烷基、四氢呋喃基、四氢吡喃基、包括1,2,4,5-四嗪基的四嗪基、包括1,2,3,4-四唑基和1,2,4,5-四唑基的四唑基、包括1,2,3-噻二唑基、1,2,5-噻二唑基和1,3,4-噻二唑基的噻二唑基、噻唑基、噻吩基、包括1,3,5-三嗪基和1,2,4-三嗪基的三嗪基、包括1,2,3-三唑基和1,3,4-三唑基的三唑基等。
本发明使用的术语“羟基”通过式—OH表示。
本发明使用的术语“酮”通过式R 1C(O)R 2表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“叠氮基”通过式—N 3表示。
本发明使用的术语“硝基”通过式—NO 2表示。
本发明使用的术语“腈”通过式—CN表示。
本发明使用的术语“甲硅烷基”通过式—SiR 1R 2R 3表示，其中R 1、R 2和R 3可独立地为氢或者本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“硫-氧代基团”通过式—S(O)R 1、—S(O) 2R 1、—OS(O) 2R 1或—OS(O) 2OR 1表示，其中R 1可为氢或者本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。在整个说明书中，“S(O)”为S＝O的简写形式。本发明使用的术语“磺酰基”是指通过式—S(O) 2R 1表示的硫-氧代基团，其中R 1可为烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“砜”通过式R 1S(O) 2R 2表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“亚砜”通过式R 1S(O)R 2表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“巯基”通过式—SH表示。
本发明使用的“R 1”、“R 2”、“R 3”、“R n”(其中n为整数)可独立地具有上面列举的基团中的一个或者多个。例如，如果R 1为直链烷基，那么烷基的一个氢原子可任选取代有羟基、烷氧基、烷基、卤素等。取决于选择的基团，第一基团可结合在第二基团内，或者第一基团可侧连(即，连接)至第二基团。例如，对于短语“包含氨基的烷基”，氨基可结合在烷基的主链内。可选择地，氨基可连接至烷基的主链。所选基团的性质将决定是否第一基团嵌入或者连接至第二基团。
本发明所述化合物可含有“任选取代的”部分。通常，术语“取代的”(无论在前面是否存在术语“任选”)意味着指定部分的一个或多个氢被合适的取代基取代。除非另作说明，否则“任选取代的”基团可在基团的每个可取代位置具有合适的取代基，并且当任何给定结构中的一个以上位置可以被选自指定基团的一个以上取代基取代时，取代基可以在每个位置上相同或不同。本发明设想的取代基组合优选为形成稳定的或化学上可行的化合物的组合。还可以设想，在某些方面，除非明确指出相反，各个取代基可进一步任选被取代(即，进一步取代或未取代)。
化合物的结构可通过下式表示：
Figure PCTCN2022086993-appb-000057
其被理解为等同于下式：
Figure PCTCN2022086993-appb-000058
其中n通常为整数。即，R n被理解为表示五个单独的取代基R n(a)、R n(b)、R n(c)、R n(d)、R n(e)。“单独的取代基”是指每个R取代基可独立地限定。例如，如果在一个情况中R n(a)为卤素，那么在这种情况下R n(b)不一定是卤素。
在本发明公开和描述的化学结构和单元中数次提及R 1、R 2、R 3、R 4、R 5、R 6等。在说明书中R 1、R 2、R 3、R 4、R 5、R 6等的任何描述分别适用于引用R 1、R 2、R 3、R 4、R 5、R 6等的任何结构或者单元，除非另作说明。
本发明使用的术语“稠环”是指相邻的两个取代基可以稠合成六元芳环、杂芳环，例如苯环、吡啶环、吡嗪环、哒嗪环、间二氮杂环等，以及饱和的六元或七元碳环或碳杂环等。
除非另有说明，以下试验中所涉及到的所有商业试剂购买后直接使用，没有进一步纯化。核磁共振氢谱和碳谱均在氘代氯仿(CDCl 3)或氘代二甲基亚砜(DMSO-d 6)溶液中测得，氢谱使用400或500兆赫兹的核磁共振谱仪，碳谱使用100或126兆赫兹的核磁共振谱仪，化学位移以四甲基硅烷(TMS)或残留溶剂为基准。如果用CDCl 3作溶剂，则氢谱和碳谱分别以TMS(δ＝0.00ppm)和CDCl 3(δ＝77.00ppm)作为内标。如果用DMSO-d 6作溶剂，则氢谱和碳谱分别以TMS(δ＝0.00ppm)和DMSO-d 6(δ＝39.52ppm)作为内标。以下缩写(或组合)用于解释氢谱峰：s＝单峰，d＝双重峰，t＝三重峰，q＝四重峰，p＝五重峰，m＝多重峰，br＝宽峰。高分辨质谱在Applied Biosystems公司的ESI-QTOF质谱仪上测得，样品电离模式为电喷雾电离。
实施例1：四齿环金属铂(II)配合物(S,R)-P-PtLA1合成路线如下：
Figure PCTCN2022086993-appb-000059
Figure PCTCN2022086993-appb-000060
(1)中间体1-Br的合成：向带有磁力转子的单口瓶中依次加入间溴苯甲腈(10g,54.94mmol,1.0当量)，甲醇钠(297mg,5.49mmol,0.1当量)，室温搅拌，反应1天。加乙酸至固体消失，减压蒸馏除去溶剂，得粗品A，加入(1S,2R)-1-氨基2,3-二氢-1H-茚-2-醇(4.10g,27.47mmol,0.5当量)，无水乙醇(30mL)，该混合物在85℃的油浴中搅拌反应1.5天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝50:1-10:1，得到产物1-Br，白色固体5.60g，收率65％。 1H NMR(500MHz,CDCl 3):δ3.40(d,J＝18.0Hz,1H),3.51-3.56(m,1H),5.57(t,J＝7.5Hz,1H),7.79(d,J＝8.0Hz,1H),7.26-7.31(m,4H),7.59-7.63(m,2H),7.96(d,J＝8.0Hz,1H),8.12(t,J＝2.0Hz,1H)。
(2)中间体4-OH的合成：向带有磁力转子的干燥封管中依次加入手性溴(1.5g,4.77mmol,1.0当量)，氯化亚铜(24mg,0.24mmol,5mol％)，配体1(87mg,0.24mmol,5mol％)和叔丁醇钠(917mg,9.55mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(8mL)，去离子水(2mL)。将封管置于110℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加稀盐酸调至中性或弱酸性，再加碳酸氢钠调至弱碱性，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物4-OH，棕色固体934mg，收率78％。 1H NMR(500MHz,DMSO-d 6):δ3.22(d,J＝18.0Hz,1H),3.46-3.51(m,1H),5.47-5.50(m,1H),5.68(d,J＝8.0Hz,1H),6.87-6.90(m,1H),7.21-7.3(m,6H),7.43-7.44(m,1H),9.67(s,1H)。
(3)中间体手性2-Br的合成：向带有磁力转子的单口瓶中依次加入间溴苯甲腈(10g,54.94mmol,1.0当量)，甲醇钠(297mg,5.49mmol,0.1当量)，室温搅拌，反应1天。加乙酸至固体消失，减压蒸馏除去溶剂，得粗品A，加入(1R,2S)-1-氨基2,3-二氢-1H-茚-2-醇(3.28g,21.97mmol,0.4当量)，无水乙醇(30mL)，该混合物在85℃的油浴中搅拌反应1.5天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝50:1-10:1，得到产物2-Br，白色固体5.74g，收率83％。 1H NMR(500MHz,CDCl 3):δ3.41(d,J＝18.5Hz,1H),3.52-3.57(m,1H),5.59(s,1H),5.81(d,J＝3.0Hz,1H),7.27-7.31(m,4H),7.60-7.65(m,2H),7.98-8.00(m,1H),8.13(s,1H)。
(4)配体(S,R)-LA1的合成：向带有磁力转子的干燥封管中依次加入1-Br(579mg,1.84mmol,1.2当量)，1-OH(400mg,1.54mmol,1.0当量)，碘化亚铜(29mg,0.15mmol,10mol％)，配体2(50mg,0.15mmol,10mol％)和磷酸钾(654mg,3.08mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(10mL)。将封管置于90℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体(S,R)-LA1，白色固体533mg，收率70％。 1H NMR(500MHz,DMSO-d 6):δ3.19(d,J＝17.5Hz,1H),3.42-3.47(m,1H),5.46-5.49(m,1H),5.65(d,J＝7.5Hz,1H),7.03(dd,J＝8.5,2.5Hz,1H),7.19-7.28(m,4H),7.35-7.40(m,3H),7.42-7.47(m,3H),7.50(d,J＝2.0Hz,1H),7.57-7.59(m,1H),7.76-7.79(m,2H),8.04-8.07(m,1H),8.23(d,J＝7.5Hz,1H),8.27(d,J＝8.0Hz,1H),8.65-8.66(m,1H)。
(5)(S,R)-P-PtLA1的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LA1(150mg,0.30mmol,1.0当量)，氯亚铂酸钾(132mg,0.32mmol,1.05当量)，四正丁基溴化铵(10mg,0.030mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(25mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(114mg,0.6mmol,2.0当量)，二氯甲烷(30mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物(S,R)-P-PtLA1，淡黄色固体126mg，收率60％。 1H NMR(500MHz,DMSO-d 6):δ3.49(d,J＝18.5Hz,1H),3.62-3.67(m,1H),6.05(t,J＝7.5Hz,1H),6.26(d,J＝7.5Hz,1H),7.01(d,J＝7.5Hz,1H),7.10(t,J＝7.5Hz,1H),7.12-7.18(m,3H),7.20-7.24(m,2H),7.35(d,J＝7.5Hz,1H),7.41-7.44(m,2H),7.48-7.52(m,1H),7.88(d,J＝8.0Hz,1H),8.15-8.17(m,1H),8.20(d,J＝8.5Hz,1H),8.26-8.29(m,1H),8.36(d,J＝8.5Hz,1H),9.57(dd,J＝6.0,1.5Hz,1H)。
实施例2：四齿环金属铂(II)配合物(R,S)-M-PtLA1的合成：
Figure PCTCN2022086993-appb-000061
(1)配体(R,S)-LA1的合成：向带有磁力转子的干燥封管中依次加入2-Br(3.19g,10.14mmol,1.2当量)，1-OH(2.20g,8.45mmol,1.0当量)，碘化亚铜(29mg,0.84mmol,10mol％)，配体2(276mg,0.84mmol,10mol％)和磷酸钾(3.59g,16.90mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(40mL)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R,S)-LA1，白色固体2.12g，收率51％。 1H NMR(500MHz,DMSO-d 6):δ3.19(d,J＝18.0Hz,1H),3.42-3.47(m,1H),5.46-5.49(m,1H),5.65(d,J＝7.5Hz,1H),7.03(dd,J＝7.5,2.0Hz,1H),7.19-7.28(m,4H),7.34-7.40(m,3H),7.43-7.48(m,3H),7.50(d,J＝2.0Hz,1H),7.57-7.59(m,1H),7.77-7.79(m,2H),8.04-8.08(m,1H),8.24(d,J＝8.0Hz,1H),8.28(d,J＝8.5Hz,1H),8.65-8.67(m,1H)。
(2)(R,S)-M-PtLA1的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(R,S)-LA1(900mg,1.82mmol,1.0当量)，氯亚铂酸钾(795mg,1.92mmol,1.05当量)，四正丁基溴化铵(59mg,0.182mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(110mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物(R,S)-M-PtLA1，淡黄色固体1.01g，收率81％。 1H NMR(500MHz,DMSO-d 6):δ3.49(d,J＝18.0Hz,1H),3.62-3.67(m,1H),6.04(t,J＝7.0Hz,1H),6.27(d,J＝7.0Hz,1H),7.01(d,J＝8.0Hz,1H),7.10(t,J＝7.0Hz,1H),7.12-7.18(m,3H),7.21-7.24(m,2H),7.35(d,J＝7.0Hz,1H),7.41-7.44(m,2H),7.48-7.52(m,1H),7.88(d,J＝8.5Hz,1H),8.16-8.18(m,1H),8.20(d,J＝8.5Hz,1H),8.26-8.30(m,1H),8.37(d,J＝8.5Hz,1H),9.57(m,1H)。
实施例3：四齿环金属铂(II)配合物(S,R)-P-PtLA2的合成：
Figure PCTCN2022086993-appb-000062
(1)配体(S,R)-LA2的合成：向带有磁力转子的干燥封管中依次加入1-Br(1.82g,5.80mmol,1.2当量)，2-OH(1.50g,4.83mmol,1.0当量)，碘化亚铜(91mg,0.48mmol,10mol％)，配体2(157mg,0.48mmol,10mol％)和磷酸钾(2.05g,9.05mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(30mL)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝20:1-5:1，得到产物(S,R)-LA2，棕色固体1.63g，收率62％。 1H NMR(600MHz,CDCl 3):δ3.45(d,J＝18.6Hz,1H),3.53-3.56(m,1H),5.66-5.69(m,1H),5.88(s,1H),7.01(dd,J＝8.4,1.8Hz,1H),7.24-7.31(m,6H),7.35-7.40(m,2H),7.44-7.47(m,1H),7.56-7.59(m,1H),7.63(t,J＝1.8Hz,1H),7.70(d,8.4Hz,1H),7.73-7.75(m,1H),7.77(d,J＝8.0Hz,1H),7.87-7.88(m,1H),7.97(d,J＝8.4Hz,1H)。8.07(d,J＝8.4Hz,1H),8.08-8.10(m,2H),8.32(d,J＝8.0Hz,1H)。
(2)(S,R)-P-PtLA2的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LA2(200mg,0.37mmol,1.0当量)，氯亚铂酸钾(161mg,0.39mmol,1.05当量)，四正丁基溴化铵(12mg,0.037mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后，先室温搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)，二氯甲烷(30mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物(S,R)-P-PtLA2，淡黄色固体101mg，收率37％。 1H NMR(600MHz,DMSO-d 6):δ3.47(d,J＝18.0Hz,1H),3.49-3.51(m,1H),5.12(d,J＝7.8Hz,1H),5.32(d,J＝4.8Hz,1H),5.93-5.95(m,1H),6.05(d,J＝8.4Hz,1H),6.93(d,J＝7.2Hz,1H),7.10(t,J＝7.2Hz,1H),7.15(t,J＝8.4Hz,1H),7.17-7.18(m,1H),7.21(d,J＝7.2Hz,1H),7.23-7.25(m,1H),7.45(t,J＝7.8Hz,1H),7.53-7.56(m,1H),7.66-7.69(m,1H),7.78(d,J＝8.4Hz,1H),8.04-8.06(m,1H),8.13(dd,J＝7.8,1.2Hz,1H),8.18(dd,J＝7.8,1.2Hz,1H),8.36(d,J＝7.8Hz,1H),8.66(d,J＝9.0Hz,1H),8.82(d,J＝9.0Hz,1H),9.40(d,J＝8.4Hz,1H)。
实施例4：四齿环金属铂(II)配合物(R,S)-M-PtLA2的合成：
Figure PCTCN2022086993-appb-000063
(1)配体(R,S)-LA2的合成：向带有磁力转子的干燥封管中依次加入2-Br(1.38g,4.40mmol,1.2当量)，2-OH(1.14g,3.67mmol,1.0当量)，碘化亚铜(70mg,0.37mmol,10mol％)，配体2(121mg,0.37mmol,10mol％)和磷酸钾(1.56g,7.34mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。将封管置于90℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R,S)-LA2，白色固体1.23g，收率 62％。 1H NMR(500MHz,CDCl 3):δ3.44(d,J＝18.0Hz,1H),3.53-3.58(m,1H),5.66-5.70(m,1H),5.85-5.88(m,1H),7.01(dd,J＝8.0,2.0Hz,1H),7.24-7.31(m,6H),7.35-7.47(m,3H),7.56-7.59(m,1H),7.62(t,J＝2.0Hz,1H),7.70(d,J＝2.0Hz,1H),7.72-7.78(m,2H),7.88(d,J＝7.5Hz,1H),7.96(d,J＝8.0Hz,1H),8.06-8.10(m,3H),8.31(d,J＝8.5Hz,1H)。
(2)(R,S)-M-PtLA2的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(R,S)-LA2(200mg,0.37mmol,1.0当量)，氯亚铂酸钾(161mg,0.39mmol,1.05当量)，四正丁基溴化铵(12mg,0.037mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后，先室温搅拌12小时，然后在110℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)，二氯甲烷(30mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物(R,S)-M-PtLA2，淡黄色固体119mg，收率44％。 1H NMR(500MHz,DMSO-d 6):δ3.29-3.34(m,1H),3.45-3.50(m,1H),5.12(d,J＝7.5Hz,1H),5.94(d,J＝7.0Hz,1H),6.04(d,J＝8.0Hz,1H),6.94(t,J＝7.5Hz,1H),7.10(t,J＝7.5Hz,1H),7.15(d,J＝8.0Hz,1H),7.17-7.21(m,3H),7.23-7.25(m,1H),7.45(t,J＝7.5Hz,1H),7.53-7.56(m,1H),7.68(t,J＝7.0Hz,1H),7.78(d,J＝8.0Hz,1H),8.04-8.07(m,1H),8.12-8.14(m,1H),8.17-8.19(m,1H),8.36(d,J＝8.0Hz,1H),8.66(d,J＝9.5Hz,1H),8.82(d,J＝9.5Hz,1H),9.40(d,J＝8.5Hz,1H)。
实施例5：四齿环金属铂(II)配合物(S,R)-P-PtLA3的合成：
Figure PCTCN2022086993-appb-000064
(1)配体(S,R)-LA3合成：向带有磁力转子的干燥封管中依次加入1-Br(477mg,1.52mmol,1.2当量)，3-OH(400mg,1.27mmol,1.0当量)，碘化亚铜(25mg,0.13mmol,10mol％)，配体2(43mg,0.13mmol,10mol％)和磷酸钾(539mg,2.54mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(10mL)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷/乙酸乙酯＝5:1:1，得到产物(S,R)-LA3，棕色固体412mg，收率59％。 1H NMR(500MHz,CDCl 3):δ1.83-1.94(m,4H),2.82(t,J＝6.0Hz,2H),2.94(d,J＝6.5Hz,2H),3.31-3.35(d,J＝17.5Hz,1H),3.44-3.49(m,1H),5.43-5.46(m,1H),5.71(d,J＝8.0Hz,1H),6.96(dd,J＝8.5,2.5Hz,1H),7.11-7.14(m,1H),7.24-7.27(m,7H),7.28-7.30(m,2H),7.32(d,J＝8.0Hz,1H),7.37-7.41(dd,J＝3.0,1.5Hz,1H),7.65-7.67(m,1H),7.77(d,J＝6.0Hz,1H),8.02-8.06(m,2H)。
(2)(S,R)-P-PtLA3的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LA3(200mg,0.37mmol,1.0当量)，氯亚铂酸钾(161mg,0.39mmol,1.05当量)，四正丁基溴化铵(12mg,0.037mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后，先室温搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1-1:2，得到产物(S,R)-P-PtLA3，淡黄色固体134mg，收率49％。 1H NMR(400MHz,CDCl 3):δ1.83-1.91(m,2H),2.85-2.92(m,4H),2.94(d,J＝6.5Hz,2H),3.41-3.46(d,J＝19.6Hz,1H),3.53-3.59(m,1H),5.61(d,J＝7.6Hz,1H),5.65-5.69(m,1H),6.96-7.00(m,1H),7.08-7.17(m, 2H),7.15-7.31(m,6H),7.36-7.40(m,2H),7.57-7.62(m 1H),7.91-7.96(m,2H),8.11-8.13(m,1H)。
实施例6：四齿环金属铂(II)配合物(R,S)-M-PtLA3的合成：
Figure PCTCN2022086993-appb-000065
(1)配体(R,S)-LA3的合成：向带有磁力转子的干燥封管中依次加入2-Br(477mg,1.52mmol,1.2当量)，3-OH(400mg,1.27mmol,1.0当量)，碘化亚铜(25mg,0.13mmol,10mol％)，配体2(43mg,0.13mmol,10mol％)和磷酸钾(539mg,2.54mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(10mL)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷/乙酸乙酯＝5:1:1，得到产物(R,S)-M-LA3，棕色固体392mg，收率56％。 1H NMR(500MHz,CDCl 3):δ1.86-1.93(m,4H),2.84(t,J＝7.5Hz,2H),2.94(d,J＝6.5Hz,2H),3.41(d,J＝18.0Hz,1H),3.49-3.55(m,1H),5.61-5.66(m,1H),5.77-5.82(m,1H),6.94-6.96(m,1H),7.24-7.27(m,7H),7.28-7.31(m,2H),7.37-7.42(m,2H),7.52-7.55(m,1H),7.56-7.58(m,1H),7.73(d,J＝8.5Hz,1H),8.03-8.06(m,2H)。
(2)(R,S)-PtLA3的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(R,S)-LA3(200mg,0.37mmol,1.0当量)，氯亚铂酸钾(161mg,0.39mmol,1.05当量)，四正丁基溴化铵(12mg,0.037mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后，先室温搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1-1:2，得到产物(R,S)-M-PtLA3，淡黄色固体128mg，收率47％。δ1.88-1.93(m,4H),2.84-2.94(m,4H),3.55(d,J＝18.0Hz,1H),3.56-3.61(m,1H),5.62(d,J＝7.5Hz,1H),5.85-5.88(m,1H),6.68(d,J＝7.5Hz,1H),6.99-7.01(m,1H),7.01-7.13(m,1H),7.18-7.24(m,5H),7.31-7.35(m,1H),7.37-7.41(m,1H),7.60(d,J＝8.0Hz,1H),7.68(d,J＝8.0Hz,1H),7.93-7.98(m,2H),8.13-8.14(d,J＝8.5Hz,1H)。
实施例7：四齿环金属铂(II)配合物P-PtLC1的合成：
Figure PCTCN2022086993-appb-000066
P-LC1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LC-OH(500mg,1.99mmol,1.0当量)、1-Br(873mg,2.39mmol,1.2当量)、碘化亚铜(76mg,0.40mmol,20mol％)、配体2(138mg,0.40mmol,20mol％)和磷酸钾(845mg,3.98mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体758mg，收率71％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)1.61(s,6H),3.23(d,J＝18.0Hz,1H), 3.48(dd,J＝18.0Hz,7.0Hz,1H),5.49-5.52(m,1H),5.68(d,J＝8.0Hz,1H),6.05(d,J＝2.5Hz,1H),6.36(dd,J＝8.0,1.5Hz,1H),6.59(dd,J＝7.5,2.5Hz,1H),6.98-7.05(m,2H),7.11(ddd,J＝7.5,2.5,1.0Hz,1H),7.22-7.31(m,4H),7.35-7.44(m,4H),7.49-7.53(m,2H),7.55-7.57(m,1H),7.89-7.92(m,1H),8.58(ddd,J＝7.5,2.0,1.0Hz,1H)。
P-PtLC1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LC1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝8:1-1:1，得淡黄色固体172mg，收率64％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.34(s,3H),1.91(s,3H),3.55(s,2H),5.79-5.84(m,2H),6.76(d,J＝7.5Hz,1H),6.90-6.93(m,1H),7.01(d,J＝8.5Hz,1H),7.05-7.15(m,4H),7.16-7.26(m,6H),7.37(d,J＝8.5Hz,1H),7.47-7.49(m,1H),7.67-7.71(m,1H),9.11(dd,J＝5.5,2.0Hz,1H)。
实施例8：四齿环金属铂(II)配合物M-PtLC1的合成：
Figure PCTCN2022086993-appb-000067
M-LC1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LC-OH(550mg,2.19mmol,1.0当量)、2-Br(961mg,2.63mmol,1.2当量)、碘化亚铜(84mg,0.44mmol,20mol％)、配体2(145mg,0.44mmol,20mol％)和磷酸钾(930mg,4.38mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体525mg，收率45％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.66(s,6H),3.35(d,J＝18.0Hz,1H),3.48(dd,J＝18.0Hz,7.0Hz,1H),5.44-5.47(m,1H),5.72(d,J＝7.5Hz,1H),6.30(d,J＝2.5Hz,1H),6.54-6.58(m,2H),6.99-7.06(m,3H),7.20(ddd,J＝7.5,5.0,1.0Hz,1H),7.25-7.30(m,5H),7.36(d,J＝8.5Hz,1H),7.47(dd,J＝7.5,2.0Hz,1H),7.52-7.56(m,2H),7.62-7.64(m,1H),7.71-7.74(m,1H),8.62(ddd,J＝5.0,2.0,1.0Hz,1H)。
M-PtLC1的合成：在具有磁子的50mL三口烧瓶中依次加入M-LC1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝8:1-1:1，得淡黄色固体132mg，收率49％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.34(s,3H),1.91(s,3H),3.55(s,2H),5.77-5.82(m,2H),6.75(d,J＝7.5Hz,1H),6.87-6.90(m,1H),7.02(d,J＝8.5Hz,1H),7.05-7.15(m,4H),7.18-7.25(m,6H),7.36(d,J＝8.5Hz,1H),7.47-7.49(m,1H),7.66-7.69(m,1H),9.12(dd,J＝5.5,1.5Hz,1H)。
实施例9：四齿环金属铂(II)配合物(S,R)-P-PtLAN的合成：
Figure PCTCN2022086993-appb-000068
(1)配体(S,R)-LAN的合成：向带有磁力搅转子的反应管中依次加入1-Br(528mg,1.68mmol,1.2当量)，1-NH(548mg,1.40mmol,1.0当量)，三(二亚苄基丙酮)二钯(39mg,0.042mmol,3mol％)，2-(二叔丁基膦)联苯(13mg,0.032mmol,8mol％)，叔丁醇钠(404mg,4.2mmol,3.0当量)，然后抽换氮气三次，在氮气保护下加入甲苯(10mL)。随后在110℃的油浴锅中搅拌反应25小时，冷却至室温，减压蒸馏除去溶剂，得到粗品。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯的体积比为6:1-2:1，得到产物(S,R)-P-LAN泡沫状固体599mg，收率68％。 1H NMR(400MHz,DMSO-d 6):δ1.27(s,9H),3.13-3.18(m,1H),3.44-3.45(m,1H),5.44(t,J＝6.0Hz,1H),5.62(d,J＝7.6Hz,1H),6.95(d,J＝7.6Hz,1H),7.00(d,J＝7.6Hz,2H),7.10(d,J＝7.6Hz,1H),7.19-7.25(m,3H),7.29-7.38(m,7H),7.41-7.43(m,2H),7.51(s,1H),7.62(d,J＝8.0Hz,1H),7.74(d,J＝8.0Hz,1H),7.90(t,J＝8.0Hz,1H),8.13-8.15(m,2H),8.55(s,1H)。
(2)(S,R)-P-PtLAN的合成：向带有磁力搅转子的三口烧瓶中，依次加入(S,R)-P-LAN(187mg,0.30mmol,1.0当量)，二氯化铂(84mg,0.315mmol,1.05当量)，然后抽换氮气三次，在氮气保护下加入苯甲腈(18mL)。随后在180℃的油浴锅中搅拌反应18小时，冷却至室温，减压蒸馏除去溶剂，得到粗品。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷的体积比为4:1-2:1，得到产物(S,R)-P-PtLAN红色固体91mg，收率37％。 1H NMR(400MHz,DMSO-d 6):δ1.39(s,9H),3.49(s,1H),3.60-3.67(m,1H),5.99(t,J＝6.8Hz,1H),6.19(d,J＝7.2Hz,1H),6.26(d,J＝8.0Hz,1H),6.32(d,J＝8.8Hz,1H),6.88-6.94(m,2H),7.00(d,J＝7.2Hz,1H),7.08(t,J＝7.6Hz,1H),7.16-7.23(m,3H),7.33-7.46(m,4H),7.57(d,J＝8.8Hz,1H),7.69(d,J＝8.0Hz,2H),7.99(d,J＝7.6Hz,1H),8.15(d,J＝8.4Hz,1H),8.22-8.30(m,2H),9.55(d,J＝5.2Hz,1H)。
实施例10：四齿环金属铂(II)配合物(R,S)-M-PtLAN的合成：
Figure PCTCN2022086993-appb-000069
(1)配体(R,S)-LAN的合成：向带有磁力搅转子的反应管中依次加入1-Br(528mg,1.68mmol,1.2当量)，1-NH(548mg,1.40mmol,1.0当量)，三(二亚苄基丙酮)二钯(39mg,0.042mmol,3mol％)，2-(二叔丁基膦)联苯(13mg,0.032mmol,8mol％)，叔丁醇钠(404mg,4.2mmol,3.0当量)，然后抽换氮气三次，在氮气保护下加入甲苯(10mL)。随后在110℃的油浴锅中搅拌反应25小时，冷却至室温，减压蒸馏除去溶剂，得到粗品。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯的体积比为6:1-2:1，得到产 物(R,S)-M-LAN泡沫状固体608mg，收率69％。 1H NMR(400MHz,DMSO-d 6):δ1.27(s,9H),3.14-3.18(m,1H),3.44-3.46(m,1H),5.44(t,J＝7.2Hz,1H),5.62(d,J＝7.6Hz,1H),6.95(d,J＝8.4Hz,1H),7.00(d,J＝7.6Hz,2H),7.10(d,J＝8.4Hz,1H),7.18-7.27(m,3H),7.29-7.38(m,7H),7.41-7.44(m,2H),7.51(s,1H),7.62(d,J＝8.0Hz,1H),7.74(d,J＝8.4Hz,1H),7.91(t,J＝8.0Hz,1H),8.13-8.15(m,2H),8.56(d,J＝4.8Hz,1H)。
(2)(R,S)-M-PtLAN的合成：向带有磁力搅转子的三口烧瓶中，依次加入(R,S)-M-LAN(250mg,0.40mmol,1.0当量)，二氯化铂(112mg,0.42mmol,1.05当量)，然后抽换氮气三次，在氮气保护下加入苯甲腈(20mL)。随后在180℃的油浴锅中搅拌反应18小时，冷却至室温，减压蒸馏除去溶剂，得到粗品。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷的体积比为4:1-2:1，得到产物(R,S)-M-PtLAN红色固体127mg，收率39％。 1H NMR(400MHz,DMSO-d 6):δ1.39(s,9H),3.49(s,1H),3.60-3.67(m,1H),5.99(t,J＝6.8Hz,1H),6.19(d,J＝7.2Hz,1H),6.26(d,J＝8.0Hz,1H),6.32(d,J＝8.8Hz,1H),6.88-6.94(m,2H),7.00(d,J＝7.2Hz,1H),7.08(t,J＝7.6Hz,1H),7.16-7.23(m,3H),7.33-7.46(m,4H),7.57(d,J＝8.8Hz,1H),7.69(d,J＝8.0Hz,2H),7.99(d,J＝7.6Hz,1H),8.15(d,J＝8.4Hz,1H),8.22-8.30(m,2H),9.55(d,J＝5.2Hz,1H)。
实施例11：四齿环金属铂(II)配合物(R,S)-M-PtLH1的合成：
Figure PCTCN2022086993-appb-000070
(1)配体(R,S)-LH1的合成：向带有磁力转子的干燥封管中加入ACzCzH(200mg,0.6mmol,1.0当量)，2-Br(245mg,0.78mmol,1.3当量)，三(二亚苄基丙酮)二钯(22mg,0.024mmol,4mol％)，2-(二叔丁基膦)联苯(14mg,0.048mmol,8mol％)和叔丁醇钠(115mg,1.2mmol,2.0当量)然后抽换氮气三次，在氮气保护下加入甲苯(12mL)。该混合物在110℃的油浴锅中搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R,S)-LH1，白色固体214mg，收率63％。 1H NMR(500MHz,DMSO-d 6):δ3.21-3.24(m,1H),3.47-3.55(m,1H),5.53-5.56(m,1H),5.72(d,J＝8.5Hz,1H),7.20-7.29(m,3H),7.31-7.43(m,5H),7.47-7.54(m,3H),7.57-7.59(m,2H),7.72(t,J＝7.5Hz,1H),7.87-7.89(m,1H),7.95(d,J＝9.0Hz,1H),8.07(t,J＝2.5Hz,1H),8.30(d,J＝8.5Hz,1H),8.37-8.38(m,2H),8.51(d,J＝9.0Hz,1H),8.64(dd,J＝8.0,1.5Hz,1H)。
(2)(R,S)-M-PtLH1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(R,S)-LH1(212mg,0.37mmol,1.0当量)，二氯化铂(104mg,0.39mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(R,S)-M-PtLH1，黄色固体207mg，收率74％。 1H NMR(500MHz,DMSO-d 6):δ3.51-3.61(m,2H),5.73-5.76(m,1H),5.98(t,J＝6.0Hz,1H),6.22(d,J＝7.0Hz,1H),6.72(t,J＝7.5Hz,1H),7.11(t,J＝7.5Hz,1H),7.27-7.29(m,1H),7.31-7.34(m,3H),7.47-7.51(m,1H),7.57(t,J＝7.5Hz,1H),7.63(dd,J＝7.5,5.5Hz,1H),7.74-7.77(m,1H),7.85(d,J＝8.5Hz,1H),8.05(d,J＝8.5Hz,1H),8.18-8.20(m,1H),8.25-8.26(m,2H),8.32(d,J＝8.5Hz,1H),8.54(d,J＝7.5Hz,1H),9.11(dd,J＝7.5,1.0Hz,1H),9.47-9.48(m,1H)。
实施例12：四齿环金属铂(II)配合物(S,R)-P-PtLH1的合成：
Figure PCTCN2022086993-appb-000071
(1)配体(S,R)-LH1的合成：向带有磁力转子的干燥封管中加入ACzCzH(200mg,0.6mmol,1.0当量)，1-Br(245mg,0.78mmol,1.3当量)，三(二亚苄基丙酮)二钯(22mg,0.024mmol,4mol％)，2-(二叔丁基膦)联苯(14mg,0.048mmol,8mol％)和叔丁醇钠(115mg,1.2mmol,2.0当量)然后抽换氮气三次，在氮气保护下加入甲苯(12mL)。该混合物在110℃的油浴锅中搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S,R)-LH1，白色固体203mg，收率60％。 1H NMR(500MHz,DMSO-d 6):δ3.21-3.24(m,1H),3.46-3.51(m,1H),5.52-5.55(m,1H),5.72(d,J＝7.5Hz,1H),7.20-7.29(m,3H),7.31-7.42(m,5H),7.47-7.53(m,3H),7.57-7.58(m,2H),7.72(t,J＝7.5Hz,1H),7.87-7.8(m,1H),7.95(d,J＝8.0Hz,1H),8.07(t,J＝1.5Hz,1H),8.29(d,J＝7.5Hz,1H),8.36-8.38(m,2H),8.51(d,J＝8.5Hz,1H),8.63(dd,J＝8.0,2.0Hz,1H)。
(2)(S,R)-P-PtLH1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(S,R)-LH1(120mg,0.21mmol,1.0当量)，二氯化铂(71mg,0.27mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(S,R)-P-PtLH1，黄色固体83mg，收率52％。 1H NMR(500MHz,DMSO-d 6):δ3.51-3.61(m,2H),5.74(d,J＝8.0Hz,1H),5.98(t,J＝5.5Hz,1H),6.22(d,J＝6.5Hz,1H),6.72(t,J＝8.0Hz,1H),7.11(t,J＝8.0Hz,1H),7.27-7.29(m,1H),7.31-7.34(m,3H),7.47-7.51(m,1H),7.58(t,J＝7.5Hz,1H),7.64(dd,J＝7.5,5.5Hz,1H),7.74-7.78(m,1H),7.85(d,J＝8.0Hz,1H),8.05(d,J＝8.5Hz,1H),8.19(d,J＝7.5Hz,1H),8.25-8.26(m,2H),8.32(d,J＝8.5Hz,1H),8.54(d,J＝7.5Hz,1H),9.12(dd,J＝7.5,1.0Hz,1H),9.47-9.48(m,1H)。
实施例13：四齿环金属铂(II)配合物P-PtLIII-1的合成：
Figure PCTCN2022086993-appb-000072
(1)配体LIII-1的合成：向带有磁力转子的干燥封管中依次加入1-Br(750mg,2.39mmol,1.5当量)，4-OH(400mg,1.59mmol,1.0当量)，碘化亚铜(37mg,0.20mmol,10mol％)，配体1(65mg,0.20mmol,10mol％)和磷酸钾(832mg,3.92mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(15mL)。 将封管置于90℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物L III-1，白色固体431mg，收率56％。 1H NMR(500MHz,DMSO-d 6):δ3.22(d,J＝18.5Hz,2H),3.45-3.50(m,2H),5.49-5.53(m,2H),5.69(d,J＝7.5Hz,2H),7.21-7.30(m,8H),7.38(s,2H),7.42(d,J＝6.5Hz,2H),7.50(t,J＝8.0Hz,2H),7.65(d,J＝7.5Hz,2H)。
(2)P-PtLIII-1的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入L6(200mg,0.41mmol,1.0当量)，氯亚铂酸钾(180mg,0.43mmol,1.05当量)，四正丁基溴化铵(13mg,0.041mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(25mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtLIII-1，淡黄色固体104mg，收率36％。 1H NMR(500MHz,DMSO-d 6):δ3.63(d,J＝18.5Hz,2H),3.67-3.72(m,2H),6.27-6.29(m,2H),6.35(d,J＝7.0Hz,2H),7.27-7.33(m,6H),7.34-7.38(m,2H),7.40-7.43(m,4H),7.87(d,J＝8.0Hz,2H)。
实施例14：四齿环金属铂(II)配合物M-PtLIII-1的合成：
Figure PCTCN2022086993-appb-000073
(1)M-LIII-1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入4-III-OH(500mg,1.99mmol,1.0当量)、2-Br(751mg,2.39mmol,1.2当量)、碘化亚铜(152mg,0.80mmol,40mol％)、2-吡啶甲酸(196mg,1.59mmol,80mol％)和磷酸钾(845mg,3.98mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于110℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝30:1-10:1，得白色固体353mg，收率37％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝17.5,1.5Hz,1H),3.48(dd,J＝17.5,6.5Hz,1H),5.44-5.48(m,1H),5.72(d,J＝8.0Hz,1H),7.06(ddd,J＝8.5,2.5,1.0Hz,1H),7.25-7.28(m,3H),7.32(d,J＝8.0Hz,1H),7.53-7.56(m,2H),7.68-7.70(m,1H)。
(2)M-PtLIII-1的合成：在具有磁子的50mL三口烧瓶中依次加入M-LIII-1(200mg,0.41mmol,1.0当量)、氯亚铂酸钾(178mg,0.43mmol,1.05当量)和四正丁基溴化铵(13mg,0.041mmol,10mol％)，抽换氮气三次，加入醋酸(25mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(155mg,0.82mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝4:1-1:1，得淡黄色固体83mg，收率30％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.60(dd,J＝18.0,5.0Hz,1H),3.65(d,J＝18.0Hz,1H),5.87(d,J＝7.0Hz,1H),5.93-5.96(m,1H),7.07-7.13(m,2H),7.19(dd,J＝7.0,2.0Hz,1H),7.29-7.34(m,3H),7.78-7.81(m,1H)。
实施例15：四齿环金属铂(II)配合物P-PtLB1的合成：
Figure PCTCN2022086993-appb-000074
(1)P-LB1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LB-OH(500mg,1.92mmol,1.0当量)、2-Br(723mg,2.30mmol,1.2当量)、碘化亚铜(36mg,0.19mmol,10mol％)、配体2(65mg,0.19mmol,10mol％)和磷酸钾(815mg,3.84mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体678mg，收率60％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.36(dd,J＝18.0,1.5Hz 1H),3.50(dd,J＝18.0,7.0Hz,1H),5.46-5.50(m,1H),5.74(d,J＝8.0Hz,1H),7.06(ddd,J＝8.0,2.5,1.0Hz,1H),7.21-7.24(m,2H),7.26-7.27(m,3H),7.29-7.32(m,2H),7.35-7.45(m,3H),7.51-7.57(m,3H),7.70-7.72(m,2H),8.10(d,J＝7.5Hz,1H),8.37(dd,J＝7.5,1.5Hz,1H),8.47(d,J＝4.5,1.5Hz,1H)。
(2)P-PtLB1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LB1(200mg,0.41mmol,1.0当量)、氯亚铂酸钾(178mg,0.43mmol,1.05当量)和四正丁基溴化铵(13mg,0.041mmol,10mol％)，抽换氮气三次，加入醋酸(25mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(155mg,0.82mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝4:1-1:1，得淡黄色固体154mg，收率55％。P-PtLB1  1H NMR(500MHz,DMSO-d 6):δ(ppm)3.48(d,J＝18.8Hz,1H),3.57(dd,J＝18.4Hz,5.6Hz,1H),5.60(d,J＝8.0Hz,1H),5.96(t,J＝6.4Hz,1H),6.14(d,J＝7.2Hz,1H),6.68(t,J＝7.2Hz,1H),7.02(dd,J＝7.6,0.8Hz,1H),7.07-7.19(m,4H),7.23(t,J＝8.0Hz,1H),7.30(d,J＝7.6Hz,1H),7.52-7.57(m,2H),7.63(dd,J＝7.6,5.6Hz,1H),7.69-7.74(m,1H),8.19(d,J＝8.4Hz,1H),8.51(d,J＝7.6Hz,1H),9.08(dd,J＝6.8,1.2Hz,1H),9.37(d,J＝5.6Hz,1H)
实施例16：四齿环金属铂(II)配合物M-PtLB1的合成：
Figure PCTCN2022086993-appb-000075
(1)M-LB1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LB-OH(500mg,1.92mmol,1.0当量)、2-Br(723mg,2.30mmol,1.2当量)、碘化亚铜(36mg,0.19mmol,10mol％)、配体2(65mg,0.19mmol,10mol％)和磷酸钾(815mg,3.84mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体678mg，收率60％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.36(d,J＝18.0Hz 1H),3.49(dd,J＝18.0,7.0Hz,1H),5.46-5.50(m,1H),5.74(d,J＝8.0Hz,1H),7.06(dd,J＝8.5,2.0Hz,1H),7.21-7.24(m,2H),7.26-7.28(m,3H),7.29-7.33(m,2H),7.35-7.45(m,3H),7.51-7.57(m,3H),7.70-7.72(m,2H),8.11(d,J＝8.0Hz,1H),8.37(dd,J＝7.5,1.5Hz,1H),8.47(d,J＝5.0,1.5Hz,1H)。
(2)M-PtLB1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LB1(200mg,0.41mmol,1.0当量)、氯亚铂酸钾(178mg,0.43mmol,1.05当量)和四正丁基溴化铵(13mg,0.041mmol,10mol％)，抽换氮气三次，加入醋酸(25mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(155mg,0.82mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝4:1-1:1，得淡黄色固体83mg，收率29％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.47(d,J＝18.0Hz,1H),3.57(dd,J＝18.0Hz,5.5Hz,1H),5.60(d,J＝8.0Hz,1H),5.96(t,J＝6.0Hz,1H),6.14(d,J＝7.0Hz,1H),6.68(t,J＝7.0Hz,1H),7.02(dd,J＝8.0,1.5Hz,1H),7.07-7.18(m,4H),7.22(t,J＝8.0Hz,1H),7.29(d,J＝7.5Hz,1H),7.51-7.56(m,2H),7.62(dd,J＝7.5,6.0Hz,1H),7.69-7.72(m,1H),8.18(d,J＝8.0Hz,1H),8.51(d,J＝7.5Hz,1H),9.08(d,J＝7.5,1.5Hz,1H),9.36(d,J＝5.5Hz,1H)
实施例17：四齿环金属铂(II)配合物P-PtLD1的合成：
Figure PCTCN2022086993-appb-000076
(1)P-LD1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LD-OH(500mg,1.65mmol,1.0当量)、1-Br(572mg,1.82mmol,1.1当量)、碘化亚铜(32mg,0.17mmol,10mol％)、配体2(59mg,0.17mmol,10mol％)和磷酸钾(700g,3.30mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于100℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝20:1-10:1，得白色固体480mg，收率54％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.64(s,6H),3.35(dd,J＝17.5,1.5Hz,1H),3.50(dd,J＝18.0,7.0Hz,1H),5.46-5.49(m,1H),5.73(d,J＝8.0Hz,1H),6.37(dd,J＝8.0,1.5Hz,1H),6.83(dd,J＝7.5,5.0Hz,1H),6.95-7.03(m,3H),7.07-7.12(m,2H),7.20(ddd,J＝8.0,2.5,1.0Hz,1H),7.26-7.28(m,3H),7.34(t,J＝8.5Hz,1H),7.42(dd,J＝7.5,1.5Hz,1H),7.52-7.57(m,2H),7.65(dd,J＝7.5,1.5Hz,1H),7.67-7.69(m,2H),8.00(dd,J＝5.0,2.0Hz,1H)。
(2)P-PtLD1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LD1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝3:1-1:1，得淡黄色固体135mg，收率50％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)1.41(s,3H),1.99(s,3H),3.42(d,J＝18.0Hz,1H),3.56(dd,J＝18.5Hz,6.0Hz,1H),5.92-5.98(m,3H),6.50(t,J＝7.5Hz,1H),6.68(dd,J＝7.5,1.0Hz,1H),6.80-6.82(m,1H),6.88(dd,J＝8.0,1.0Hz,1H),6.98(t,J＝7.5Hz,1H),7.06-7.20(m,6H),7.27(d,J＝7.5Hz,1H),7.34(dd,J＝7.5,5.5Hz,1H),7.57-7.59(m,1H),8.26(dd,J＝7.5,1.5Hz,1H),9.06(dd,J＝5.5,1.5Hz,1H)。
实施例18：四齿环金属铂(II)配合物M-PtLD1的合成：
Figure PCTCN2022086993-appb-000077
(1)M-LD1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LD-OH(500mg,1.65mmol,1.0当量)、2-Br(572mg,1.82mmol,1.1当量)、碘化亚铜(32mg,0.17mmol,10mol％)、配体2(59mg,0.17mmol,10mol％)和磷酸钾(700g,3.30mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝20:1-10:1，得白色固体433mg，收率49％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.64(s,6H),3.35(d,J＝17.5Hz,1H),3.50(dd,J＝17.5,6.5Hz,1H),5.46-5.49(m,1H),5.73(d,J＝8.0Hz,1H),6.37(dd,J＝8.0,1.5Hz,1H),6.83(dd,J＝7.5,4.5Hz,1H),6.95-7.03(m,3H),7.07-7.12(m,2H),7.20(ddd,J＝7.5,2.5,1.5Hz,1H),7.26-7.28(m,3H),7.34(t,J＝8.0Hz,1H),7.42(dd,J＝7.5,2.0Hz,1H),7.52-7.57(m,2H),7.65(dd,J＝8.0,1.5Hz,1H),7.67-7.69(m,2H),8.00(dd,J＝4.5,1.5Hz,1H)。
(2)M-PtLD1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LD1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝4:1-1:1，得淡黄色固体134mg，收率50％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)1.41(s,3H),1.99(s,3H),3.43(d,J＝18.5Hz,1H),3.56(dd,J＝18.5Hz,5.5Hz,1H),5.92-5.98(m,3H),6.50(t,J＝7.5Hz,1H),6.68(dd,J＝8.0,1.5Hz,1H),6.80-6.82(m,1H),6.88(dd,J＝8.0,1.5Hz,1H),6.98(t,J＝7.5Hz,1H),7.06-7.20(m,6H),7.27(d,J＝7.5Hz,1H),7.34(d,J＝8.0,6.0Hz,1H),7.57-7.59(m,1H),8.26(dd,J＝7.5,1.5Hz,1H),9.06(dd,J＝5.5,1.5Hz,1H)。
实施例19：四齿环金属铂(II)配合物P-PtLE1的合成：
Figure PCTCN2022086993-appb-000078
(1)P-LE1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LE-OH(500mg,1.66mmol,1.0当量)、1-Br(575mg,1.83mmol,1.1当量)、碘化亚铜(32mg,0.17mmol,10mol％)、配体2(59mg,0.17mmol,10mol％)和磷酸钾(705g,3.32mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于100℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体0.55g，收率62％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.73(s,6H),3.34(dd,J＝17.5,1.5Hz,1H),3.46(dd,J＝18.0Hz,7.0Hz,1H),5.43-5.47(m,1H),5.72(d,J＝7.5Hz,1H),7.00(dd,J＝8.5,2.0Hz,1H),7.04(dd,J＝7.5,4.5Hz,1H),7.17(ddd,J＝8.0,2.5,1.0Hz,1H),7.24-7.25(m,3H),7.32-7.36(m,2H),7.39(dd,J＝ 7.5,1.0Hz,1H),7.53-7.55(m,1H),7.63(dd,J＝2.5,1.5Hz,1H),7.67-7.69(m,1H),7.80(dd,J＝7.5,1.5Hz,1H),7.84(dd,J＝7.5,1.5Hz,1H),8.00(d,J＝8.5Hz,1H),8.26(dd,J＝5.0,2.0Hz,1H),8.82(d,J＝2.0Hz,1H)。
(2)P-PtLE1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LE1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝3:1-1:1，得淡黄色固体138mg，收率51％。 1H NMR(400MHz,DMSO-d 6):δ(ppm)1.72(s,3H),1.94(s,3H),3.48(d,J＝18.8Hz,1H),3.48(dd,J＝18.8Hz,6.4Hz,1H),5.98(t,J＝6.4Hz,1H),6.21(d,J＝7.2Hz,1H),6.42(d,J＝8.0Hz,1H),6.95(t,J＝7.6Hz,1H),7.13-7.24(m,5H),7.32-7.37(m,2H),7.44(t,J＝7.6Hz,1H),7.57(d,J＝7.6Hz,1H),7.89(d,J＝8.0Hz,1H),7.95(d,J＝8.0Hz,1H),8.50(dd,J＝7.6,1.6Hz,1H),9.30(d,J＝5.6Hz,1H)。
实施例20：四齿环金属铂(II)配合物M-PtLE1的合成：
Figure PCTCN2022086993-appb-000079
(1)M-LE1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LE-OH(500mg,1.66mmol,1.0当量)、2-Br(575mg,1.83mmol,1.1当量)、碘化亚铜(32mg,0.17mmol,10mol％)、配体2(59mg,0.17mmol,10mol％)和磷酸钾(705g,3.32mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(8mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体444mg，收率48％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.73(s,6H),3.34(dd,J＝18.0,2.0Hz,1H),3.46(dd,J＝17.5,6.5Hz,1H),5.43-5.47(m,1H),5.71(d,J＝8.0Hz,1H),7.00(dd,J＝8.5,2.0Hz,1H),7.04(dd,J＝7.5,4.5Hz,1H),7.17(ddd,J＝8.0,2.5,1.0Hz,1H),7.25-7.26(m,3H),7.32-7.40(m,3H),7.53-7.55(m,1H),7.63(dd,J＝2.5,1.5Hz,1H),7.68(d,J＝8.0Hz,1H),7.80(dd,J＝7.5,1.5Hz,1H),7.83(dd,J＝7.5,1.0Hz,1H),8.00(d,J＝7.5Hz,1H),8.26(dd,J＝5.0,2.0Hz,1H),8.82(d,J＝2.0Hz,1H)。
(2)M-PtLE1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LE1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝3:1-1:1，得淡黄色固体158mg，收率59％。 1H NMR(400MHz,DMSO-d 6):δ(ppm)1.72(s,3H),1.94(s,3H),3.48(d,J＝18.8Hz,1H),3.48(dd,J＝18.0Hz,6.0Hz,1H),5.98(t,J＝6.4Hz,1H),6.21(d,J＝7.2Hz,1H),6.42(d,J＝7.6Hz,1H),6.95(t,J＝7.2Hz,1H),7.13-7.24(m,5H),7.32-7.37(m,2H),7.44(t,J＝7.6Hz,1H),7.57(d,J＝7.6Hz,1H),7.89(d,J＝8.0Hz,1H),7.95(dd,J＝7.6,0.8Hz,1H),8.50(dd,J＝7.6,1.2Hz,1H),9.30(d,J＝6.0Hz,1H)。
实施例21：四齿环金属铂(II)配合物P-PtLF1的合成：
Figure PCTCN2022086993-appb-000080
(1)P-LF1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LF-OH(500mg,1.66mmol,1.0当量)、1-Br(575mg,1.83mmol,1.1当量)、碘化亚铜(32mg,0.17mmol,10mol％)、配体2(59mg,0.17mmol,10mol％)和磷酸钾(705g,3.32mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝10:1-5:1，得白色固体455mg，收率47％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.76(s,6H),3.35(dd,J＝18.0,2.0Hz,1H),3.48(dd,J＝18.0,7.0Hz,1H),5.46-5.49(m,1H),5.73(d,J＝8.0Hz,1H),6.75(dd,J＝8.5,2.5Hz,1H),7.19-7.22(m,2H),7.25-7.26(m,3H),7.35-7.40(m,2H),7.49-7.56(m,3H),7.69-7.72(m,2H),7.87(dd,J＝7.5,1.0Hz,1H),8.32(dd,J＝8.0,2.0Hz,1H),8.47(dd,J＝5.0,1.5Hz,1H),9.40(d,J＝2.5Hz,1H)。
(2)P-PtLF1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LF1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝8:1-1:1，得淡黄色固体96mg，收率34％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)1.66(s,3H),1.85(s,3H),3.49(d,J＝18.5Hz,1H),3.61(dd,J＝18.5Hz,6.0Hz,1H),5.98(t,J＝6.5Hz,1H),6.30(d,J＝7.5Hz,1H),6.32(d,J＝7.0Hz,1H),6.89(t,J＝7.5Hz,1H),7.03(d,J＝8.5Hz,1H),7.07(dd,J＝8.0,1.5Hz,1H),7.11-7.18(m,3H),7.32(d,J＝7.5Hz,1H),7.50(d,J＝8.5Hz,1H),7.55-7.59(m,2H),7.80(dd,J＝8.0,1.0Hz,1H),8.23(dd,J＝8.0,1.0Hz,1H),9.04(dd,J＝7.5,1.5Hz,1H),9.41(dd,J＝5.5,1.0Hz,1H)。
实施例22：四齿环金属铂(II)配合物M-PtLF1的合成：
Figure PCTCN2022086993-appb-000081
(1)M-LF1的合成：在具有磁子的干燥的50mL三口烧瓶中依次加入LF-OH(500mg,1.66mmol,1.0当量)、2-Br(625mg,1.99mmol,1.2当量)、碘化亚铜(32mg,0.17mmol,10mol％)、配体2(59mg,0.17mmol,10mol％)和磷酸钾(705g,3.32mmol,2.0当量)，抽换氮气3次，加入二甲基亚砜(10mL)，置于90℃油浴锅中，反应2天。冷却至室温后，反应液水洗，乙酸乙酯萃取3次，合并有机相，有机相水洗1次，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：乙酸乙酯＝15:1-8:1，得白色固体546mg，收率62％。 1H NMR(500MHz,CDCl 3):δ(ppm)1.76(s,6H),3.35(dd,J＝18.0,2.0Hz,1H),3.48(dd,J＝18.0,7.0Hz,1H),5.46-5.49(m,1H),5.73(d,J＝8.0Hz,1H),6.75(dd,J＝8.5,2.5Hz,1H), 7.19-7.22(m,2H),7.25-7.27(m,3H),7.35-7.40(m,2H),7.49-7.56(m,3H),7.69-7.73(m,2H),7.87(dd,J＝7.5,1.0Hz,1H),8.32(dd,J＝7.5,1.5Hz,1H),8.47(dd,J＝5.0,1.5Hz,1H),9.40(d,J＝2.5Hz,1H)。
(2)M-PtLF1的合成：在具有磁子的50mL三口烧瓶中依次加入P-LF1(200mg,0.37mmol,1.0当量)、氯亚铂酸钾(162mg,0.39mmol,1.05当量)和四正丁基溴化铵(12mg,0.037mmol,10mol％)，抽换氮气三次，加入醋酸(22mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝8:1-1:1，得淡黄色固体145mg，收率54％。 1H NMR(400MHz,DMSO-d 6):δ(ppm)1.66(s,3H),1.85(s,3H),3.49(d,J＝18.4Hz,1H),3.61(dd,J＝18.5Hz,6.0Hz,1H),5.99(t,J＝6.4Hz,1H),6.29(d,J＝8.0Hz,1H),6.32(d,J＝7.2Hz,1H),6.89(t,J＝7.2Hz,1H),7.02-7.19(m,5H),7.32(d,J＝7.6Hz,1H),7.50(d,J＝8.4Hz,1H),7.55-7.60(m,2H),7.81(d,J＝7.6Hz,1H),8.23(dd,J＝7.6,0.8Hz,1H),9.05(dd,J＝7.6,1.6Hz,1H),9.41(d,J＝5.6Hz,1H)。
实施例23：四齿环金属铂(II)配合物P-PtB1的合成：
Figure PCTCN2022086993-appb-000082
(1)配体P-B1的合成：向带有磁力转子的干燥封管中依次加入1-Br(689mg,2.20mmol,1.1当量)，B1-OH(340mg,2.00mmol,1.0当量)，碘化亚铜(76mg,0.40mmol,20mol％)，配体2(69mg,0.20mmol,10mol％)和磷酸钾(849mg,4.00mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(5mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体P-B1，白色固体430mg，收率53％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝18.0,1.5Hz,1H),3.48(dd,J＝18.0,7.0Hz,1H),5.46(ddd,J＝8.5,7.0,1.5Hz,1H),5.72(d,J＝8.0Hz,1H),7.03(ddd,J＝8.0,2.5,1.0Hz,1H),7.13(ddd,J＝8.5,2.5,1.0Hz,1H),7.22(ddd,J＝7.5,4.5,1.0Hz,1H),7.25–7.27(m,3H),7.34(t,J＝8.0Hz,1H),7.43(t,J＝8.0Hz,1H),7.53–7.56(m,1H),7.61(dd,J＝2.0,1.5Hz,1H),7.62(t,J＝2.0Hz,1H),7.67(dt,J＝8.0,1.0Hz,1H),7.69(dt,J＝7.5,1.0Hz,1H),7.72(dd,J＝7.5,2.0Hz,1H),7.75(ddd,J＝7.5,1.5,1.0Hz,1H),8.66(ddd,J＝5.0,2.0,1.0Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.73,76.98,83.24,117.53,118.82,119.41,120.59,121.86,122.05,122.34,123.36,125.24,125.60,127.43,128.44,129.64,129.70,130.10,136.71,139.68,141.43,141.85,149.64,156.61,157.16,157.50,163.41.HRMS(ESI):C 27H 21N 2O 2[M+H] +计算值405.1598，实测值405.1581。
(2)P-PtB1的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入P-B1(243mg,0.60mmol,1.0当量)，氯亚铂酸钾(262mg,0.63mmol,1.05当量)，四正丁基溴化铵(19mg,0.060mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(36mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应3天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(228mg,1.2mmol,2.0当量)，二氯甲烷(60mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相， 减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtB1，红色固体190mg，收率53％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.57(dd,J＝18.0,5.0Hz,1H),3.63(d,J＝18.0Hz,1H),5.76(d,J＝7.0Hz,1H),5.83(ddd,J＝6.5,5.0,0.5Hz,1H),7.11–7.16(m,2H),7.19(dd,J＝10.5,1.0Hz,1H),7.21–7.22(m,1H),7.23–7.28(m,3H),7.29–7.33(m,2H),7.47–7.48(m,1H),7.56(d,J＝8.0Hz,1H),7.90–7.96(m,2H),9.00(d,J＝5.5Hz,1H).HRMS(ESI):C 27H 19N 2O 2Pt[M+H] +计算值598.1089，实测值598.1090。
实施例24：四齿环金属铂(II)配合物M-PtB1的合成：
Figure PCTCN2022086993-appb-000083
(1)配体M-LB1的合成：向带有磁力转子的干燥封管中依次加入2-Br(689mg,2.20mmol,1.1当量)，B1-OH(340mg,2.00mmol,1.0当量)，碘化亚铜(76mg,0.40mmol,20mol％)，配体2(69mg,0.20mmol,10mol％)和磷酸钾(849mg,4.00mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(5mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体M-B1，白色固体560mg，收率69％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝17.5,1.0Hz,1H),3.48(dd,J＝18.0,7.0Hz,1H),5.46(ddd,J＝8.5,7.0,1.5Hz,1H),5.72(d,J＝8.0Hz,1H),7.03(ddd,J＝8.0,2.5,0.5Hz,1H),7.13(ddd,J＝8.0,2.5,1.0Hz,1H),7.23(ddd,J＝7.5,4.5,1.0Hz,1H),7.25–7.28(m,3H),7.34(t,J＝8.5Hz,1H),7.43(t,J＝8.0Hz,1H),7.54–7.56(m,1H),7.61(dd,J＝2.5,1.5Hz,1H),7.62(t,J＝2.0Hz,1H),7.67(dt,J＝7.5,1.0Hz,1H),7.69(dt,J＝8.0,1.0Hz,1H),7.72(dd,J＝7.5,2.0Hz,1H),7.74–7.76(m,1H),8.66(ddd,J＝5.0,1.5,1.0Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.73,76.97,83.24,117.52,118.81,119.40,120.59,121.86,122.05,122.34,123.36,125.23,125.60,127.42,128.44,129.64,129.69,130.10,136.71,139.67,141.42,141.85,149.64,156.60,157.16,157.49,163.41.HRMS(ESI):C 27H 21N 2O 2[M+H] +计算值405.1598，实测值405.1587。
(2)M-PtB1的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入M-B1(243mg,0.60mmol,1.0当量)，氯亚铂酸钾(262mg,0.63mmol,1.05当量)，四正丁基溴化铵(19mg,0.060mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(36mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应3天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(228mg,1.2mmol,2.0当量)，二氯甲烷(60mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtB1，红色固体106mg，收率30％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.58(dd,J＝18.0,5.0Hz,1H),3.64(d,J＝18.0Hz,1H),5.78(d,J＝7.0Hz,1H),5.85(ddd,J＝6.5,5.0,1.0Hz,1H),7.11–7.17(m,2H),7.19(dd,J＝10.5,1.5Hz,1H),7.21–7.22(m,1H),7.24–7.28(m,3H),7.30–7.34(m,2H),7.47–7.49(m,1H),7.57(d,J＝7.5Hz,1H),7.91–7.97(m,2H),9.02(d,J＝5.0Hz,1H).HRMS(ESI):C 27H 19N 2O 2Pt[M+H] +计算值598.1089，实测值598.1090。
实施例25：四齿环金属铂(II)配合物P-PtB2的合成：
Figure PCTCN2022086993-appb-000084
(1)配体P--B2的合成：向带有磁力转子的干燥封管中依次加入1-Br(689mg,2.20mmol,1.1当量)，1-OH(443mg,2.00mmol,1.0当量)，碘化亚铜(76mg,0.40mmol,20mol％)，配体2(69mg,0.20mmol,10mol％)和磷酸钾(849mg,4.00mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(5mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体P--B2，白色固体623mg，收率68％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝13.0,1.5Hz,1H),3.49(dd,J＝18.0,7.0Hz,1H),5.47(ddd,J＝8.5,7.0,1.5Hz,1H),5.73(d,J＝8.0Hz,1H),7.12(ddd,J＝8.0,2.5,1.5Hz,1H),7.17(ddd,J＝8.0,2.5,1.0Hz,1H),7.25–7.27(m,3H),7.30–7.31(m,1H),7.34(t,J＝8.0Hz,1H),7.44–7.51(m,3H),7.53–7.56(m,1H),7.63–7.67(m,3H),7.68(dt,J＝7.5,1.0Hz,1H),7.86(d,J＝8.0Hz,1H),8.08(d,J＝8.5,1.0Hz,1H),8.58(d,J＝6.0Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.72,76.95,83.26,118.91,118.92,120.12,120.33,122.10,123.48,125.01,125.23,125.62,126.55,126.93,127.28,127.44,128.45,129.66,129.69,129.85,130.02,136.79,139.67,141.33,141.82,142.07,157.00,159.75,163.38.HRMS(ESI):C 31H 23N 2O 2[M+H] +计算值455.1754，实测值455.1748。
(2)P-PtB2的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入P-B1(182mg,0.40mmol,1.0当量)，氯亚铂酸钾(174mg,0.42mmol,1.05当量)，四正丁基溴化铵(13mg,0.040mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(24mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应3天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(152mg,0.8mmol,2.0当量)，二氯甲烷(40mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtB2，红色固体57mg，收率22％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.57(dd,J＝18.0,4.0Hz,1H),3.63(d,J＝18.0Hz,1H),5.80–5.83(m,2H),7.09(t,J＝7.5Hz,1H),7.14(t,J＝8.0Hz,1H),7.20–7.24(m,3H),7.25–7.28(m,1H),7.31(t,J＝6.5Hz,2H),7.56(d,J＝7.5Hz,1H),7.59(d,J＝6.0Hz,1H),7.71–7.74(m,1H),7.77(t,J＝7.0Hz,1H),7.88(d,J＝8.0Hz,1H),7.98(d,J＝7.5Hz,1H),8.89(d,J＝6.0Hz,1H),8.94(d,J＝8.5Hz,1H).HRMS(ESI):C 31H 21N 2O 2Pt[M+H] +计算值648.1245，实测值648.1226。
实施例26：四齿环金属铂(II)配合物M-PtB2的合成：
Figure PCTCN2022086993-appb-000085
(1)配体M-B2的合成：向带有磁力转子的干燥封管中依次加入2-Br(689mg,2.20mmol,1.1当量)，B2-OH(443mg,2.00mmol,1.0当量)，碘化亚铜(76mg,0.40mmol,20mol％)，配体2(69mg,0.20mmol,10mol％)和磷酸钾(849mg,4.00mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(5mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体M-B2，白色固体487mg，收率54％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝13.0,1.5Hz,1H),3.49(dd,J＝18.0,7.0Hz,1H),5.47(ddd,J＝8.0,7.0,1.5Hz,1H),5.73(d,J＝8.0Hz,1H),7.12(ddd,J＝8.0,2.5,1.0Hz,1H),7.18(ddd,J＝8.0,2.5,1.0Hz,1H),7.25–7.27(m,3H),7.29–7.32(m,1H),7.34(t,J＝8.0Hz,1H),7.44–7.52(m,3H),7.53–7.57(m,1H),7.62–7.67(m,3H),7.68(dt,J＝7.5,1.0Hz,1H),7.86(d,J＝8.0Hz,1H),8.04–8.09(m,1H),8.58(d,J＝6.0Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.74,76.96,83.27,118.92,118.93,120.13,120.35,122.11,123.49,125.02,125.24,125.64,126.57,126.94,127.30,127.45,128.46,129.68,129.70,129.86,130.03,136.80,139.68,141.34,141.83,142.09,156.98,159.77,163.39.HRMS(ESI):C 31H 23N 2O 2[M+H] +计算值455.1754，实测值455.1742。
(2)M-PtB2的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入M-B2(273mg,0.60mmol,1.0当量)，氯亚铂酸钾(262mg,0.63mmol,1.05当量)，四正丁基溴化铵(19mg,0.060mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(36mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应3天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(228mg,1.2mmol,2.0当量)，二氯甲烷(60mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtB2，红色固体52mg，收率13％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.59(dd,J＝18.0,4.0Hz,1H),3.64(d,J＝18.0Hz,1H),5.82–5.85(m,2H),7.11(t,J＝7.5Hz,1H),7.16(t,J＝8.0Hz,1H),7.21–7.26(m,3H),7.27–7.30(m,1H),7.33(t,J＝6.5Hz,2H),7.58(d,J＝7.5Hz,1H),7.61(d,J＝6.0Hz,1H),7.72–7.76(m,1H),7.78–7.81(m,1H),7.90(d,J＝8.0Hz,1H),8.00(d,J＝7.5Hz,1H),8.91(d,J＝6.0Hz,1H),8.96(d,J＝8.5Hz,1H).HRMS(ESI):C 31H 21N 2O 2Pt[M+H] +计算值648.1245，实测值648.1230。
实施例27：四齿环金属铂(II)配合物P-PtB3的合成：
Figure PCTCN2022086993-appb-000086
(1)配体P-B2的合成：向带有磁力转子的干燥封管中依次加入1-Br(689mg,2.20mmol,1.1当量)，B3-OH(443mg,2.00mmol,1.0当量)，碘化亚铜(76mg,0.40mmol,20mol％)，配体2(69mg,0.20mmol,10mol％)和磷酸钾(849mg,4.00mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(5mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体P-B3，白色固体590mg，收率65％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝18.0,1.5Hz,1H),3.49(dd,J＝18.0,7.0Hz,1H), 5.47(ddd,J＝8.0,7.0,1.5Hz,1H),5.72(d,J＝8.0Hz,1H),7.07(ddd,J＝8.0,2.5,1.0Hz,1H),7.16(ddd,J＝8.0,2.5,1.0Hz,1H),7.25–7.27(m,3H),7.36(t,J＝8.0Hz,1H),7.49(t,J＝8.0Hz,1H),7.51–7.56(m,2H),7.63(dd,J＝2.5,1.5Hz,1H),7.70–7.74(m,2H),7.80–7.83(m,3H),7.93(ddd,J＝8.0,1.5,1.0Hz,1H),8.14(d,J＝8.5Hz,1H),8.21(d,J＝8.5Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.69,76.94,83.22,118.20,118.70,118.85,119.77,121.81,122.72,123.34,125.22,125.57,126.38,127.22,127.37,127.40,128.42,129.65,129.67,129.73,130.19,136.77,139.65,141.67,141.81,148.14,156.38,157.17,157.45,163.38.HRMS(ESI):C 31H 23N 2O 2[M+H] +计算值455.1754，实测值455.1744。
(2)P-PtB3的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入P-B3(182mg,0.40mmol,1.0当量)，氯亚铂酸钾(174mg,0.42mmol,1.05当量)，四正丁基溴化铵(13mg,0.040mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(24mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应3天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(152mg,0.8mmol,2.0当量)，二氯甲烷(40mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtB3，红色固体91mg，收率35％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.55(d,J＝3.5Hz,2H),5.90–5.93(m,1H),6.23(d,J＝7.0Hz,1H),6.45(d,J＝7.5Hz,1H),6.73(t,J＝7.5Hz,1H),7.05(t,J＝8.0Hz,1H),7.15–7.20(m,2H),7.25–7.30(m,4H),7.54–7.58(m,1H),7.65(d,J＝7.5Hz,1H),7.78(ddd,J＝8.5,7.0,1.5Hz,1H),7.92(dd,J＝8.0,1.0Hz,1H),8.14(d,J＝8.5Hz,1H),8.42(d,J＝8.5Hz,1H),9.03(d,J＝8.5Hz,1H).HRMS(ESI):C 31H 21N 2O 2Pt[M+H] +计算值648.1245，实测值648.1242。
实施例28：四齿环金属铂(II)配合物M-PtB3的合成：
Figure PCTCN2022086993-appb-000087
(1)配体M-B3的合成：向带有磁力转子的干燥封管中依次加入2-Br(689mg,2.20mmol,1.1当量)，B3-OH(443mg,2.00mmol,1.0当量)，碘化亚铜(76mg,0.40mmol,20mol％)，配体2(69mg,0.20mmol,10mol％)和磷酸钾(849mg,4.00mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(5mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体M-B3，白色固体590mg，收率64％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.35(dd,J＝18.0,1.5Hz,1H),3.48(dd,J＝18.0,7.0Hz,1H),5.47(ddd,J＝8.0,7.0,1.5Hz,1H),5.72(d,J＝8.0Hz,1H),7.07(ddd,J＝8.0,2.5,1.0Hz,1H),7.16(ddd,J＝8.0,2.5,1.0Hz,1H),7.25–7.27(m,3H),7.36(t,J＝8.0Hz,1H),7.49(t,J＝8.0Hz,1H),7.51–7.56(m,2H),7.63(dd,J＝2.5,1.5Hz,1H),7.70–7.74(m,2H),7.80–7.83(m,3H),7.93(ddd,J＝8.0,1.5,1.0Hz,1H),8.14(d,J＝8.5Hz,1H),8.21(d,J＝8.5Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.73,76.96,83.25,118.23,118.74,118.90,119.79,121.84,122.75,123.37,125.24,125.60,126.41,127.26,127.40,127.43,128.44,129.68,129.76,130.21,136.81,139.68,141.70,141.84,148.17,156.44,157.19,157.48,163.42.HRMS(ESI):C 31H 23N 2O 2[M+H] +计算值455.1754，实测值455.1744。
(2)M-PtB3的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入M-B3(273mg,0.60 mmol,1.0当量)，氯亚铂酸钾(262mg,0.63mmol,1.05当量)，四正丁基溴化铵(19mg,0.060mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(36mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在100℃下搅拌反应3天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡(228mg,1.2mmol,2.0当量)，二氯甲烷(60mL)，室温搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtB3，红色固体46mg，收率12％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.55(d,J＝3.5Hz,2H),5.89–5.92(m,1H),6.23(d,J＝7.0Hz,1H),6.45(d,J＝7.5Hz,1H),6.73(t,J＝7.0Hz,1H),7.05(t,J＝7.5Hz,1H),7.16–7.20(m,2H),7.25–7.30(m,4H),7.56(ddd,J＝8.0,7.0,1.0Hz,1H),7.65(d,J＝7.0Hz,1H),7.78(ddd,J＝8.5,7.0,1.5Hz,1H),7.92(dd,J＝8.0,1.0Hz,1H),8.14(d,J＝9.0Hz,1H),8.42(d,J＝8.5Hz,1H),9.03(d,J＝8.5Hz,1H).HRMS(ESI):C 31H 21N 2O 2Pt[M+H] +计算值648.1245，实测值648.1253。
实施例29：四齿环金属铂(II)配合物M-PtB8的合成：
Figure PCTCN2022086993-appb-000088
(1)M-B8的合成：向带有磁力转子的干燥封管中依次加入2-Br(1.50g,4.77mmol,1.0当量)，B8-OH(1.0g,4.77mmol,1.0当量)，碘化亚铜(91mg,0.48mmol,10mol％)，配体2(165mg,0.48mmol,10mol％)和磷酸钾(2.02g,9.54mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(30mL)。将封管置于80℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到M-B8，白色固体1.05g，收率50％。 1H NMR(400MHz,DMSO-d 6)δ3.23(d,J＝18.0Hz,1H),3.49(dd,J＝18.0,6.8Hz,1H),5.53(t,J＝7.2Hz,1H),5.71(d,J＝7.6Hz,1H),7.12(d,J＝8.4Hz,1H),7.21–7.35(m,6H),7.37–7.45(m,2H),7.46–7.56(m,3H),7.60–7.68(m,3H),7.77(d,J＝7.6Hz,1H),8.59(s,1H)。
(2)配体M-B8-Me的合成：向带有磁力转子的干燥封管中依次加入M-B8(1.0g,2.25mmol,1.0当量)，抽换氮气三次，在氮气保护下加入甲苯(30mL)和碘甲烷(384mg,2.71mmol,1.2当量)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，加水后过滤，固体转移至封管，加入甲醇(30mL)，溶解后再加入六氟磷酸铵(550mg,3.38mmol,1.5当量)水(10mL)溶液，50℃反应5天，冷却至室温，减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，淋洗剂：甲醇/二氯甲烷＝100:1-5:1，得到配体M-B8-Me，白色固体460mg，收率34％。 1H NMR(400MHz,DMSO-d 6)δ3.22(d,J＝18.0Hz,1H),3.49(dd,J＝18.0,6.8Hz,1H),4.13(s,3H),5.53(ddd,J＝8.0,6.8,1.6Hz,1H),5.71(d,J＝7.6Hz,1H),7.21–7.31(m,3H),7.35–7.39(m, 2H),7.40–7.43(m,1H),7.47(t,J＝2.4Hz,1H),7.52–7.57(m,2H),7.60(ddd,J＝8.0,2.0,0.8Hz,1H),7.66(ddd,J＝8.4,7.2,1.2Hz,1H),7.70(dt,J＝7.6,1.2Hz,1H),7.74–7.79(m,2H),7.84(dt,J＝8.4,0.8Hz,1H),8.12(dt,J＝8.4,0.8Hz,1H),10.08(s,1H)。
(3)M-PtB8的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入M-B8-Me(237mg,0.39mmol,1.0当量)，(1,5-环辛二烯)二氯化铂(154mg,0.41mmol,1.05当量)，醋酸钠(160mg,1.18mmol,3.0当量)，抽换氮气三次，加入乙二醇二甲醚(25mL)，反应液氮气鼓泡30分钟后，在120℃下反应72小时，冷却至室温，加水淬灭，DCM萃取后减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtB8黄色固体23mg，收率9％。 1H NMR(400MHz,DMSO-d 6)δ3.39(d,J＝14Hz,1H),3.46-3.52(m,1H),4.36(s,3H),5.92–6.00(m,1H),6.17(d,J＝6.8Hz,1H),6.93(d,J＝8.0Hz,1H),7.13–7.31(m,6H),7.39(d,J＝7.6Hz,1H),7.48–7.54(m,2H),7.57(d,J＝7.6Hz,1H),7.73(d,J＝7.6Hz,1H),7.81–7.86(m,1H),8.36–8.38(m,1H)。
实施例30：四齿环金属铂(II)配合物P-PtB9的合成：
Figure PCTCN2022086993-appb-000089
(1)配体P-B9的合成：向带有磁力转子的干燥封管中依次加入1-Br(500mg,1.60mmol,1.0当量)，B9-OH(301mg,1.60mmol,1.0当量)，碘化亚铜(31mg,0.16mmol,10mol％)，配体2(55mg,0.16mmol,10mol％)和磷酸钾(680mg,3.20mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(10mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体P-B9，白色固体526mg，收率78％。 1H NMR(400MHz,DMSO-d 6)δ2.14(s,3H),2.27(s,3H),3.21(d,J＝18.0Hz,1H),3.42-3.47(m,1H),5.51(t,J＝7.2Hz,1H),5.68(d,J＝7.6Hz,1H),6.05(s,1H),7.02(d,J＝7.6Hz,1H),7.12-7.14(m,1H),7.21–7.32(m,5H),7.40–7.43(m,2H),7.50(t,J＝8.0Hz,2H),7.64(d,J＝7.6Hz,1H)。 13C NMR(125MHz,CDCl 3)δ12.42,13.43,39.70,76.94,83.26,107.19,114.91,117.16,119.05,119.43,122.19,123.74,125.24,125.56,127.42,128.45,129.72,129.74,130.08,139.35,139.64,141.19,141.78,149.08,156.49,157.51,163.25。
(2)P-PtB9的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入P-B9(200mg,0.48mmol,1.0当量)，氯亚铂酸钾(208mg,0.50mmol,1.05当量)，四正丁基溴化铵(15mg,0.048mmol,0.1当量)，抽换氮气三次，加入醋酸(30mL)，反应液氮气鼓泡30分钟后，室温先搅拌12小时，再在110℃下反应48小时，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtB9，黄色固体100mg，收率34％。 1H NMR(400MHz,DMSO-d 6)δ2.74(s,3H),2.78(s,3H),3.49(d,J＝14Hz,1H),3.56-3.62(m,1H),5.89–5.94(m,1H),5.98(d,J＝6.8Hz,1H),6.51(s,1H),6.89(dd,J＝8.0,0.8Hz,1H),7.08–7.15(m,3H),7.17–7.23(m,2H),7.27–7.31(m,2H),7.39(d,J＝7.6Hz,1H),7.44(d,J＝7.6Hz,1H)。 13C NMR(125MHz,CDCl 3)δ14.49,15.06,38.25,73.92,88.08,106.69,109.71,111.11,113.94,120.48,121.45,123.38,123.94,125.18,125.34,125.51,128.07,129.00,133.24,139.27,140.27,141.04, 147.62,149.57,150.57,152.44,180.59。
实施例31：四齿环金属铂(II)配合物M-PtB9的合成：
Figure PCTCN2022086993-appb-000090
(1)配体M-B9的合成：向带有磁力转子的干燥封管中依次加入2-Br(500mg,1.60mmol,1.0当量)，B9-OH(301mg,1.60mmol,1.0当量)，碘化亚铜(31mg,0.16mmol,10mol％)，配体2(55mg,0.16mmol,10mol％)和磷酸钾(680mg,3.20mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(10mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到配体M-B9，白色固体514mg，收率77％。 1H NMR(500MHz,CDCl 3)δ2.26(s,3H),2.27(s,3H),3.33–3.37(m,1H),3.49(dd,J＝18.0,7.0Hz,1H),5.47(ddd,J＝8.0,7.0,1.5Hz,1H),5.72(d,J＝8.0Hz,1H),5.96(s,1H),6.94(ddd,J＝8.0,2.5,1.0Hz,1H),7.04(t,J＝2.0Hz,1H),7.13(ddd,J＝8.0,2.5,1.0Hz,1H),7.19(ddd,J＝8.0,2.0,1.0Hz,1H),7.26–7.29(m,3H),7.33–7.36(m,1H),7.38(t,J＝7.0Hz,1H),7.53–7.56(m,1H),7.60–7.61(m,1H),7.71(dt,J＝7.5,1.0Hz,1H)。 13C NMR(125MHz,CDCl 3)δ12.34,13.36,39.62,76.87,83.19,107.14,114.83,117.08,118.96,119.34,122.10,123.66,125.16,125.48,127.33,128.37,129.67,130.01,139.26,139.55,141.14,141.71,148.99,156.43,157.43,163.14。
(2)M-PtB9的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入M-B9(200mg,0.48mmol,1.0当量)，氯亚铂酸钾(208mg,0.50mmol,1.05当量)，四正丁基溴化铵(15mg,0.048mmol,0.1当量)，抽换氮气三次，加入醋酸(30mL)，反应液氮气鼓泡30分钟后，室温先搅拌12小时，再在110℃下反应48小时，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtB9，黄色固体101mg，收率34％。 1H NMR(400MHz,DMSO-d 6)δ2.74(s,3H),2.78(s,3H),3.49(d,J＝14Hz,1H),3.56-3.62(m,1H),5.89–5.94(m,1H),5.98(d,J＝6.8Hz,1H),6.51(s,1H),6.89(d,J＝8.0Hz,1H),7.08–7.15(m,3H),7.17–7.23(m,2H),7.27–7.31(m,2H),7.39(d,J＝7.6Hz,1H),7.44(d,J＝7.6Hz,1H)。 13C NMR(125MHz,CDCl 3)δ14.53,15.08,38.28,73.95,88.10,106.71,109.74,111.06,113.99,120.55,121.47,123.43,123.98,125.19,125.36,125.43,128.11,129.04,133.20,139.27,140.26,141.10,147.63,149.55,150.59,152.46,180.67。
实施例32：四齿环金属铂(II)配合物(R,S)-M-PtLI1的合成：
Figure PCTCN2022086993-appb-000091
(1)配体(R,S)-LI1的合成：向带有磁力转子的干燥封管中加入PyCz-NH(409mg,1.09mmol,1.0当量)，2-Br(515mg,1.64mmol,1.5当量)，三(二亚苄基丙酮)二钯(40mg,0.044mmol,4mol％)，2-(二叔丁基膦)联苯(26mg,0.088mmol,8mol％)和叔丁醇钠(209mg,2.18mmol,2.0当量)然后抽换氮气三次，在氮气保护下加入甲苯(15mL)。该混合物在110℃的油浴锅中搅拌反应2.5天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R,S)-LI1，白色固体651mg，收率98％。 1H NMR(400MHz,CDCl 3):δ1.80(s,6H),3.34-3.38(m,1H),3.47-3.52(m,1H),5.48-5.52(m,1H),5.77(d,J＝8.0Hz,1H),6.24-6.29(m,1H),6.72(s,1H),6.95-7.00(m,3H),7.28-7.33(m,6H),7.44(td,J＝7.6,2.0Hz,1H),7.51-7.54(m,2H),7.58-7.59(m,1H),7.64(t,J＝8.0Hz,1H),7.78(d,J＝8.0Hz,1H),7.98(t,J＝1.6Hz,1H),8.02-8.04(m,1H),8.09-8.13(m,2H),8.35(dd,J＝4.8,1.2Hz,1H)。
(2)(R,S)-M-PtLI1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(R,S)-LI1(304mg,0.50mmol,1.0当量)，二氯化铂(141mg,0.53mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(R,S)-M-PtLI1，黄色固体112mg，收率28％。 1H NMR(500MHz,DMSO-d 6):δ1.76(s,6H),3.25-3.29(m,1H),3.47-3.52(m,1H),5.53-5.57(m,1H),5.74(d,J＝8.0Hz,1H),6.15(dd,J＝7.5,2.0Hz,1H),6.68(s,1H),6.93-7.00(m,2H),7.13-7.16(m,1H),7.22-7.33(m,5H),7.43-7.46(m,2H),7.57(dd,J＝7.5,2.0Hz,1H),7.61-7.70(m,3H),7.77(t,J＝7.5Hz,1H),7.81(t,J＝1.5Hz,1H),8.03(dt,J＝8.0,1.5Hz,1H),8.19-8.22(m,2H),8.35(s,1H)。
实施例33：四齿环金属铂(II)配合物(R,S)-P-PtLI1的合成：
Figure PCTCN2022086993-appb-000092
(1)配体(S,R)-LI1的合成：向带有磁力转子的干燥封管中加入PyCz-NH(409mg,1.09mmol,1.0当量)，2-Br(515mg,1.64mmol,1.5当量)，三(二亚苄基丙酮)二钯(40mg,0.044mmol,4mol％)，2-(二叔丁基膦)联苯(26mg,0.088mmol,8mol％)和叔丁醇钠(209mg,2.18mmol,2.0当量)然后抽换氮气三次，在氮气保护下加入甲苯(15mL)。该混合物在110℃的油浴锅中搅拌反应2.5天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S,R)-LI1，白色固体511mg，收率77％。 1H NMR(400MHz,CDCl 3):δ1.81(s,6H),3.34-3.38(m,1H),3.47-3.53(m,1H), 5.48-5.52(m,1H),5.77(d,J＝8.0Hz,1H),6.24-6.28(m,1H),6.72(s,1H),6.94-7.0(m,3H),7.27-7.33(m,6H),7.44(td,J＝7.6,2.0Hz,1H),7.51-7.56(m,2H),7.57-7.59(m,1H),7.64(t,J＝8.0Hz,1H),7.78(d,J＝7.6Hz,1H),7.99(t,J＝1.6Hz,1H),8.02-8.04(m,1H),8.09-8.13(m,2H),8.35(dd,J＝4.8,1.2Hz,1H)。
(2)(S,R)-P-PtLI1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(S,R)-LI1(300mg,0.49mmol,1.0当量)，二氯化铂(136mg,0.51mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(S,R)-P-PtLI1，黄色固体122mg，收率31％。 1H NMR(500MHz,DMSO-d 6):δ1.76(s,6H),3.25-3.29(m,1H),3.47-3.52(m,1H),5.54-5.57(m,1H),5.74(d,J＝7.5Hz,1H),6.15(dd,J＝8.0,1.5Hz,1H),6.68(s,1H),6.93-7.00(m,2H),7.13-7.16(m,1H),7.23-7.34(m,5H),7.44-7.46(m,2H),7.57(dd,J＝7.5,2.0Hz,1H),7.61-7.70(m,3H),7.77(t,J＝8.0Hz,1H),7.81(t,J＝2.0Hz,1H),8.03(dt,J＝8.0,1.5Hz,1H),8.19-8.22(m,2H),8.35(s,1H)。
实施例34：四齿环金属铂(II)配合物(R,S)-M-PtLK1的合成：
Figure PCTCN2022086993-appb-000093
(1)(R,S)-LJ1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(R,S)-OH(512mg,1.23mmol,1.0当量)，2-溴吡啶(389mg,2.46mmol,2.0当量)，碘化亚铜(141mg,0.74mmol,60mol％)，配体2(41mg,0.12mmol,10mol％)和磷酸钾(522mg,2.46mmol,2.0当量)。抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(15mL)。该混合物在80℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R,S)-LJ1，白色固体182mg，收率30％。 1H NMR(500MHz,DMSO-d 6):δ3.22-3.26(m,1H),3.47-3.52(m,1H),5.56(t,J＝8.0Hz,1H),5.73(d,J＝8.0Hz,1H),7.01-7.12(m,4H),7.21-7.34(m,5H),7.42(t,J＝8.0Hz,2H),7.74(t,J＝7.5Hz,1H),7.80-7.84(m,2H),7.95-7.98(m,2H),8.10(d,J＝4.0Hz,1H),8.23-8.28(m,2H)。
(2)(R,S)-M-PtLJ1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(R,S)-LJ1(160mg,0.32mmol,1.0当量)，二氯化铂(90mg,0.34mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(10mL)。该混合物在180℃的油浴锅中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(R,S)-M-PtLJ1，黄色固体123mg，收率56％。 1H NMR(400MHz,DMSO-d 6):3.50-3.56(m,1H),3.60-3.66(m,1H),6.00(t,J＝8.0Hz,1H),6.21(d,J＝6.8Hz,1H),6.45(d,J＝8.0Hz,1H),7.05(t,J＝7.6Hz,1H),7.20-7.25(m,2H),7.28-7.48(m,6H),7.69(d,J＝8.0Hz,1H),7.94(d,J＝8.4Hz,1H),8.20-8.31(m,4H),9.25(dd,J＝4.4,1.6Hz,1H)。
实施例35：四齿环金属铂(II)配合物(R,S)-P-PtLK1的合成：
Figure PCTCN2022086993-appb-000094
(1)(S,R)-LJ1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(S,R)-OH(550mg,1.32mmol,1.0当量)，2-溴吡啶(259mg,2.64mmol,2.0当量)，碘化亚铜(150mg,0.79mmol,60mol％)，配体2(45mg,0.13mmol,10mol％)和磷酸钾(560mg,2.64mmol,2.0当量)。抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(15mL)。该混合物在80℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S,R)-LJ1，白色固体150mg，收率23％。 1H NMR(500MHz,DMSO-d 6):δ3.22-3.26(m,1H),3.47-3.52(m,1H),5.56(t,J＝8.0Hz,1H),5.73(d,J＝8.0Hz,1H),7.01-7.12(m,4H),7.21-7.34(m,5H),7.42(t,J＝8.0Hz,2H),7.74(t,J＝7.5Hz,1H),7.80-7.84(m,2H),7.95-7.98(m,2H),8.10(d,J＝4.0Hz,1H),8.23-8.28(m,2H)。
(2)(S,R)-P-PtLJ1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(S,R)-LJ1(150mg,0.30mmol,1.0当量)，二氯化铂(85mg,0.32mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(10mL)。该混合物在180℃的油浴锅中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(S,R)-P-PtLJ1，黄色固体97mg，收率47％。 1H NMR(500MHz,DMSO-d 6):δ3.51-3.54(m,1H),3.60-3.65(m,1H),6.00(t,J＝6.5Hz,1H),6.21(d,J＝6.8Hz,1H),6.46(d,J＝8.0Hz,1H),7.05(t,J＝7.5Hz,1H),7.20-7.25(m,2H),7.29-7.48(m,6H),7.68-7.70(m,1H),7.93(d,J＝8.0Hz,1H),8.20-8.30(m,4H),9.25(dd,J＝6.0,1.5Hz,1H)。
实施例36：四齿环金属铂(II)配合物(R,S)-M-PtLK1的合成：
Figure PCTCN2022086993-appb-000095
(1)配体(R,S)-LK1的合成：向带有磁力转子的干燥封管中加入PyCz(300mg,1.23mmol,1.0当量)，1-Br(578mg,1.84mmol,1.5当量)，三(二亚苄基丙酮)二钯(21mg,0.023mmol,2mol％)，2-(二叔丁基膦)联苯(14mg,0.046mmol,4mol％)和叔丁醇钠(236mg,2.46mmol,2.0当量)然后抽换氮气三次，在氮气保护下加入甲苯(15mL)。该混合物在110℃的油浴锅中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R,S)-LK1，白色固体564 mg，收率96％。 1H NMR(400MHz,CDCl 3):δ3.34-3.39(m,1H),3.47-3.53(m,1H),5.49-5.53(m,1H),5.78(d,J＝7.6Hz,1H),7.19-7.22(m,1H),7.27-7.34(m,5H),7.39-7.43(m,1H),7.54-7.57(m,1H),7.62-7.71(m,2H),7.72-7.77(m,2H),7.91(dd,J＝8.0,1.6Hz,1H),7.95(d,1H),8.08(dt,J＝7.6,1.2Hz,1H),8.15-8.17(m,2H),8.21(d,J＝8.4Hz,1H),8.66(d,J＝4.4Hz,1H)。
(2)(R,S)-M-PtLI1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(R,S)-LI1(253mg,0.53mmol,1.0当量)，二氯化铂(149mg,0.56mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(R,S)-M-PtLI1，黄色固体120mg，收率34％。 1H NMR(500MHz,DMSO-d 6):δ3.55-3.59(m,1H),δ3.63-3.68(m,1H),6.05(t,J＝6.5Hz,1H),6.16(d,J＝7.0Hz,1H),7.21-7.34(m,6H),7.42-7.47(m,3H),7.48-7.53(m,1H),7.77(d,J＝8.5Hz,1H),7.90(d,J＝8.0Hz,1H),8.10(td,J＝8.0,1.0Hz,1H),8.20-8.23(m,2H),8.27-8.29(m,2H),9.14(d,J＝4.5Hz,1H)。
实施例37：四齿环金属铂(II)配合物(R,S)-P-PtLK1的合成：
Figure PCTCN2022086993-appb-000096
(1)配体(S,R)-LK1的合成：向带有磁力转子的干燥封管中加入PyCz(303mg,1.24mmol,1.0当量)，1-Br(584mg,1.86mmol,1.5当量)，三(二亚苄基丙酮)二钯(23mg,0.025mmol,2mol％)，2-(二叔丁基膦)联苯(15mg,0.050mmol,4mol％)和叔丁醇钠(238mg,2.48mmol,2.0当量)然后抽换氮气三次，在氮气保护下加入甲苯(15mL)。该混合物在110℃的油浴锅中搅拌反应2.5天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S,R)-LK1，白色固体425mg，收率72％。 1H NMR(400MHz,CDCl 3):δ3.34-3.39(m,1H),3.47-3.53(m,1H),5.49-5.53(m,1H),5.78(d,J＝7.6Hz,1H),7.19-7.22(m,1H),7.27-7.34(m,5H),7.39-7.43(m,1H),7.54-7.57(m,1H),7.62-7.71(m,2H),7.72-7.77(m,2H),7.91(dd,J＝8.0,1.6Hz,1H),7.95(d,1H),8.08(dt,J＝7.6,1.2Hz,1H),8.15-8.17(m,2H),8.21(d,J＝8.4Hz,1H),8.66(d,J＝4.4Hz,1H)。
(2)(S,R)-P-PtLK1的合成：向带有磁力转子的干燥三口烧瓶中依次加入配体(S,R)-LK1(258mg,0.54mmol,1.0当量)，二氯化铂(152mg,0.57mmol,1.05当量)。然后抽换氮气三次，在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-2:1，得到产物(S,R)-P-PtLK1，黄色固体40mg，收率11％。 1H NMR(500MHz,DMSO-d 6):δ3.56-3.60(m,1H),δ3.64-3.69(m,1H),6.06(t,J＝6.5Hz,1H),6.17(d,J＝7.0Hz,1H),7.22-7.35(m,6H),7.43-7.50(m,3H),7.51-7.53(m,1H),7.78(d,J＝8.0Hz,1H),7.91(d,J＝8.0Hz,1H),8.11(td,J＝8.0,1.5Hz,1H),8.20-8.24(m,2H),8.28-8.30(m,2H),9.15(d,J＝5.5Hz,1H)。
实施例38：四齿环金属钯(II)配合物P-PdLA1的合成：
Figure PCTCN2022086993-appb-000097
P-PdLA1的合成：在具有磁子的50mL三口烧瓶中依次加入M-LA1(200mg,0.41mmol,1.0当量)、醋酸钯(101mg,0.45mmol,1.1当量)和四正丁基溴化铵(13mg,0.041mmol,10mol％)，抽换氮气三次，加入醋酸(25mL)，氮气鼓泡30分钟，室温搅拌12小时，再升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，加入氯化亚锡(140mg,0.74mmol,2.0当量)、二氯甲烷(15mL)，室温搅拌一天，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝8:1-1:1，得淡黄色固体63mg，收率26％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.46(d,J＝18.5Hz,1H),3.64(dd,J＝18.5Hz,6.5Hz,1H),5.97(t,J＝6.5Hz,1H),6.22(d,J＝7.0Hz,1H),7.00(d,J＝7.5Hz,1H),7.11(t,J＝8.0Hz,1H),7.17-7.24(m,4H),7.28(dd,J＝6.5,2.0Hz,1H),7.35(d,J＝7.5Hz,1H),7.39-7.42(m,1H),7.47-7.51(m,2H),7.92(d,J＝8.5Hz,1H),8.15-8.17(m,2H),8.20-8.23(m,1H),8.28(d,J＝8.5Hz,1H),9.34(dd,J＝6.0,2.0Hz,1H)。
实施例39：四齿环金属钯(II)配合物M-PdLA1的合成：
Figure PCTCN2022086993-appb-000098
M-PdLA1的合成：在具有磁子的50mL三口烧瓶中依次加入M-LA1(200mg,0.41mmol,1.0当量)、醋酸钯(101mg,0.45mmol,1.1当量)和四正丁基溴化铵(13mg,0.041mmol,10mol％)，抽换氮气三次，加入醋酸(25mL)，氮气鼓泡30分钟，升温至120℃，反应2天。冷却至室温后，减压旋蒸除去溶剂，水洗，萃取3次，合并有机相，无水硫酸钠干燥，过滤，硅胶拌样，干法上样，柱层析分离提纯，洗脱剂为石油醚：二氯甲烷＝2:1-1:1，得白色固体133mg，收率54％。 1H NMR(500MHz,CDCl 3):δ(ppm)3.51-3.60(m,2H),5.78-5.81(m,1H),5.87(d,J＝7.0Hz,1H),7.04-7.08(m,2H),7.12(d,J＝7.5Hz,1H),7.16-7.19(m,2H),7.24(d,J＝8.0Hz,1H),7.26-7.27(m,1H),7.29-7.31(m,2H),7.34-7.42(m,2H),7.82-7.86(m,2H),7.99(d,J＝8.0Hz,1H),8.04(dd,J＝7.5,1.0Hz,1H),8.17(d,J＝8.5Hz,1H),9.20(dd,J＝6.0,2.0Hz,1H)。
实施例40：四齿环金属铂(II)配合物P-PtL1的合成：
Figure PCTCN2022086993-appb-000099
(1)配体(S)-L1的合成：向带有磁力转子的干燥封管中依次加入(S)-iPr-Br(1.19g,2.99mmol,1.2当量)， 2-OH(426g,2.49mmol,1.0当量)，碘化亚铜(95mg,0.50mmol,20mol％)，配体2(86mg,0.25mmol,10mol％)和磷酸钾(1.06g,4.98mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(25mL)。将封管置于85℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S)L1，白色固体475mg，收率39％。 1H NMR(400MHz,DMSO-d 6):δ0.86(d,J＝6.4Hz,3H),0.94(d,J＝6.4Hz,3H),1.17(s,9H),1.70-1.78(m,1H),3.54-3.59(m,1H),3.89-3.95(m,1H),3.97-4.03(m,1H),6.70(d,J＝8.8Hz,2H),6.87-6.90(m,1H),7.00(t,J＝2.0Hz,1H),7.11-7.14(m,1H),7.17-7.21(m,2H),7.27(d,J＝7.6Hz,1H),7.35-7.44(m,3H),7.69(t,J＝1.6Hz,1H),7.83-7.90(m,2H),7.95(d,J＝8.0Hz,1H)。
(2)P-PtL1的合成：向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S)-L1(431mg,0.88mmol,1.0当量)，氯亚铂酸钾(346mg,0.92mmol,1.05当量)，四正丁基溴化铵(28mg,0.088mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(52mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtL1，红色固体102mg，收率17％。 1H NMR(400MHz,DMSO-d 6):δ0.86(d,J＝6.8Hz,3H),1.03(d,J＝6.8Hz,3H),1.33(s,9H),4.03-4.06(m,1H),4.30-4.36(m,1H),4.46-4.50(m,1H),6.36-6.38(m,1H),6.83(t,J＝7.6Hz,1H),6.99-7.03(m,2H),7.17(t,J＝7.6Hz,1H),7.29-7.31(m,2H),7.52-7.55(m,3H),7.62(d,J＝7.2Hz,1H),8.07-8.11(m,1H),8.20(d,J＝7.6Hz,1H),8.77(d,J＝4.8Hz,1H)。
实施例41：四齿环金属铂(II)配合物M-PtL1的合成：
Figure PCTCN2022086993-appb-000100
(1)配体(R)-L1的合成：向带有磁力转子的干燥封管中依次加入(R)-iPr-Br(1.19g,2.99mmol,1.2当量)，2-OH(426g,2.49mmol,1.0当量)，碘化亚铜(95mg,0.50mmol,20mol％)，配体2(86mg,0.25mmol,10mol％)和磷酸钾(1.06g,4.98mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(25mL)。将封管置于85℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R)-L1，白色固体549mg，收率45％。
(2)M-PtL1的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入L2(150mg,0.31mmol,1.0当量)，氯亚铂酸钾(124mg,0.33mmol,1.05当量)，四正丁基溴化铵(10mg,0.031mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(19mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtL1，红色固体81mg，收率38％。 1H NMR(400MHz,DMSO-d 6):δ0.85(d,J＝6.8Hz,3H),1.03(d,J＝6.8Hz,3H),1.34(s,9H),4.03-4.08(m,1H),4.30-4.36(m,1H),4.46-4.50(m,1H),6.36-6.38(m,1H),6.83(t,J＝7.6Hz,1H),6.99-7.03(m,2H),7.16(t,J＝7.6Hz,1H),7.29-7.31(m,2H),7.52-7.55(m,3H),7.62(d,J＝7.2Hz,1H),8.07-8.11(m,1H),8.20(d,J＝7.6Hz,1H),8.78(d,J＝4.8Hz,1H)。
实施例42：四齿环金属铂(II)配合物P-PtL2的合成：
Figure PCTCN2022086993-appb-000101
(1)配体(S)-L2的合成：向带有磁力转子的干燥封管中依次加入(S)-iPr-Br(891mg,2.03mmol,1.2当量)，1-OH(440g,1.69mmol,1.0当量)，碘化亚铜(65mg,0.34mmol,20mol％)，配体2(59mg,0.17mmol,10mol％)和磷酸钾(717mg,3.38mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(20mL)。将封管置于85℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S)-L2，白色固体450mg，收率46％。 1H NMR(500MHz,DMSO-d 6):δ0.89-0.92(m,6H),1.18(s,9H),1.90-1.97(m,1H),3.09-3.14(m,1H),3.16-3.21(m,1H),3.97-4.03(m,1H),5.24(t,J＝6.0Hz,1H),6.48-6.51(m,2H),7.03-7.06(m,3H),7.17-7.19(m,1H),7.33-7.36(m,1H),7.43-7.47(m,3H),7.49(d,J＝2.0Hz,1H),7.52-7.53(m,1H),7.61(dt,J＝8.0,1.0Hz,1H),7.77(d,J＝8.0Hz,2H),8.06-8.09(m,1H),8.13(d,J＝9.0Hz,1H),8.23(d,J＝7.5Hz,1H),8.27(d,J＝8.5Hz,1H),8.67-8.68(m,1H)。
(2)P-PtL3的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(S)-L2(249mg,0.43mmol,1.0当量)，氯亚铂酸钾(169mg,0.45mmol,1.05当量)，四正丁基溴化铵(14mg,0.043mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(26mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtL3，红色固体129mg，收率39％。 1H NMR(600MHz,DMSO-d 6):δ0.76(d,J＝7.2Hz,3H),0.82(d,J＝7.2Hz,3H),1.30(s,9H),1.90-1.95(m,1H),3.83(dd,J＝9.6,3.6Hz,1H),4.49-4.52(m,1H),4.60-4.63(m,1H),6.43(dd,J＝7.8,1.2Hz,1H),6.85(t,J＝7.8Hz,1H),6.99(dd,J＝7.8,0.6Hz,1H),7.12-7.25(m,3H),7.33-7.36(m,1H),7.38-7.40(m,1H),7.44-7.49(m,3H),7.82(d,J＝8.4Hz,1H),8.11-8.14(m,2H),8.17-8.20(m,1H),8.23(d,J＝7.8Hz,1H),9.26-9.27(m,1H)。
实施例43：四齿环金属铂(II)配合物M-PtL2的合成：
Figure PCTCN2022086993-appb-000102
(1)配体(R)-L2的合成：向带有磁力转子的干燥封管中依次加入(R)-iPr-Br(891mg,2.03mmol,1.2当量)，1-OH(440g,1.69mmol,1.0当量)，碘化亚铜(65mg,0.34mmol,20mol％)，配体2(59mg,0.17mmol,10mol％)和磷酸钾(717mg,3.38mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(20mL)。将封管置于85℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R)-L2，白色固体421mg，收率43％。 1H NMR(500MHz,DMSO-d 6):δ0.89-0.92(m,6H),1.18(s,9H),1.90-1.97(m,1H),3.09-3.14(m,1H),3.16-3.21(m,1H),3.97-4.03(m,1H),5.24(t,J＝6.0Hz,1H),6.48-6.51(m,2H),7.03-7.06(m,3H), 7.17-7.19(m,1H),7.33-7.36(m,1H),7.43-7.47(m,3H),7.49(d,J＝2.0Hz,1H),7.52-7.53(m,1H),7.61(dt,J＝8.0,1.0Hz,1H),7.77(d,J＝8.0Hz,2H),8.06-8.09(m,1H),8.13(d,J＝9.0Hz,1H),8.23(d,J＝7.5Hz,1H),8.27(d,J＝8.5Hz,1H),8.67-8.68(m,1H)。
(2)M-PtL2的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(R)-L2(150mg,0.26mmol,1.0当量)，氯亚铂酸钾(102mg,0.27mmol,1.05当量)，四正丁基溴化铵(8mg,0.026mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(16mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtL2，红色固体48mg，收率24％。 1H NMR(600MHz,DMSO-d 6):δ0.78(d,J＝6.6Hz,3H),0.83(d,J＝6.6Hz,3H),1.32(s,9H),1.92-1.95(m,1H),3.87(dd,J＝10.2,4.2Hz,1H),4.50-4.53(m,1H),4.62-4.65(m,1H),6.43(dd,J＝7.8,1.2Hz,1H),6.85(t,J＝7.8Hz,1H),6.99(dd,J＝7.8,0.6Hz,1H),7.12-7.26(m,3H),7.34-7.37(m,1H),7.38-7.41(m,1H),7.44-7.51(m,3H),7.82(d,J＝7.8Hz,1H),8.11-8.14(m,2H),8.17-8.20(m,1H),8.24(d,J＝8.4Hz,1H),9.27-9.28(m,1H)。
实施例44：四齿环金属铂(II)配合物P-PtL3的合成：
Figure PCTCN2022086993-appb-000103
(1)配体(S)-L3的合成：向带有磁力转子的干燥封管中依次加入Py-Ph-Br(440mg,1.88mmol,1.5当量)，(S)-Ph-OH(300g,1.25mmol,1.0当量)，碘化亚铜(48mg,0.25mmol,20mol％)，配体2(45mg,0.13mmol,10mol％)和磷酸钾(531mg,2.50mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(S)-L3，白色固体280mg，收率57％。 1H NMR(400MHz,DMSO-d 6):δ4.18(t,J＝8.4Hz,1H),4.82(t,J＝9.6Hz,1H),5.37(t,J＝8.8Hz,1H),7.17(d,J＝8.0Hz,1H),7.26-7.38(m,6H),7.49-7.58(m,3H),7.73(d,J＝7.6Hz,1H),7.80(s,1H),7.86-7.93(m,2H),8.00(d,J＝8.0Hz,1H),8.64(d,J＝4.8Hz,1H)。
(2)P-PtL3的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(S)-L3(173mg,0.44mmol,1.0当量)，氯亚铂酸钾(173mg,0.46mmol,1.05当量)，四正丁基溴化铵(14mg,0.043mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(26mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物P-PtL3，红色固体18mg，收率7％。 1H NMR(400MHz,DMSO-d 6):δ4.65(t,J＝7.2Hz,1H),5.35(t,J＝9.6Hz,1H),5.81(t,J＝7.2Hz,1H),7.06-7.10(m,2H),7.16-7.20(m,1H),7.25(d,J＝2.4Hz,2H),7.31-7.42(m,2H),7.40(t,J＝7.6Hz,2H),7.53-7.59(m,3H),7.92(t,J＝8.0Hz,1H),8.05-8.09(m,2H)。
实施例45：四齿环金属铂(II)配合物M-PtL3的合成：
Figure PCTCN2022086993-appb-000104
(1)配体(R)-L3的合成：向带有磁力转子的干燥封管中依次加入Py-Ph-Br(735mg,3.14mmol,1.5当量)，(R)-Ph-OH(500g,2.09mmol,1.0当量)，碘化亚铜(80mg,0.42mmol,20mol％)，配体2(72mg,0.21mmol,10mol％)和磷酸钾(887mg,4.18mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。将封管置于100℃的油浴锅中搅拌，反应2天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝10:1-5:1，得到产物(R)-L3，白色固体420mg，收率51％。 1H NMR(400MHz,CDCl 3):δ4.26(t,J＝8.4Hz,1H),4.78(dd,J＝10,8.4Hz,1H),5.37(dd,J＝10,8.4Hz,1H),7.07-7.09(m,1H),7.20-7.25(m,2H),7.27-7.30(m,3H),7.33-7.37(m,2H),7.39-7.47(m,2H),7.68-7.77(m,5H),7.81(dt,J＝8.0,1.2Hz,1H),8.67-7.69(m,1H)。
(2)M-PtL3的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(R)-L3(200mg,0.51mmol,1.0当量)，氯亚铂酸钾(224mg,0.54mmol,1.05当量)，四正丁基溴化铵(16mg,0.051mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(31mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝1:1，得到产物M-PtL3，红色固体40mg，收率13％。 1H NMR(500MHz,DMSO-d 6):δ4.66(dd,J＝8.5,6.5Hz,1H),5.35(dd,J＝10,8.5Hz,1H),5.82(dd,J＝10,6.0Hz,1H),7.06-7.10(m,2H),7.23-7.27(m,2H),7.30-7.33(m,2H),7.40(t,J＝8.0Hz,2H),7.54-7.60(m,3H),7.93(td,J＝8.0,2.0Hz,1H),8.05-8.10(m,2H)。
实施例46：四齿环金属铂(II)配合物P-PtOO的合成：
Figure PCTCN2022086993-appb-000105
(1)配体(S,R)-L-OO的合成：向带有磁力转子的干燥封管中依次加入1-Br(800mg,2.55mmol,1.2当量)，PyOPh-OH(512mg,2.12mmol,1.0当量)，碘化亚铜(40mg,0.21mmol,10mol％)，配体2(69mg,0.21mmol,10mol％)和磷酸钾(900mg,4.24mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝15:1-5:1，得到配体(S,R)-L-OO，黑色固体480mg，收率54％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.22(d,J＝18.0Hz,1H),3.60(dd,J＝18.0,7.0Hz, 1H),5.51(ddd,J＝8.0,7.0,1.5Hz,1H),5.69(d,J＝8.0Hz,1H),6.80(t,J＝2.5Hz,1H),6.85(ddd,J＝8.5,2.5,0.5Hz,1H),6.93(ddd,J＝8.5,2.0,0.5Hz,1H),7.04(d,J＝8.0Hz,1H),7.12(ddd,J＝7.0,5.0,1.0Hz,1H),7.22-7.30(m,4H),7.40-7.44(m,3H),7.48(t,J＝8.0Hz,1H),7.62(dt,J＝7.5,1.0Hz,1H),7.84(ddd,J＝8.0,7.0,2.0Hz,1H),8.14(ddd,J＝5.0,2.0,0.5Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.73,83.27,111.61,111.72,114.53,115.77,118.72,119.16,122.26,123.66,125.25,125.60,127.44,128.47,129.66,130.33,139.45,139.67,141.80,147.73,155.39,156.53,158.20,163.24,163.36.HR(ESI):calcd for C 27H 21N 2O 3[M+H] +421.15,found 421.15.
(2)P-PtOO的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(S,R)-L-OO(200mg,0.48mmol,1.0当量)，氯亚铂酸钾(208mg,0.50mmol,1.05当量)，四正丁基溴化铵(16mg,0.048mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(15mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，二氯甲烷溶解，加入水洗，水层用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-1:1，得到产物P-PtOO，淡黄色固体140mg，收率48％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.48(d,J＝18.5Hz,1H),3.61(dd,J＝18.5,6.5Hz,1H),5.98(t,J＝7.0Hz,1H),6.10(d,J＝7.0Hz,1H),6.44(d,J＝7.5Hz,1H),6.89(dq,J＝7.5,1.0Hz,2H),7.03-7.10(m,3H),7.12(t,J＝7.5Hz,1H),7.18(dd,J＝7.0,1.0Hz,1H),7.23(t,J＝7.5Hz,1H),7.35(d,J＝8.0Hz,1H),7.40(ddd,J＝7.0,5.5,1.0Hz,1H),7.22-7.30(m,4H),7.61(dd,J＝8.5,0.5Hz,1H),8.25(ddd,J＝8.0,7.0,2.0Hz,1H),9.12(dd,J＝5.5,1.5Hz,1H).HR(ESI):calcd for C 27H 19N 2O 3Pt[M+H] +614.10,found 614.10.
实施例47：四齿环金属铂(II)配合物M-PtOO的合成：
Figure PCTCN2022086993-appb-000106
(1)配体(R,S)-L-OO的合成：向带有磁力转子的干燥封管中依次加入2-Br(800mg,2.55mmol,1.2当量)，PyOPh-OH(512mg,2.12mmol,1.0当量)，碘化亚铜(40mg,0.21mmol,10mol％)，配体2(69mg,0.21mmol,10mol％)和磷酸钾(900mg,4.24mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(15mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/乙酸乙酯＝15:1-5:1，得到配体(R,S)-L-OO，黄棕色固体750mg，收率84％。 13C NMR(125MHz,CDCl 3):δ(ppm)39.74,83.28,111.61,111.73,114.53,115.77,118.73,119.19,122.28,123.68,125.26,125.62,127.46,128.48,129.67,130.33,139.46,139.68,141.82,147.75,155.40,156.53,158.23,163.26,163.37.HR(ESI):calcd for C 27H 21N 2O 3[M+H] +421.15,found 421.15.
(2)M-PtOO的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(R,S)-L-OO(210mg,0.50mmol,1.0当量)，氯亚铂酸钾(220mg,0.53mmol,1.05当量)，四正丁基溴化铵(16mg,0.050mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(15mL)。反应液氮气鼓泡30分钟后，室温先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡二水合物(1.10 g,5.00mmol,10.0当量)，二氯甲烷(15mL)，在40℃下搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-1:1，得到产物M-PtOO，淡黄色固体185mg，收率60％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.48(d,J＝18.5Hz,1H),3.61(dd,J＝18.5,6.5Hz,1H),5.98(t,J＝7.0Hz,1H),6.11(d,J＝7.0Hz,1H),6.44(d,J＝7.5Hz,1H),6.89(dq,J＝7.5,1.5Hz,2H),7.03-7.14(m,4H),7.18(dd,J＝7.5,1.5Hz,1H),7.22-7.25(m,1H),7.35(d,J＝7.5Hz,1H),7.40(ddd,J＝7.0,6.0,1.5Hz,1H),7.61(dd,J＝8.0,0.5Hz,1H),8.26(ddd,J＝8.5,7.0,1.5Hz,1H),9.13(dd,J＝5.5,1.5Hz,1H).HR(ESI):calcd for C 27H 19N 2O 3Pt[M+H] +614.10,found 614.10.
实施例48：四齿环金属铂(II)配合物P-PtOC的合成：
Figure PCTCN2022086993-appb-000107
(1)配体(S,R)-L-OC的合成：向带有磁力转子的干燥封管中依次加入1-Br(337mg,1.07mmol,1.2当量)，C-OH(300mg,0.89mmol,1.0当量)，碘化亚铜(17mg,0.09mmol,10mol％)，配体2(29mg,0.09mmol,10mol％)和磷酸钾(378mg,1.78mmol,2.0当量)，抽换氮气三次，在氮气保护下加入二甲基亚砜(15mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-1:1，得到配体(S,R)-L-OC，浅棕色固体305mg，收率60％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.23(d,J＝17.5Hz,1H),3.50(dd,J＝18.0,6.5Hz,1H),5.52(ddd,J＝8.0,7.0,1.5Hz,1H),5.71(d,J＝8.0Hz,1H),6.57(t,J＝2.0Hz,1H),6.74(dq,J＝8.0,1.0Hz,1H),6.84(ddd,J＝8.0,2.0,0.5Hz,1H),7.02(d,J＝8.0Hz,1H),7.13(ddd,J＝8.0,2.5,1.0Hz,1H),7.18(ddd,J＝7.5,5.0,1.0Hz,1H),7.22-7.31(m,5H),7.30-7.31(m,2H),7.37-7.46(m,4H),7.51-7.60(m,4H),7.90(d,J＝8.0Hz,2H),8.53(ddd,J＝4.5,2.0,1.0Hz,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.74,53.38,66.98,83.24,116.52,118.59,119.00,120.12,121.30,121.71,121.74,122.80,123.12,125.25,125.65,126.67,127.46,127.73,127.80,128.47,129.42,129.46,129.47,136.23,139.68,140.41,141.88,148.08,149.43,149.68,156.66,156.90,163.35,163.47.HR(ESI):calcd for C 40H 29N 2O 2[M+H] +569.22,found 569.22.
(2)M-PtOC的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(S,R)-L-OC(200mg,0.35mmol,1.0当量)，氯亚铂酸钾(154mg,0.37mmol,1.05当量)，四正丁基溴化铵(11mg,0.035mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(15mL)。反应液氮气鼓泡30分钟后，在30℃下先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，二氯甲烷溶解，加入水洗，水层用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-1:1，得到产物M-PtOC，淡黄色固体57mg，收率21％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.51(d,J＝18.5Hz,1H),3.60(dd,J＝18.5,5.5Hz,1H),5.73-5.75(m,1H),5.98-6.02(m,2H),6.26(dd,J＝8.0,1.0Hz,1H),6.38(t,J＝7.0Hz,1H),6.63-6.67(m,2H),6.88-6.90(m,2H),7.05(dd,J＝ 7.5,1.0Hz,1H),7.13-7.19(m,2H),7.23(dd,J＝7.0,1.0Hz,1H),7.27(td,J＝7.5,1.0Hz,1H),7.34(d,J＝7.5Hz,1H),7.39(d,J＝7.5Hz,1H),7.52-7.58(m,2H),7.66(td,J＝7.5,1.0Hz,1H),7.86-7.90(m,2H),8.12(d,J＝7.5Hz,1H),9.23(d,J＝8.0Hz,1H),9.52(dd,J＝5.5,1.5Hz,1H).HR(ESI):calcd for C 40H 27N 2O 2Pt[M+H] +762.17,found 762.17.
实施例49：四齿环金属铂(II)配合物M-PtOC的合成：
Figure PCTCN2022086993-appb-000108
(1)配体(R,S)-L-OC的合成：向带有磁力转子的干燥封管中依次加入2-Br(337mg,1.07mmol,1.2当量)，C-OH(300mg,0.89mmol,1.0当量)，碘化亚铜(17mg,0.09mmol,10mol％)，配体2(29mg,0.09mmol,10mol％)和磷酸钾(378mg,1.78mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(10mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-1:1，得到配体(R,S)-L-OC，浅黄色固体278mg，收率55％。
13C NMR(125MHz,CDCl 3):δ(ppm)26.89,39.72,60.36,66.98,83.30,116.60,118.56,119.02,120.12,121.34,121.75,122.86,123.11,125.23,125.71,126.67,127.47,127.74,127.81,128.17,128.33,128.51,128.80,129.10,129.27,129.44,129.53,136.27,139.65,140.40,141.78,149.41,149.70,156.61,156.90,163.33,163.56.HR(ESI):calcd for C 40H 29N 2O 2[M+H] +569.22,found 569.22.
(2)M-PtOC的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(R,S)-L-OC(200mg,0.35mmol,1.0当量)，氯亚铂酸钾(154mg,0.37mmol,1.05当量)，四正丁基溴化铵(11mg,0.035mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(15mL)。反应液氮气鼓泡30分钟后，在40℃下先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡二水合物(790mg,3.50mmol,10.0当量)，二氯甲烷(15mL)，在40℃下搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝2:1-1:1，得到产物M-PtOC，淡黄色固体80mg，收率30％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.51(d,J＝18.0Hz,1H),3.60(dd,J＝18.5,5.5Hz,1H),5.74(d,J＝8.0Hz,1H),5.98-6.02(m,2H),6.26(dd,J＝8.0,1.0Hz,1H),6.38(t,J＝7.5Hz,1H),6.63-6.67(m,2H),6.88-6.90(m,2H),7.05(dd,J＝8.0,1.5Hz,1H),7.13-7.19(m,2H),7.23(dd,J＝7.5,1.0Hz,1H),7.27(td,J＝7.5,1.0Hz,1H),7.34(d,J＝8.0Hz,1H),7.40(d,J＝8.0Hz,1H),7.53-7.58(m,2H),7.66(td,J＝7.5,1.0Hz,1H),7.86-7.90(m,2H),8.13(d,J＝7.5Hz,1H),9.23(d,J＝7.5Hz,1H),9.52(dd,J＝6.0,1.5Hz,1H).HR(ESI):calcd for C 40H 27N 2O 2Pt[M+H] +762.17,found762.17.
实施例50：四齿环金属铂(II)配合物P-PtS的合成：
Figure PCTCN2022086993-appb-000109
(1)配体(S,R)-L-S的合成：向带有磁力转子的干燥封管中依次加入1-Br(830mg,2.64mmol,1.2当量)，S-OH(500mg,2.20mmol,1.0当量)，碘化亚铜(42mg,0.22mmol,10mol％)，配体2(72mg,0.22mmol,10mol％)和磷酸钾(934mg,4.40mmol,2.0当量)，抽换氮气三次，在氮气保护下加入N,N-二甲基甲酰胺(20mL)。将封管置于85℃的油浴锅中搅拌，反应3天，冷却至室温，水洗，加入乙酸乙酯萃取，水层用乙酸乙酯萃取三次，合并有机相，有机相用盐水洗涤一次，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝3:1-1:1，得到配体(S,R)-L-S，浅棕色固体650mg，收率64％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.22(d,J＝18Hz,1H),3.48(dd,J＝18,6.5Hz,1H),5.52(td,J＝8.0,1.5Hz,1H),5.69(d,J＝8.0Hz,1H),7.21-7.34(m,4H),7.32(ddd,J＝8.0,2.5,1.0Hz,1H),7.41-7.43(m,1H),7.50-7.49(m,2H),7.52-7.56(m,2H),7.61(t,J＝8.0Hz,1H),7.67-7.70(m,2H),7.88(ddd,J＝8.0,1.5,0.5Hz,1H),8.04-8.05(m,1H),8.14-8.16(m,1H). 13C NMR(125MHz,CDCl 3):δ(ppm)39.74,83.31,117.73,119.02,121.12,121.59,122.10,122.62,123.35,123.77,125.26,125.32,125.61,126.35,127.46,128.48,129.8,129.83,130.43,135.09,135.43,139.68,141.80,154.02,156.69,157.69,163.35,167.10.
(2)P-PtS的合成：向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入(S,R)-L-S(300mg,0.65mmol,1.0当量)，氯亚铂酸钾(282mg,0.68mmol,1.05当量)，四正丁基溴化铵(21mg,0.065mmol,0.1当量)，然后抽换氮气三次，加入预先鼓氮气的醋酸(20mL)。反应液氮气鼓泡30分钟后，在30℃下先搅拌12小时，然后在120℃下搅拌反应2天，冷却至室温，减压蒸馏除去溶剂，加入氯化亚锡二水合物(734mg,3.25mmol,5.0当量)，二氯甲烷(15mL)，在40℃下搅拌1天。反应液水洗，水相用二氯甲烷萃取三次，合并有机相，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝4:1-2:1，得到产物P-PtS，淡黄色固体120mg，收率28％。 1H NMR(500MHz,DMSO-d 6):δ(ppm)3.54(d,J＝18.5Hz,1H),3.66(dd,J＝18.5,6.0Hz,1H),6.05(t,J＝6.0Hz,1H),6.46(d,J＝7.0Hz,1H),7.01(t,J＝7.5Hz,1H),7.13(dd,J＝8.0,1.0Hz,1H),7.15-7.18(m,1H),7.19-7.25(m,4H),7.30(t,J＝7.5Hz,1H),7.38(d,J＝7.5Hz,1H),7.57-7.60(m,1H),7.65-7.70(m,2H),8.33(dd,J＝8.0,1.0Hz,1H),8.51(d,J＝8.0Hz,1H).
电化学、光物理测试和理论计算说明：
吸收光谱在Agilent 8453紫外-可见光光谱仪上测量，使用Horiba Jobin Yvon FluoroLog-3光谱仪上进行稳态发射实验和寿命测量,或SHIMADZU RF-6000光谱仪上进行稳态发射光谱测试。低温(77K)发射光谱和寿命在用液氮冷却的2-甲基四氢呋喃(2-MeTHF)溶液中测量。Pt(II)配合物使用Gaussian 09软件包进行理论计算，利用密度泛函理论(DFT)优化了基态(S 0)分子的几何结构，使用B3LYP泛函进行DFT计算，其中C、H、O和N原子使用6-31G(d)基组，Pt原子使用LANL2DZ基组。对映异构体纯度(ee值)在手性色谱柱EnantiopakR-C(规格：4.6×250mm，5um)上测试完成。
实验数据及分析：
附图1为光学纯的以金属离子为中心的螺手性四齿环金属配合物圆偏振光发光材料设计思路：光学纯原料经济易得；中心手性自主诱导螺手性的产生；圆偏振光发光材料无需手性拆分，大大节省光学纯材料的制备成本，且可以大量制备，不受手性制备色谱柱拆分的限制。由表1中的对映异构体过量数值(ee值)可知由上述材料设计思路所得到的均为光学纯度极高的单一手性材料分子，其ee值均>99％。上述实验数据也说明此材料设计思路是成功的。
由附图2至附图5中系列不同配体结构的四齿环金属铂(II)配合物密度泛函理论(DFT)计算优化后的分子结构可知，对于含有中心手性为(R,S)的配体均可主诱导M型螺手性的产生，对于含有中心手性为(S,R)的配体均可主诱导P型螺手性的产生，且M型螺手性分子和P型螺手性分子互为对映异构体；材料分子的绝对构型得到了(R,S)-M-PtLA1的X-衍射单晶结构结构的支持(附图1左图)。此外，DFT计算优化后的四齿环金属钯(II)配合物分子结构具有相似的结果。
本申请的对比四齿环金属铂(II)配合物结构如下所示，由于其均为非手性分子，故比旋光度([a] 20 D)和不对称因子(g PL)均为零。
Figure PCTCN2022086993-appb-000110
由附图6至附图20及表2中所合成的光学纯螺手性材料分子在二氯甲烷溶液中室温下的发射光谱图可知，通过四齿配体结构的调控可以对环金属配合物的发光颜色近性高效的调节，可实现从约360nm的紫外区到650nm的红光区的调控；相信通过四齿配体结构的进一步调控，亦可实现红外发光。此外，由附图6至附图20中发射光谱图基本完全重合，进一步证明了附图中相应的材料分子为对映异构体。
由附图21中(S,R)-P-PtLA1和(R,S)-M-PtLA1在二氯甲烷溶液中的圆二色光谱可知，其中CD为圆二色光谱，样品浓度为5×10 -5M；其谱图具有很高的镜面对称性，且在大约248、275、300和248nm具有很强的科顿效应(Cotton effect)，说明对映异构体(S,R)-P-PtLA1和(R,S)-M-PtLA1对直线偏振光具有很强的偏转能力。在下表1中的比旋光度([a] 20 D)数据也可看出本申请中的螺手性四齿环金属材料分子均显示出很强的直线偏振光偏转能力，其它部分材料分子的圆二色光谱如附图22至附图25所示；而对比材料分子PtON1、PtON3和PtOO3的比旋光度([a] 20 D)则均为零。
由表二可知本申请中的螺手性材料分子均表现出很强的圆偏振发光，其不对称因子(g PL)绝对值可高达4.0×10 -3，附图26至附图33为部分材料分子的圆偏振发光光谱。而对比材料分子PtON1、PtON3和PtOO3的均无圆偏振发光。
材料化学稳定性和热稳定性高。所设计发展的四齿配体可以和dsp 2杂化的铂(II)和钯(II)金属离子很好的配位形成稳定而刚性的四边形构型分子，化学稳定性高；同时，由于所设计的中心手性配体L a和另一末端配体L 1或L b之间具有较大空间位阻效应，使整个金属配合物分子可形成稳定的螺手性四齿环金属配合物，使其在溶液或高温升华过程中均不会发生消旋而丧失圆偏振发光性质。附图34自上而下分别为(R,S)-M-PtLA1和(S,R)-P-PtLA1混合物的高效液相色谱谱图(HPLC)、光学纯(R,S)-M-PtLA1高效液相色谱谱图、光学纯(S,R)-P-PtLA1高效液相色谱谱图以及升华后的(R,S)-M-PtLA1高效液相色谱谱图可知，此类材料具有很高的热稳定性，升华实验表明在320℃下分别升华出的(R,S)-M-PtLA1和(S,R)-P-PtLA1材料均未发生消旋。由附图35中(R,S)-M-PtLA1的热重分析曲线可知其分解温度(质量损失5％时的温度)高达405℃。
由下表1中部分手性原料中间体和手性金属配合物的比旋光度数据可知，即使含有相同中心手性的原 料中间体和手性金属配合物的旋光方向完全不一样，且比旋光度数值也差距巨大，说明配合物以中金属离子为中心的螺手性对整个化合物的旋光性质有着决定性的影响；此外，具有相同中心手性和螺手性的配合物，配体结构不同，比旋光度相差也会很大，如(S,R)-P-PtLA1(+477.2)和(S,R)-P-PtLA1(+784.6)，说明配体结构对其旋光影响很大。同时，由于金属配合物受激发辐射发光主要涉及到金属到配体电荷转移态(MLCT)和配体内的电荷转移态(ILCT)，因此金属配合物的螺手性和配体结构对其圆偏振光性质亦会有重大影响。
表1：部分手性原料中间体和手性金属配合物的比旋光度([a] 20 D)
Figure PCTCN2022086993-appb-000111
注：所有样品的比旋光度数值均在二氯甲烷溶液中测定。
表2：手性金属配合物的最大发射波长(λ max)和不对称因子(g PL)
金属配合物 λ max(nm) g PL(×10 -3) 金属配合物 λ max(nm) g PL(×10 -3)
PtON1   0 PtON3   0
      PtOO3   0
(R,S)-M-PtLA1 535 -2.8 (S,R)-P-PtLA1 535 +2.7
(R,S)-M-PtLA2 610 -1.8 (S,R)-P-PtLA2 610 +1.8
(R,S)-M-PtLA3 546 -4.1 (S,R)-P-PtLA3 546 +3.7
M-PtLB1 536 -2.8 P-PtLB1 536 +2.9
M-PtLC1 541 -3.1 P-PtLC1 541 +3.3
M-PtLD1 543 -3.8 P-PtLD1 543 +3.6
M-PtLE1 538 -3.2 P-PtLE1 538 +3.1
M-PtLF1 522 -2.4 P-PtLF1 522 +2.4
(R,S)-M-PtLAN 620 -1.1 (S,R)-P-PtLAN 620 +1.2
(S,R)-M-PtLH1 556 -1.8 (S,R)-P-PtLH1 556 +1.6
(S,R)-M-PtLI1 574   (S,R)-P-PtLI1 574  
(S,R)-M-PtLJ1 545 -2.2 (S,R)-P-PtLJ1 545 +2.30
(R,S)-M-PtLK1 592 -0.38 (S,R)-P-PtLK1 592 +0.40
M-PtLIII-1 358   P-PtLIII-1 358  
M-PtB1 536 -0.23 P-PtB1 536 +0.26
M-PtB2 624 -0.65 P-PtB2 624 +0.59
M-PtB3 603 -2.02 P-PtB3 603 +1.95
M-PtB9 523 -1.14 P-PtB9 523 +1.03
M-PdLA1 479 -1.80 P-PdLA1 479 +1.10
M-PtL1 563 -0.57 P-Pt L1 563 +0.40
M-PtL2 562 -2.94 P-Pt L2 562 +3.50
M-PtL3 536 -2.00 P-Pt L3 536 +2.00
M-PtOO 542 -4.00 P-PtOO 542 +3.70
M-PtOC 531 -2.50 P-PtOC 531 +2.70
      P-PtS    
注：所有样品的最大发射波长(λ max)和不对称因子(g PL)均在二氯甲烷溶液中测定。
由下表3中部分手性金属配合物材料分子的理论计算实验数据可知，此类含有手性结构单元的分子母核均为扭曲的四边形结构；且由于配位杂环中邻位手性位阻的存在，可以使和中心金属离子配位的末端两个杂环分别处于平面的两侧，从而形成以中心金属为中心的螺手性分子，均可以用作圆偏振发光材料。
此外，上述大量理论计算实验数据也说明和中心金属配位的手性结构单元中邻位基团位阻的重要性，是配体手性结构单元中心手性诱导产生整个材料分子以金属为中心螺手性的关键。同时，上述大量的合成实验实施例及其光物理性质表征和测试亦说明了本申请圆偏振发光材料分子设计的方法是完全成功的。
表3：部分手性金属配合物材料分子的理论计算实验数据
Figure PCTCN2022086993-appb-000112
Figure PCTCN2022086993-appb-000113
Figure PCTCN2022086993-appb-000114
Figure PCTCN2022086993-appb-000115
Figure PCTCN2022086993-appb-000116
Figure PCTCN2022086993-appb-000117
Figure PCTCN2022086993-appb-000118
注：二面角是指和中心金属离子配位的末端两个杂环之间形成的角度。
在有机发光元件中，从正负两电极向发光材料中注入载子，产生激发态的发光材料并使其发光。通过通式(1)代表的本发明的络合物可作为磷光发光材料应用于有机光致发光元件或有机电致发光元件等优异的有机发光元件。有机光致发光元件具有在衬底上至少形成了发光层的结构。另外，有机电致发光元件具有至少形成了阳极、阴极、及阳极和阴极之间的有机层的结构。有机层至少包含发光层，可以仅由发光层构成，也可以除发光层以外具有1层以上的有机层。作为这种其它有机层，可以列举空穴传输层、空穴注入层、电子阻挡层、空穴阻挡层、电子注入层、电子传输层、激子阻挡层等。空穴传输层也可以是具有空穴 注入功能的空穴注入传输层，电子传输层也可以是具有电子注入功能的电子注入传输层。具体的有机发光元件的结构示意如图35所示。在图35中，从下到上共7层，依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极，其中发光层为客体材料掺杂入主体材料的混合层。
将实施例1-50中所表示的化合物作为磷光发光材料应用于OLED器件，结构表示为：
ITO/HATCN(10nm)/TAPC(65nm)/主体材料:发光材料(10wt.％,20nm)/TmPyPB(55nm)/LiF/Al
其中，ITO为透明阳极；HATCN是空穴注入层，TAPC是空穴传输层，主体材料分别为mCBP和26mCPy，TmPyPB为电子传输层，LiF为电子注入层，Al为阴极。括号中单位为纳米(nm)的数字为薄膜的厚度。
器件中应用材料的分子式如下：
Figure PCTCN2022086993-appb-000119
进一步，在有机发光器件中，从正负两电极向发光材料中注入载子，产生激发态的发光材料并使其发光。通过本发明的络合物可作为磷光发光材料应用于有机光致发光器件或有机电致发光器件等优异的有机发光器件。有机光致发光器件具有在衬底上至少形成了发光层的结构。另外，有机电致发光元件具有至少形成了阳极、阴极、及阳极和阴极之间的有机层的结构。有机层至少包含发光层，可以仅由发光层构成，也可以除发光层以外具有1层以上的有机层。作为这种其它有机层，可以列举空穴传输层、空穴注入层、电子阻挡层、空穴阻挡层、电子注入层、电子传输层、激子阻挡层等。空穴传输层也可以是具有空穴注入功能的空穴注入传输层，电子传输层也可以是具有电子注入功能的电子注入传输层。具体的有机发光元件的结构示意如图6所示。在图6中，从下到上共7层，依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极，其中发光层为客体材料掺杂入主体材料的混合层。
本发明的有机发光器件的各层可采用真空蒸镀、溅射、离子电镀等方法，或湿法成膜如旋涂、打印、印刷等方法形成，所用的溶剂没有特别限制。
在本发明的一种优选实施方式中，本发明的OLED器件中含有空穴传输层，空穴传输材料可以优选自已知或未知的材料，特别优选地选自以下结构，但并不代表本发明限于以下结构：
Figure PCTCN2022086993-appb-000120
在本发明的一种优选实施方式中，本发明的OLED器件中含有的空穴传输层，其包含一种或多种p型掺杂剂。本发明优选的p型掺杂剂为以下结构，但并不代表本发明限于以下结构：
Figure PCTCN2022086993-appb-000121
本发明的一种优选实施方式中，所述的电子传输层可以选自化合物ET-1至ET-13的至少一种，但并 不代表本发明限于以下结构：
Figure PCTCN2022086993-appb-000122
电子传输层可以有机材料与一种或多种n型掺杂剂(如LiQ)共同形成。
将实施例1中所表示的化合物作为圆偏振光发光材料应用于OLED器件，其结构亦可表示为：在含有ITO的玻璃上，空穴注入层(HIL)为HT-1:P-3(95:5v/v％)，厚度为10纳米；空穴传输层(HTL)为HT-1，厚度为90纳米；电子阻挡层(EBL)为HT-10，厚度为10纳米，发光层(EML)为主体材料(H-1或H-2或H-3或H-4或H-5或H-6):本发明铂金属配合物(95:5v/v％)，厚度为35纳米，电子传输层(ETL)为ET-13：LiQ(50:50v/v％)，厚度为35纳米，然后蒸镀阴极Al为70纳米。
Figure PCTCN2022086993-appb-000123
制作的有机发光器件采用本领域公知的标准方法在10mA/cm 2电流条件下测试，其中以(S,R)-P-PtLA1 为发光材料的一个器件具有显著的圆偏振电致发光信号，不对称因子(g EL)达1.4×10 -3，且其最大外量子效率(EQE)达到18％。
需要说明的是，所述结构为本发明圆偏振光发光材料的一个应用的举例，不构成本发明所示圆偏振光发光材料的具体OLED器件结构的限定，圆偏振光发光材料也不限于实施例中所表示的化合物。
需要说明的是，所述结构为本发明磷光材料的一个应用的举例，不构成本发明所示磷光材料的具体OLED器件结构的限定，磷光发光材料也不限于实施例中所表示的化合物。
本领域的普通技术人员可以理解，上述各实施方式是实现本发明的具体实施例，而在实际应用中，可以在形式上和细节上对其作各种改变，而不偏离本发明的精神和范围。例如，在不背离本发明的精神的情况下，这里描述的许多取代基结构可以用其它结构代替。

Claims (10)

  1. 一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料，其特征在于，其化学式如通式(I)、(I')、(II)、(II')、(III)和(III')所示，其中(I)和(I')、(II)和(II')、(III)和(III')互为对映异构体：
    Figure PCTCN2022086993-appb-100001
    其中M为Pt或Pd；V 1、V 2、V 3和V 4各自独立的为N或C；
    L 1、L 2和L 3是各自独立的为五元或六元碳环、杂环、芳环或者杂芳环；L a和L b是各自独立的为五元中心手性碳环或者杂环；
    A 1、A 2、X和X 1各自独立地为O、S、CR xR y、C＝O、SiR xR y、GeR xR y、NR z、PR z、R zP＝O、AsR z、R zAs＝O、S＝O、SO 2、Se、Se＝O、SeO 2、BH、BR z、R zBi＝O或BiR z；
    R 1、R 2和R 3各自独立地表示单、双、三、四-取代或者无取代，同时R 1、R 2、R 3、R a、R b、R c、R d、R e、R f、R g、R h、R x、R y和R z各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R 1、R 2和R 3可以选择性连接形成稠环；R a、R b、R c和R d中的任意两个基团可连接形成环状体系，R e、R f、R g和R h中的任意两个基团可连接形成环状体系。
  2. 根据权利要求1所述的具有通式(I)、(I')、(II)和(II')的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料，优选如下通式(I-A)、(I-A)、(I-B)、(I-C)、(I-D)、(I-E)、(I-F)、(I-G)、(I-H)、(I-I)、(II-A)和其对映异构体(I'-A)、(I'-A)、(I'-B)、(I'-C)、(I'-D)、(I'-E)、(I'-F)、(I'-G)、(I'-H)、(I'-I)、(II'-A)：
    Figure PCTCN2022086993-appb-100002
    Z和Z 1各自独立地为O、S、CR xR y、C＝O、SiR xR y、GeR xR y、NR z、PR z、R zP＝O、AsR z、R zAs＝O、S＝O、SO 2、Se、Se＝O、SeO 2、BH、BR z、R zBi＝O或BiR z；
    R 4和R 5各自独立地表示单、双、三、或四-取代或者无取代，同时R 1、R 2、R 3、R 3、R 4、R 5、R a、R b、R c、R d、R x、R y和R z各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R 1、R 2、R 3、R 4和R 5可以选择性连接形成稠环；R a、R b、R c和R d中的任意两个基团可连接形成环状体系。
  3. 根据权利要求1或2所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料通式结构中的L a和L b的结构优选自：
    Figure PCTCN2022086993-appb-100003
    其中R a1、R a2和R a3各自独立地表示氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；
    其中R b1、R c1和R c2各自独立地表示单、双、三、四-取代或者无取代，同时R b1、R c1和R c2各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R b1、R c1和R c2可以选择性连接形成稠环。
  4. 根据权利要求3所述的L a和L b的具体结构优选自：
    Figure PCTCN2022086993-appb-100004
    Figure PCTCN2022086993-appb-100005
    其中R d1、R e1、R e2、R e3和R e4各自独立地表示单、双、三、四-取代或者无取代，同时R b1、R c1和R c2各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、 卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合；两个或者多个邻近的R b1、R c1和R c2可以选择性连接形成稠环。
  5. 根据权利要求1或2所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料优选自：
    Figure PCTCN2022086993-appb-100006
    Figure PCTCN2022086993-appb-100007
    Figure PCTCN2022086993-appb-100008
  6. 根据权利要求1或2所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料，可进一步选自如下的铂(II)金属配合物及其对应异构体圆偏振发光材料以及它们对应的金属钯(II)配合物圆偏振发光材料：
    Figure PCTCN2022086993-appb-100009
    Figure PCTCN2022086993-appb-100010
    Figure PCTCN2022086993-appb-100011
    Figure PCTCN2022086993-appb-100012
    Figure PCTCN2022086993-appb-100013
    Figure PCTCN2022086993-appb-100014
    Figure PCTCN2022086993-appb-100015
    Figure PCTCN2022086993-appb-100016
    Figure PCTCN2022086993-appb-100017
    Figure PCTCN2022086993-appb-100018
    Figure PCTCN2022086993-appb-100019
    Figure PCTCN2022086993-appb-100020
    Figure PCTCN2022086993-appb-100021
    Figure PCTCN2022086993-appb-100022
    Figure PCTCN2022086993-appb-100023
    Figure PCTCN2022086993-appb-100024
    Figure PCTCN2022086993-appb-100025
    Figure PCTCN2022086993-appb-100026
    Figure PCTCN2022086993-appb-100027
    Figure PCTCN2022086993-appb-100028
    Figure PCTCN2022086993-appb-100029
    Figure PCTCN2022086993-appb-100030
    Figure PCTCN2022086993-appb-100031
    Figure PCTCN2022086993-appb-100032
    Figure PCTCN2022086993-appb-100033
    Figure PCTCN2022086993-appb-100034
    Figure PCTCN2022086993-appb-100035
    Figure PCTCN2022086993-appb-100036
    Figure PCTCN2022086993-appb-100037
    Figure PCTCN2022086993-appb-100038
    Figure PCTCN2022086993-appb-100039
    Figure PCTCN2022086993-appb-100040
    Figure PCTCN2022086993-appb-100041
    Figure PCTCN2022086993-appb-100042
    Figure PCTCN2022086993-appb-100043
    Figure PCTCN2022086993-appb-100044
    Figure PCTCN2022086993-appb-100045
    Figure PCTCN2022086993-appb-100046
    Figure PCTCN2022086993-appb-100047
    Figure PCTCN2022086993-appb-100048
    Figure PCTCN2022086993-appb-100049
    Figure PCTCN2022086993-appb-100050
    Figure PCTCN2022086993-appb-100051
    Figure PCTCN2022086993-appb-100052
    Figure PCTCN2022086993-appb-100053
    Figure PCTCN2022086993-appb-100054
  7. 一种权利要求1至2中任一项所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料在有机发光元件、3D显示器件、三维成像器件、光学信息加密器件、信息存储器件、生物成像器件中的应用。
  8. 根据权利要求7所述的应用，其特征在于，所述有机发光元件为有机发光二极管、发光二极管或发光电化学电池。
  9. 根据权利要求8所述的应用，其特征在于，所述发光元件包括第一电极、第二电极及设置于所述第一电极和所述第二电极之间的至少一个有机层，所述有机层包括中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料。
  10. 显示装置，其包括有机发光元件，其中，所述有机发光元件包括第一电极、第二电极及设置于所述第一电极和所述第二电极之间的至少一个有机层，所述有机层包括权利要求1至2中任一项所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料。
PCT/CN2022/086993 2021-04-15 2022-04-15 中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用 WO2022218399A1 (zh)

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