CN115010763A - Circular polarization phosphorescence platinum (II) complex and preparation method and application thereof - Google Patents
Circular polarization phosphorescence platinum (II) complex and preparation method and application thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a circular polarization phosphorescence platinum (II) complex, the structure of which is shown as the following formula:
wherein R is 1 Is one of hydrogen, deuterium, alkenyl, alkynyl, amido, nitryl, carbonyl, sulfuryl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic chiral alkyl chain of C3-C60;R 2 is an arylamine group. On one hand, 2, 6-bis (N-alkyl benzimidazolyl) benzene is used as a tridentate chelating ligand, so that certain interaction force exists between the molecules in an excited state to form an excimer; on the other hand, the unit with the chiral center is connected with the tridentate chelating ligand and/or the isonitrile part through a covalent bond, circular polarization luminescence is realized through chiral transmission, and convenience is provided for the improvement and application of the circular polarization luminescent material through the regulation and control of the molecular structure of the material.
Description
Technical Field
The invention relates to the field of metal complex luminescent materials, in particular to a circular polarization phosphorescence platinum (II) complex and a preparation method and application thereof.
Background
In recent years, chiral optical functional materials with Circular Polarized Luminescence (CPL) have received increasing attention due to their wide potential applications in three-dimensional optical displays, information encryption transmission and storage, bio-coding, opto-electronics, and the like. In developing CPL materials, a key issue is achieving a high luminescence asymmetry factor (g) lum ) To facilitate the quantification of CPL, the formula g is usually used lum ＝2×(I L -I R )/(I L +I R ) Performing a calculation in which I L And I R Respectively, left/right circularly polarized light emission intensity. | g lum The maximum value of | is 2, indicating complete left or right handed circular polarized light. Although the highest g lum From chiral lanthanide metal complexes, however, these materials exhibit small luminous efficiencies, and thus, scientists have gradually focused on developing transition metal complexes and small organic molecules with CPL activity.
Generally, there are two main design strategies for novel circular polarization luminescent materials, one is to introduce a chiral unit on a chromophore through a covalent bond or a coordination bond, and then realize circular polarization luminescence through chiral transfer; the other is to construct a spiro chirality through steric hindrance effect so as to realize high-efficiency circularly polarized emission. However, most of the chiral molecules constructed by the two strategies show a weaker CPL signal, | g lum The | values are almost all 10 -5 -10 -3 In order to increase the CPL signal, researchers have demonstrated that the | g' of perylene-bisimide systems can be modified by supramolecular self-assembly lum The | value increased from 0.003 to 0.008. Although this strategy is effective in enhancing the CPL signal, in general, not only are the materials used for self-assembly difficult to select, but the self-assembly process is also difficult to achieve, and the ratio between the multiple phases, and thus the requirements, are often precisely controlledThe solvent, concentration, temperature, etc. Compared with the method, the strategy of realizing the amplification of the CPL signal by singly regulating and controlling the concentration to form the excimer is easy to control and convenient to operate. The amplification of CPL signals by controlling the concentration of small organic molecules (especially organometallic complexes) has been rarely reported.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a circular polarization phosphorescent platinum (II) complex, and a preparation method and application thereof, and aims to solve the problem that the CPL signal of the existing circular polarization luminescent material is weak.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a circular polarization phosphorescent platinum (II) complex, wherein the structure of the circular polarization phosphorescent platinum (II) complex is shown as the following formula:
wherein R is 1 Is one of hydrogen, deuterium, alkenyl, alkynyl, amido, nitryl, carbonyl, sulfuryl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic chiral alkyl chain of C3-C60; r 2 Is an arylamine group.
The preparation method of the circular polarization phosphorescent platinum (II) complex according to the scheme of the invention comprises the following steps:
providing 2, 6-bis (N-alkylbenzimidazolyl) benzene;
reacting the 2, 6-bis (N-alkylbenzimidazolyl) benzene with a first reactant to obtain a first intermediate;
reacting the first intermediate with potassium tetrachloroplatinate to obtain a second intermediate;
reacting the second intermediate with a second reactant to obtain the circular polarization phosphorescence platinum (II) complex;
wherein, the instituteThe first reactant is a compound containing one of hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfonyl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic radical chiral alkyl chain of C3-C60, and the structure of the first intermediate is
The second reactant is a compound containing an aromatic amine group, and the structure of the second intermediate is
The preparation method of the circular polarization phosphorescence platinum (II) complex comprises the following steps of reacting the 2, 6-bis (N-alkyl benzimidazolyl) benzene with a first reactant to obtain a first intermediate, wherein the first intermediate comprises the following steps:
mixing 2, 6-bis (N-alkyl benzimidazolyl) benzene, sodium hydride, a first reactant and N, N-dimethylformamide, reacting at 100 ℃ for 12 hours, cooling to room temperature after the reaction is finished, and evaporating to remove the solvent to obtain a first crude product;
dissolving the first crude product in dichloromethane, adding dichloromethane and water, extracting, and collecting an organic phase;
and drying, filtering, concentrating and purifying the organic phase to obtain the first intermediate.
The preparation method of the circular polarization phosphorescence platinum (II) complex comprises the following steps of:
and (3) mixing the first intermediate and potassium tetrachloroplatinate in a container, vacuumizing and blowing nitrogen, adding glacial acetic acid, refluxing and filtering to obtain the second intermediate.
The preparation method of the circular polarization phosphorescence platinum (II) complex comprises the following steps of:
placing the second intermediate and the second reactant in a container, mixing, sealing, vacuumizing and blowing nitrogen, adding a mixed solution of ultra-dry dichloromethane and acetonitrile, and stirring at room temperature to react to obtain a reaction solution;
adding potassium hexafluorophosphate into the reaction liquid, and reacting to obtain a suspension;
filtering the suspension, collecting filtrate, and removing the organic solvent in the filtrate to obtain a second crude product;
and purifying the second crude product to obtain the circular polarization phosphorescence platinum (II) complex.
The invention relates to application of a circular polarization phosphorescence platinum (II) complex in acetonitrile solution to realizing circular polarization luminescence.
The invention relates to application of a circular polarization phosphorescence platinum (II) complex doped in a PMMA (polymethyl methacrylate) film to realize circular polarization luminescence.
Has the advantages that: the invention discloses a circular polarization phosphorescence platinum (II) complex and a preparation method and application thereof, on one hand, 2, 6-bis (N-alkyl benzimidazolyl) benzene with larger conjugation is used as a tridentate chelating ligand, so that certain interaction force exists in the molecule in an excited state to form an excimer; on the other hand, a unit with a chiral center is connected with the tridentate chelating ligand and/or the isonitrile part through a covalent bond, circular polarization luminescence is realized through chiral transmission, and a circular polarization luminescent material with excellent performance can be obtained by regulating the molecular structure of the material, so that convenience is brought to the improvement and application of the performance of the circular polarization luminescent material.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of the preparation method of the circularly polarized phosphorescent platinum (II) complex of the present invention.
FIG. 2 shows the complexes prepared in examples 1-1 to 1-3 of the present invention at a concentration of 1X 10 -5 Absorption spectrum of M in acetonitrile.
FIG. 3 shows the complexes prepared in examples 1-1 to 1-3 of the present invention at a concentration of 1X 10 -5 Emission spectrum in acetonitrile solution of M.
Figure 4 is the bookThe complex R-Ph-Iso prepared in inventive example 1-1 was used at a concentration of 1X 10 -6 M to 1X 10 -3 Emission spectrum in acetonitrile solution of M.
FIG. 5 shows the concentration of R-Ph-Iso in the complex prepared in example 1-1 of the present invention at 1X 10 -5 M and 1X 10 -3 Circular polarized luminescence spectrum in acetonitrile solution of M.
FIG. 6 shows the emission spectrum of the complex R-Ph-Iso prepared in example 1-1 of the present invention in a PMMA-doped thin film.
FIG. 7 is a circular polarized luminescence spectrum of the complex R-Ph-Iso prepared in inventive example 1-1 at doping concentrations of 1 wt% and 9 wt%, respectively.
Detailed Description
The invention provides a circular polarization phosphorescence platinum (II) complex and a preparation method and application thereof, and the invention is further detailed below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a circular polarization phosphorescence platinum (II) complex, the structure of which is shown as the following formula:
wherein R is 1 Is one of hydrogen, deuterium, alkenyl, alkynyl, amido, nitryl, carbonyl, sulfuryl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic chiral alkyl chain of C3-C60; r 2 Is an arylamine group.
Specifically, the 2, 6-bis (N-alkyl benzimidazolyl) benzene with larger conjugation is used as a tridentate chelating ligand, so that certain interaction force exists in the molecule in an excited state to form an excimer; on the other hand, a unit with a chiral center is connected with the tridentate chelating ligand and/or the isonitrile part through a covalent bond, circular polarization luminescence is realized through chiral transmission, and a circular polarization luminescent material with excellent performance can be obtained by regulating the molecular structure of the material, so that convenience is brought to the improvement and application of the performance of the circular polarization luminescent material.
Wherein (II) represents the valence of the metal platinum, the metal platinum having two valences and three valences, and (II) represents the valence thereof being two valences; said R is 1 Either chiral or achiral. In some embodiments, R 1 One selected from the following structures:
in some embodiments, R 2 One selected from the following structures:
in some embodiments, the circular polarization phosphorescent platinum (II) complex is selected from any one of the following compounds:
the invention also provides a preparation method of the circular polarization phosphorescence platinum (II) complex, as shown in figure 1, which comprises the following steps:
s10, providing 2, 6-bis (N-alkylbenzimidazolyl) benzene;
s20, reacting the 2, 6-bis (N-alkyl benzimidazolyl) benzene with a first reactant to obtain a first intermediate;
s30, reacting the first intermediate with potassium tetrachloroplatinate to obtain a second intermediate;
s40, reacting the second intermediate with a second reactant to obtain the circular polarization phosphorescence platinum (II) complex.
Wherein the first reactant is a compound containing one of hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfonyl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic radical chiral alkyl chain of C3-C60, the hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfonyl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic radical chiral alkyl chain of C3-C60 are chiral or achiral, and the first intermediate has a structure of chiral or achiral
The second reactant is a compound containing an aromatic amine group, and the structure of the second intermediate is
In some embodiments, the step of reacting said 2, 6-bis (N-alkylbenzimidazolyl) benzene with a first reactant to provide a first intermediate comprises the steps of:
mixing 2, 6-bis (N-alkyl benzimidazolyl) benzene, sodium hydride, a first reactant and N, N-dimethylformamide, reacting at 100 ℃ for 12 hours, cooling to room temperature after the reaction is finished, and evaporating to remove the solvent to obtain a first crude product;
dissolving the first crude product in dichloromethane, adding dichloromethane and water, extracting, and collecting an organic phase;
and drying, filtering, concentrating and purifying the organic phase to obtain the first intermediate.
Specifically, the volume ratio of the dichloromethane to the water is 1:1, the drying is drying by adding anhydrous sodium sulfate, the purification is purification by adopting a column chromatography separation method, in the step, a chiral center is mainly introduced into 2, 6-bis (N-alkylbenzimidazolyl) benzene, so that a chiral signal can be effectively transmitted to a light-emitting part, and therefore circular polarization emission is realized.
In some embodiments, the step of reacting the first intermediate with potassium tetrachloroplatinate to obtain a second intermediate comprises the steps of:
and (3) mixing the first intermediate and potassium tetrachloroplatinate in a container, vacuumizing and blowing nitrogen, adding glacial acetic acid, refluxing and filtering to obtain the second intermediate.
Specifically, the vacuum drum was cycled 3 times with nitrogen for 3 days.
In some embodiments, the step of reacting the second intermediate with a second reactant to obtain the circularly polarized phosphorescent platinum (II) complex comprises the steps of:
placing the second intermediate and the second reactant in a container, mixing, sealing, vacuumizing and blowing nitrogen, adding a mixed solution of ultra-dry dichloromethane and acetonitrile, and stirring at room temperature to react to obtain a reaction solution;
adding potassium hexafluorophosphate into the reaction liquid, and reacting to obtain a suspension;
filtering the suspension, collecting filtrate, and removing the organic solvent in the filtrate to obtain a second crude product;
and purifying the second crude product to obtain the circular polarization phosphorescence platinum (II) complex.
Specifically, the second intermediate and the second reactant are mixed in a molar ratio of 1:1, the volume ratio of the ultra-dry dichloromethane to the acetonitrile in the mixed solution of the ultra-dry dichloromethane and the acetonitrile is 1:1, and the organic solvent in the filtrate is removed by adopting a rotary evaporator, wherein the step mainly comprises introducing an arylamine group, so that on one hand, the molecular aggregation can be effectively inhibited, the quenching caused by overlarge doping concentration is avoided, on the other hand, the material has good solution processing capacity, and the film forming stability of the material is ensured.
The invention also provides application of the circular polarization phosphorescence platinum (II) complex in realizing circular polarization luminescence in acetonitrile solution.
The invention also provides application of the circular polarization phosphorescent platinum (II) complex doped in the PMMA film to realize circular polarization luminescence.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1-1: preparation of Complex R-Ph-Iso
(1) Preparation of intermediate 1
The reaction formula is as follows:
1.2g (10.0mmol) of (R) - (+) - α -methylbenzylamine was placed in a 250mL round-bottom flask, then evacuated, charged with nitrogen gas, and circulated three times, to which about 20mL of toluene was added as a solvent, followed by dropwise addition of 0.4mL (11.8mmol) of formic acid at room temperature and refluxing thereof for 24 hours. After the reaction is finished, useRemoving the solvent by a reduced pressure rotary evaporator to obtain a crude product, and further purifying by a column chromatography separation method to obtain the product. Yield: 88 percent. The structural characterization data of intermediate 1 has a hydrogen spectrum, which is: 1 H NMR(400MHz,CDCl 3 ,δ):8.52(d,J＝7.2Hz,0.95H)；8.28(m,0.15H)；8.06(d,J＝11.6Hz,0.15H)；8.01(s,0.85H)；7.32(m,4.33H)；7.22(m,1.08H)；4.97(m,1.0H)；4.67(m,0.12H)；1.39(d,J＝6.8Hz,0.36H)；1.33(d,J＝6.8Hz,2.78H)。
(2) preparation of intermediate 2
The reaction formula is as follows:
1.0g (6.7mmol) of Compound 1 are placed in a 250mL two-necked flask, evacuated and flushed with nitrogen three times in succession, whereupon 50mL of ultra-dry dichloromethane are added as solvent and subsequently 5.6mL (40.2mmol) of triethylamine are added. The whole mixed system is placed in an environment at 0 ℃, 0.6mL (6.7mmol) of phosphorus oxychloride is slowly added into the mixed system, the mixed system is stirred and reacted for 1 hour at a low temperature, and then the temperature is increased to be heated to the ambient temperature and the stirring is continued for 12 hours. After the reaction is finished, the whole system is placed in an environment with the temperature of 0 ℃, an aqueous solution of sodium carbonate is slowly dripped into the system to completely quench the reaction, then dichloromethane and water are used for extraction for three times, an organic phase is collected, anhydrous sodium sulfate is used for drying and filtering, and then the solvent is removed by rotary evaporation to obtain the product. Yield: and 64 percent. The structural characterization data of intermediate 2 has a hydrogen spectrum, which is: 1 H NMR(400MHz,CDCl 3 ,δ):7.37(m,5.0H)；4.83(m,1.0H)；1.69(dt,J 1 ＝2.4Hz,J 2 ＝4.4Hz,3.0H)。
(3) preparation of intermediate 7
The reaction formula is as follows:
placing 4.0g (24.1mmol) of isophthalic acid and 5.76g (53.3mmol) of o-phenylenediamine in a 500mL double-neck flask, then slowly adding 120mL of phosphoric acid, stirring at normal temperature for 1h, then placing in a 70 ℃ oil bath kettle, stirring for 2h, pouring the mixture into an appropriate amount of ice water after the reaction is finished, then adding a 15 wt% sodium hydroxide aqueous solution to adjust the pH to 7, precipitating a white solid, and collecting the white solid. Yield: 54 percent.
(4) Preparation of intermediate 8
The reaction formula is as follows:
1.0g (0.33mmol) of the compound 2, 6-bis (N-alkylbenzimidazolyl) benzene, 60mg (0.8mmol) of sodium hydride, 0.07mL (2S) -monobromo-dimethylbutane were placed in a round-bottomed flask, and then the appropriate amount of N, N-dimethylformamide was added and allowed to react at 100 ℃ for 12 h. And after the reaction is finished, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude product. The crude product was then dissolved with a small amount of dichloromethane, followed by addition and extraction of 1:1 by volume of dichloromethane and water, and the organic phase was collected. Adding anhydrous sodium sulfate into the organic phase, drying, filtering, concentrating, and purifying by column chromatography to obtain the final product. Yield: 86 percent.
(5) Preparation of intermediate NCN-Pt-Cl
The reaction formula is as follows:
1.0g (2.2mmol) of intermediate 8, 1.1g (2.6mmol) of potassium tetrachloroplatinate are placed in a 250mL round-bottomed flask, evacuated and sparged with nitrogen three times in succession, whereupon 15mL of glacial acetic acid are added as solvent, which is then refluxed for 3 d. Cooling to room temperature after the reaction is finished, and then carrying out suction filtration to obtain the product. Yield: 75 percent.
(6) Preparation of Complex R-Ph-Iso
The reaction formula is as follows:
100mg (0.2mmol) of the compound NCN-Pt-Cl and 31mg (0.2mmol) of intermediate 2 were placed in a 100mL single-neck flask, sealed and then evacuated under nitrogen and circulated three times in succession, 20.0mL of an ultra-dry dichloromethane and acetonitrile solution (volume ratio 1:1) were added thereto and allowed to react for 24h at room temperature with stirring. After the reaction was completed, an excess of potassium hexafluorophosphate was added to the reaction solution for ion exchange, followed by reaction for 12 hours. And filtering the suspension after the reaction, collecting the filtrate, removing the organic solvent by rotary evaporation with a rotary evaporator to obtain a crude product, and continuously purifying by using a column chromatography separation method to obtain the product. Yield: 39 percent. ESI-MS (m/z) Calcd.for C 39 H 42 N 5 PtPF 6 ,920.2735；Found,775.3112(M-PF 6 ) + .
Examples 1 to 2: preparation of Complex S-Ph-Iso
(1) Preparation of intermediate 3
The reaction formula is as follows:
1.2g (10.0mmol) of (S) - (+) - α -methylbenzylamine was placed in a 250mL round-bottom flask, then evacuated, charged with nitrogen gas, and circulated three times, to which about 20mL of toluene was added as a solvent, followed by dropwise addition of 0.4mL (11.8mmol) of formic acid at room temperature and refluxing thereof for 24 hours. After the reaction is finished, removing the solvent by using a reduced pressure rotary evaporator to obtain a crude product, and further purifying by using a column chromatography separation method to obtain the product. Yield: 88 percent. The structural characterization data of the intermediate 3 has a hydrogen spectrum, which is as follows: 1 H NMR(400MHz,CDCl 3 ,δ):8.54(d,J＝6.4Hz,1.0H)；8.31(m,0.12H)；8.08(dd,J 1 ＝4Hz,J 2 ＝11.6Hz,0.13H)；8.03(d,J＝3.2Hz,1.05H)；7.32(m,4.44H)；7.24(m,1.12H)；4.99(m,1.09H)；4.69(m,0.13H)；1.41(dd,J 1 ＝1.2Hz,J 2 ＝6.8Hz,0.39H)；1.35(dd,J 1 ＝2.4Hz,J 2 ＝7.2Hz,3.25H)。
(2) preparation of intermediate 4
The reaction formula is as follows:
1.0g (6.7mmol) of Compound 1 are placed in a 250mL two-necked flask, evacuated and flushed with nitrogen three times in succession, whereupon 50mL of ultra-dry dichloromethane are added as solvent and subsequently 5.6mL (40.2mmol) of triethylamine are added. The whole mixed system is placed in an environment at 0 ℃, 0.6mL (6.7mmol) of phosphorus oxychloride is slowly added into the mixed system, the mixed system is stirred and reacted for 1 hour at a low temperature, and then the temperature is increased to be heated to the ambient temperature and the stirring is continued for 12 hours. After the reaction is finished, the whole system is placed in an environment with the temperature of 0 ℃, an aqueous solution of sodium carbonate is slowly dripped into the system to completely quench the reaction, then dichloromethane and water are used for extraction for three times, an organic phase is collected, anhydrous sodium sulfate is used for drying and filtering, and then the solvent is removed by rotary evaporation to obtain the product. Yield: and 64 percent. The structural characterization data of intermediate 4 has a hydrogen spectrum, which is: 1 H NMR(400MHz,CDCl 3 ,δ):7.36(m,5.0H)；4.82(m,1.0H)；1.68(dt,J 1 ＝2.0Hz,J 2 ＝4.4Hz,3.0H)。
(3) preparation of Complex S-Ph-Iso
The reaction formula is as follows:
150mg (0.3mmol) of the compound NCN-Pt-Cl and 47mg (0.3mmol) of intermediate 4 were placed in a 100mL single-neck flask, sealed and then evacuated under nitrogen and circulated three times in succession, 20.0mL of an ultra-dry dichloromethane and acetonitrile solution (volume ratio 1:1) were added thereto and allowed to react for 24h at room temperature with stirring. After the reaction was completed, an excess of potassium hexafluorophosphate was added to the reaction solution for ion exchange, followed by reaction for 12 hours. And filtering the suspension after the reaction, collecting filtrate, removing the organic solvent by rotary evaporation with a rotary evaporator to obtain a crude product, and continuously purifying by using a column chromatography separation method to obtain the product. Yield of：39％。ESI-MS(m/z):Calcd.for C 39 H 42 N 5 PtPF 6 ,920.2735；Found,775.3076(M-PF 6 ) + .
Examples 1 to 3: preparation of the Complex Phen-NCN
(1) Preparation of intermediate 5
The reaction formula is as follows:
1.0g (10.9mmol) of aniline was placed in a 250mL round-bottom flask, and then about 20mL of toluene was added thereto as a solvent, followed by dropwise addition of 0.4mL (43.6mmol) of formic acid at room temperature and refluxing thereof for 24 hours. After the reaction is finished, removing the solvent by using a reduced pressure rotary evaporator to obtain a crude product, and further purifying by using a column chromatography separation method to obtain the product. Yield: 88 percent. The structural characterization data of intermediate 5 has a hydrogen spectrum, which is: 1 H NMR(400MHz,CDCl 3 ,δ):10.16-10.10(m,1.0H)；8.77-8.24(m,1.0H)；7.57-7.55(m,1.5H)；7.32-7.27(m,2.0H)；7.17-7.16(m,0.5H)；7.08-7.03(m,1.0H)。
(2) preparation of Compound 6
The reaction formula is as follows:
1.0g (8.3mmol) of Compound 5 are placed in a 250mL two-necked flask, evacuated and sparged with nitrogen three times in succession, whereupon 100mL of ultra-dry dichloromethane are added as solvent, followed by 6.9mL (49.8mmol) of triethylamine. The whole mixed system is placed in an environment at 0 ℃, 0.7mL (8.3mmol) of phosphorus oxychloride is slowly added into the mixed system, the mixed system is stirred and reacted for 1h at low temperature, and then the temperature is increased to be heated to the ambient temperature and the stirring is continued for 12 h. After the reaction is finished, the whole system is placed in an environment with the temperature of 0 ℃, an aqueous solution of sodium carbonate is slowly dripped into the system to completely quench the reaction, then dichloromethane and water are used for extraction for three times, an organic phase is collected, and anhydrous water is used for extractionDrying with sodium sulfate, filtering, and rotary evaporating to remove solvent to obtain the final product. Yield: and 64 percent. The structural characterization data of intermediate 6 has a hydrogen spectrum, which is: 1 H NMR(400MHz,CDCl 3 ,δ):7.36-7.34(m,5.0H)。
(3) preparation of the Complex Phen-Iso
The reaction formula is as follows:
150mg (0.3mmol) of the compound NCN-Pt-Cl and 60mg (0.3mmol) of intermediate 6 were placed in a 100mL single-neck flask, sealed and then evacuated under nitrogen and circulated three times in succession, 20.0mL of an ultra-dry dichloromethane and acetonitrile solution (volume ratio 1:1) were added thereto and allowed to react for 24h at room temperature with stirring. After the reaction was completed, an excess of potassium hexafluorophosphate was added to the reaction solution for ion exchange, followed by reaction for 12 hours. And filtering the suspension after the reaction, collecting the filtrate, removing the organic solvent by rotary evaporation with a rotary evaporator to obtain a crude product, and continuously purifying by using a column chromatography separation method to obtain the product. Yield: 39 percent. ESI-MS (m/z) Calcd. for C 37 H 38 N 5 PtPF 6 ,892.2422；Found,747.2792(M-PF 6 ) + 。
And (3) testing:
the ultraviolet absorption spectrum, photoluminescence spectrum and circularly polarized photoluminescence spectrum of the complexes of examples 1-1 to 1-3 were measured. Table 1 shows the physical property data of the complexes of examples 1-1 to 1-3.
TABLE 1
As can be seen from the data in Table 1, the complexes of examples 1-1 to 1-3 all emit green light, and the decomposition temperatures at 5 wt% are all higher than 230 degrees Celsius, indicating that the complexes of examples 1-1 to 1-3 have good thermal stability.
Further, the complexes obtained in examples 1-1, 1-2 and 1-3 were used for the test of amplification of circularly polarized signals. The effect of the circularly polarizing phosphorescent platinum (II) complex of the present invention in realizing CPL signal amplification is illustrated in detail by the following examples.
Example 2-1: emission spectra of the Complex obtained according to example 1-1 in acetonitrile solutions of various concentrations
The concentration of the spectrum test adopted by the invention is 1 MuM, 10 MuM, 100 MuM and 1000 MuM respectively, and the test solvent is acetonitrile. When the emission spectrum is measured, the excitation wavelength under different concentrations is 365 nm.
The emission spectra in acetonitrile solutions of different concentrations are shown in FIG. 4. At concentrations of 100. mu.M or less, the complex exhibits distinct emission peaks at 489nm and 523nm, whereas when the concentration is increased to 1000. mu.M, a new emission peak appears at a wavelength of 575nm, which results from the excimer emission.
Example 2-2: circular polarized luminescence spectra of the complexes obtained according to example 1-1 in acetonitrile solutions of different concentrations
The concentration of the spectrum test adopted by the invention is respectively 10 mu M and 1000 mu M, and the test solvent is acetonitrile. When the circular polarization luminescence spectrum is measured, the excitation wavelength under different concentrations is 320 nm.
The circular polarization luminescence spectra in acetonitrile solutions of different concentrations are shown in FIG. 5. At a concentration of 10. mu.M, little CPL signal was observed in the acetonitrile solution, whereas at an increase of 1000. mu.M, a very significant CPL was observed, with an asymmetry calculated at 10 -4 In order of magnitude, it is shown that in a high concentration solution, the excimer formation can be promoted, thereby realizing the amplification of the CPL signal.
Examples 2 to 3: emission spectra of the complexes obtained according to example 1-1 in PMMA-doped films
The invention adopts the steps of doping the complex with different concentrations in a PMMA film, and then measuring the photoluminescence spectrum of the PMMA film, wherein the doping concentrations are respectively 1 wt%, 2 wt%, 5 wt%, 9 wt%, 14 wt%, 20 wt%, 25 wt%, 33 wt%, 40 wt% and 44 wt%, and the excitation wavelengths under different concentrations are 365 nm.
The emission spectrum in the PMMA-doped film is shown in FIG. 6. At a doping concentration of 1 wt%, the spectrum exhibited is similar to that in solution, with emission maxima at 494, 530 and 575nm, respectively. In addition, it can be observed that the emission intensity at the long wavelength side is significantly higher than that in the solution state, indicating that eximer exists in the doped thin film, and as the doping concentration increases, a new emission peak appears at the long wavelength side, the wavelength is 625nm, and when the doping concentration reaches 9 wt%, the emission peak intensity does not change any more.
Examples 2 to 4: circular polarized luminescence spectra of the complexes obtained according to example 1-1 in PMMA-doped thin films
The invention adopts the steps of doping the complexes with different doping concentrations in a PMMA film, and then measuring the circular polarization luminescence spectrum of the PMMA film, wherein the doping concentrations are 1 wt% and 9 wt%, and the excitation wavelengths under different concentrations are all 320 nm.
The circular polarized luminescence spectrum in the PMMA doped thin film is shown in FIG. 7. When the doping concentration is 1 wt%, a relatively weak CPL signal is presented, and the light-emitting asymmetry value is 10 -4 In order of magnitude, when the doping concentration is increased to 9 wt%, the CPL signal is rapidly intensified, and the light-emitting asymmetry value is 10 -3 In order of magnitude, this is mainly because increasing the doping concentration can strengthen the intermolecular interaction force, thereby inducing the formation of excimers, further amplifying the CPL signal.
In summary, the invention discloses a circular polarization phosphorescence platinum (II) complex and a preparation method and application thereof, on one hand, 2, 6-bis (N-alkyl benzimidazolyl) benzene with larger conjugation is used as a tridentate chelating ligand, so that certain interaction force exists in the molecule in an excited state to form an excimer; on the other hand, a unit with a chiral center is connected with the tridentate chelating ligand and/or the isonitrile part through a covalent bond, circular polarization luminescence is realized through chiral transmission, and a circular polarization luminescent material with excellent performance can be obtained by regulating the molecular structure of the material, so that convenience is brought to the improvement and application of the performance of the circular polarization luminescent material.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A circular polarization phosphorescent platinum (II) complex, which is characterized in that the structure of the circular polarization phosphorescent platinum (II) complex is shown as the following formula:
wherein R is 1 Is one of hydrogen, deuterium, alkenyl, alkynyl, amido, nitryl, carbonyl, sulfuryl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic chiral alkyl chain of C3-C60; r 2 Is an arylamine group.
2. The circularly polarizing phosphorescent platinum (II) complex according to claim 1, wherein R is 1 One selected from the following structures:
3. the circularly polarizing phosphorescent platinum (II) complex according to claim 1, wherein R is 2 One selected from the following structures:
4. the circularly polarizing phosphorescent platinum (II) complex according to claim 1, wherein the circularly polarizing phosphorescent platinum (II) complex is selected from any one of the following compounds:
5. a method for preparing a circularly polarizing phosphorescent platinum (II) complex as claimed in any of claims 1 to 4, comprising the steps of:
providing 2, 6-bis (N-alkylbenzimidazolyl) benzene;
reacting the 2, 6-bis (N-alkylbenzimidazolyl) benzene with a first reactant to obtain a first intermediate;
reacting the first intermediate with potassium tetrachloroplatinate to obtain a second intermediate;
reacting the second intermediate with a second reactant to obtain the circular polarization phosphorescence platinum (II) complex;
wherein the first reactant is a compound containing one of hydrogen, deuterium, alkenyl, alkynyl, amino, nitro, carbonyl, sulfuryl, halogen, cyano, alkyl, alkoxy, substituted aromatic ring group of C6-C60, unsubstituted aromatic ring group of C7-C60 and substituted or unsubstituted aromatic heterocyclic radical chiral alkyl chain of C3-C60, and the structure of the first intermediate is
The second reactant is a compound containing an aromatic amine group, and the structure of the second intermediate is
6. The method of claim 5, wherein the 2, 6-bis (N-alkylbenzimidazolyl) benzene is reacted with a first reactant to form a first intermediate, the method comprising:
mixing 2, 6-bis (N-alkyl benzimidazolyl) benzene, sodium hydride, a first reactant and N, N-dimethylformamide, reacting at 100 ℃ for 12 hours, cooling to room temperature after the reaction is finished, and evaporating to remove the solvent to obtain a first crude product;
dissolving the first crude product in dichloromethane, adding dichloromethane and water, extracting, and collecting an organic phase;
and drying, filtering, concentrating and purifying the organic phase to obtain the first intermediate.
7. The method for preparing a circularly polarized phosphorescent platinum (II) complex according to claim 5, wherein the step of reacting the first intermediate with potassium tetrachloroplatinate to obtain a second intermediate comprises:
and (3) mixing the first intermediate and potassium tetrachloroplatinate in a container, vacuumizing and blowing nitrogen, adding glacial acetic acid, refluxing and filtering to obtain the second intermediate.
8. The preparation method of the circularly polarizing phosphorescent platinum (II) complex according to claim 5, wherein the second intermediate is reacted with a second reactant to obtain the circularly polarizing phosphorescent platinum (II) complex, and the steps comprise:
placing the second intermediate and the second reactant in a container, mixing, sealing, vacuumizing and blowing nitrogen, adding a mixed solution of ultra-dry dichloromethane and acetonitrile, and stirring at room temperature to react to obtain a reaction solution;
adding potassium hexafluorophosphate into the reaction liquid, and reacting to obtain a suspension;
filtering the suspension, collecting filtrate, and removing the organic solvent in the filtrate to obtain a second crude product;
and purifying the second crude product to obtain the circular polarization phosphorescence platinum (II) complex.
9. Use of a circularly polarized phosphorescent platinum (II) complex as claimed in any of claims 1 to 4 for achieving circularly polarized luminescence in acetonitrile solutions.
10. Use of a circular polarized phosphorescent platinum (II) complex as claimed in any of claims 1 to 4 doped in a PMMA film to achieve circular polarized luminescence.
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