CN113621002A - Metal organic complex containing monocarborane and nitrogen heterocyclic carbene and preparation method thereof - Google Patents

Metal organic complex containing monocarborane and nitrogen heterocyclic carbene and preparation method thereof Download PDF

Info

Publication number
CN113621002A
CN113621002A CN202111122875.5A CN202111122875A CN113621002A CN 113621002 A CN113621002 A CN 113621002A CN 202111122875 A CN202111122875 A CN 202111122875A CN 113621002 A CN113621002 A CN 113621002A
Authority
CN
China
Prior art keywords
organic complex
carborane
metal organic
compound
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111122875.5A
Other languages
Chinese (zh)
Other versions
CN113621002B (en
Inventor
张玉贞
姚海波
沈云军
边贺东
聂传丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi University for Nationalities
Original Assignee
Guangxi University for Nationalities
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangxi University for Nationalities filed Critical Guangxi University for Nationalities
Priority to CN202111122875.5A priority Critical patent/CN113621002B/en
Publication of CN113621002A publication Critical patent/CN113621002A/en
Application granted granted Critical
Publication of CN113621002B publication Critical patent/CN113621002B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Abstract

The invention discloses a metal organic complex containing monocarborane nitrogen heterocyclic carbene and a preparation method thereof, belonging to the technical field of organic synthesis, wherein the structural general formula of the organic complex is as follows:
Figure DDA0003277637640000011
wherein-CB11H11As monocarboranes
Figure DDA0003277637640000012
(
Figure DDA0003277637640000013
Is BH), -R1Represents C4～12The linear alkyl group of (A) is 1-3, X is C or N, and when the linear alkyl group is benzimidazoleAnd the azole or imidazole ligand is C element, and the triazole is N element. The carborane-containing N-heterocyclic carbene platinum complex has the advantages of cheap and easily-obtained raw materials, good economy, mild and easily-controlled reaction conditions and high yield; the compound has high quantum yield and long luminescent life; is beneficial to industrial production and provides an economic and efficient new method for preparing luminescent materials with good phosphorescence luminescent properties.

Description

Metal organic complex containing monocarborane and nitrogen heterocyclic carbene and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of synthesis of organic complexes, and particularly relates to a metal organic complex containing monocarborane and nitrogen heterocyclic carbene and a preparation method thereof.
[ background of the invention ]
Organic light emitting diodes (oled) are novel photoelectric devices, which emit light autonomously without a backlight, have high light emitting efficiency, high resolution, and lighter weight, can effectively reduce the load of light emitting devices, enlarge the light emitting area, and have been widely used in mobile phones, computers, and outdoor large displays. Organic light emitting diodes (oled) containing heavy metal coordination phosphorescent materials can enhance intersystem crossing (ISC) of electrons from singlet states to triplet states, greatly improve internal quantum efficiency, and are more and more favored by people. Compared with the research on red and green electrophosphorescent materials, the research on blue phosphorescent materials is relatively slow, the number of metal organic compounds suitable for serving as blue phosphorescent ligands is relatively small, and in addition, the low luminous efficiency of blue phosphorescent devices is also an important problem.
[ summary of the invention ]
In order to solve the problems, the invention aims to provide a synthesis method of a phosphorescent light-emitting material with good economy, mild and easily-controlled reaction conditions and high yield, and particularly relates to a monocarboane-containing N-heterocyclic carbene metal organic complex and a preparation method thereof.
The invention is realized by the following technical scheme, and provides a monocarbon borane-containing N-heterocyclic carbene metal organic complex which has the following structural general formula:
Figure BDA0003277637620000021
wherein, -CB11H11As monocarboranes
Figure BDA0003277637620000022
(
Figure BDA0003277637620000023
Is BH), -R1Represents C4～12The linear alkyl group of (1) or (3), wherein X is a C element or an N element, the C element is a benzimidazole or imidazole ligand, and the N element is a triazole.
The invention also provides a preparation method of the metal organic complex containing the monocarborane nitrogen heterocyclic carbene, which comprises the following steps:
s1 introduction of organometallic Complex I into N2Bubbling for 15min, adding silver trifluoromethanesulfonate, and adding2Under protection, adding a solvent to react for 1 hour in a dark place, and heating a reaction container to enable the reaction temperature to reach 80 ℃ in the dark place until precipitation is separated out;
s2, adding carborane-containing ligand II to carry out reflux reaction under the same condition;
s3, filtering, decompressing, removing the solvent, and separating and purifying by column chromatography to obtain the organic metal complex containing the carborane and the azacyclo-carbene;
wherein, the structural formula of the metal organic complex I is as follows:
Figure BDA0003277637620000024
the structural formula of the carborane-containing ligand II is as follows:
Figure BDA0003277637620000031
particularly, the solvent is acetonitrile or tetrahydrofuran, the molar ratio of the metal organic complex I to the silver trifluoromethanesulfonate is 1: 2.5-3, and the metal organic complex I and the silver trifluoromethanesulfonate undergo a light-shielding reaction in an N reaction2The atmosphere is carried out without water and oxygen, and the metal is organicThe molar ratio of the complex I to the carborane-containing ligand II is 1: 1.1-1.2, and the reflux reaction time is 6-8 h.
In particular, the preparation method of the compound I comprises the following steps:
s11, adding a platinum compound and a second solvent into a flask respectively;
s12 adding compound III into the second solvent, after dissolving, dropping into S11 flask at 110 deg.C under N2And refluxing for 24h under protection, wherein the structural formula of the compound III is as follows:
Figure BDA0003277637620000032
s13, decompressing, removing the second solvent, adding dichloromethane, washing, drying, filtering, decompressing, and separating and purifying by column chromatography to obtain the compound I.
In particular, the molar ratio of the compound III to the platinum compound is 1:1 to 1.2, the platinum compound is platinum acetylacetonate, and the second solvent is dimethyl sulfoxide.
In particular, the preparation method of the carborane-containing ligand II comprises the following steps:
s21 reaction of carborane [ NMe ]3H][CB11H12]Adding a third solvent for dissolving;
s22 addition of N-butyllithium in an ice bath under N2Under protection, adding cuprous iodide after reacting for 1.4-1.6h, and reacting for 40 min;
s23 adding palladium catalyst, phosphine ligand and compound IV in ice bath2Reacting for 20-24 h at room temperature under protection, wherein the structural formula of the compound IV is as follows:
Figure BDA0003277637620000041
R2is a halo group;
s24 filtering and washing the product obtained in S23, spin-drying the filtrate, balancing with a counter cation reagent, and separating and purifying by column chromatography to obtain the carborane-containing ligand II.
In particular, the third solvent is dried tetrahydrofuran, the molar ratio of the compound IV to the carborane is 1: 2-2.5, the molar ratio of the carborane to the n-butyllithium is 1:1 (1-1.3), and the molar ratio of the carborane to the cuprous iodide is 1:1 (1-1.3).
In particular, the palladium catalyst is palladium acetate, and the molar ratio of the palladium catalyst to the cuprous iodide is 1: 10.
In particular, the counter cation agent is tetraethylammonium bromide.
In particular, the phosphine ligand is tris (2-methoxyphenyl) phosphine at a molar ratio of 3: 10 to cuprous iodide.
The synthesis general route of the invention is as follows:
Figure BDA0003277637620000051
the invention provides a metal organic complex containing monocarborane and nitrogen heterocyclic carbene and a preparation method thereof, and the metal organic complex has the following beneficial effects:
(1) the carborane-containing N-heterocyclic carbene platinum complex has the advantages of cheap and easily-obtained raw materials, good economy, mild and easily-controlled reaction conditions and high yield; the compound has high quantum yield and long luminescent life; is beneficial to industrial production and provides an economic and efficient new method for preparing luminescent materials with good phosphorescence luminescent properties.
(2) The method has the advantages of cheap and easily-obtained raw materials, capability of synthesizing the carborane-containing organic metal platinum (II) complex luminescent material step by step, high quantum yield, long luminescent life, low manufacturing cost, good development prospect, easily-controlled reaction conditions, capability of being carried out under normal pressure and nitrogen atmosphere, high yield, convenience in operation and suitability for industrial production, and the complex has potential application value in the fields of medicines, chemical engineering, luminescent materials and the like.
[ description of the drawings ]
FIG. 1 shows a metal-organic complex C according to example 1 of the present invention1The structure of the single crystal of (1);
FIG. 2 shows a metal-organic complex C according to example 2 of the present invention2Nuclear magnetic hydrogen spectrum diagram (deuterated reagent is deuterated CKetones);
FIG. 3 shows a metal-organic complex C according to example 2 of the present invention2Nuclear magnetic carbon spectrum (deuterated reagent is deuterated acetone);
FIG. 4 shows a metal-organic complex C according to example 2 of the present invention2[M+Na]+High resolution mass spectrograms of (a);
FIG. 5 shows a metal-organic complex C according to example 3 of the present invention3Nuclear magnetic hydrogen spectrum (deuterated reagent is deuterated acetone);
FIG. 6 shows a metal-organic complex C according to example 3 of the present invention3Nuclear magnetic carbon spectrum (deuterated reagent is deuterated acetone);
FIG. 7 shows a metal-organic complex C according to example 3 of the present invention3[M+Na]+ high resolution mass spectrum.
FIG. 8 shows a metal-organic complex C according to example 2 of the present invention2Ultraviolet-visible absorption spectrum in solution state;
FIG. 9 shows a metal-organic complex C according to example 3 of the present invention3Ultraviolet-visible absorption spectrum in solution state;
FIG. 10 shows a metal-organic complex C according to example 2 of the present invention2Emission spectra in the solid state;
FIG. 11 is a drawing showing a metal-organic complex C according to example 3 of the present invention3Emission spectra in the solid state;
FIG. 12 shows a metal-organic complex C according to example 2 of the present invention2Emission spectrum in PMMA film state;
FIG. 13 shows a metal-organic complex C according to example 3 of the present invention3Emission spectrum in PMMA film state;
FIG. 14 shows a metal-organic complex C according to example 2 of the present invention2Emission spectra in solution;
FIG. 15 shows a metal-organic complex C according to example 3 of the present invention3Emission pattern in solution state.
[ detailed description ] embodiments
The valence electron configuration of the boron atom is 2s22p1Due to its empty pπpπThe track is provided with a track which is provided with a plurality of tracks,is a strong electron-deficient atom, has good charge transport properties, and is a carborane anion [ CB11H12]-The organic boride has special chemical stability and thermal stability due to the fact that 13 pairs of covalent electrons are delocalized in the whole ions and have three-dimensional aromaticity. The carborane and the halogenated bipyridine form a certain conjugated system, so that the LUMO energy of the system can be reduced, and the photophysical properties of the substance can be changed. The metal complex of the aza-carbene Pt (II) has strong electron donating property, can reduce d-d transition of a metal center, improves quantum yield, and can promote charge transmission and MLCT (metal to ligand charge transition) by being connected with a carborane conjugated system, thereby improving phosphorescence luminous efficiency. The invention provides a metal organic complex containing monocarborane nitrogen heterocyclic carbene, which belongs to the technical field of organic synthesis and has the following structural general formula:
Figure BDA0003277637620000071
wherein, -CB11H11As monocarboranes
Figure BDA0003277637620000072
(
Figure BDA0003277637620000073
Is BH), -R1Represents C4～12The linear alkyl group of (1) or (3), wherein X is a C element or an N element, the C element is a benzimidazole or imidazole ligand, and the N element is a triazole.
The invention also provides a method for preparing the organic complex containing the monocarboane nitrogen heterocyclic carbene metal, which comprises the following steps:
s1 introduction of organometallic Complex I into N2Bubbling for 15min, adding silver trifluoromethanesulfonate, and adding2Under protection, adding a solvent to react for 1 hour in a dark place, and heating a reaction container to enable the reaction temperature to reach 80 ℃ in the dark place until precipitation is separated out;
s2, adding carborane-containing ligand II to carry out reflux reaction under the same condition;
s3, filtering, decompressing, removing the solvent, and separating and purifying by column chromatography to obtain the organic metal complex containing the carborane and the azacyclo-carbene;
wherein, the structural formula of the metal organic complex I is as follows:
Figure BDA0003277637620000081
the structural formula of the carborane-containing ligand II is as follows:
Figure BDA0003277637620000082
in the invention, the solvent is acetonitrile or tetrahydrofuran, the molar ratio of the metal organic complex I to the silver trifluoromethanesulfonate is 1: 2.5-3, and the metal organic complex I and the silver trifluoromethanesulfonate undergo a light-shielding reaction in the presence of N2The atmosphere is carried out under anhydrous and oxygen-free conditions, the molar ratio of the metal organic complex I to the carborane-containing ligand II is 1: 1.1-1.2, and the reflux reaction time is 6-8 h, preferably 8 h.
In the invention, the preparation method of the compound I and the complex VII comprises the following steps:
s11, adding a platinum compound and a second solvent into a flask respectively;
s12 adding compound III into the second solvent, after dissolving, dropping into S11 flask at 110 deg.C under N2And refluxing for 24h under protection, wherein the structural formula of the compound III is as follows:
Figure BDA0003277637620000091
s13, decompressing, removing the second solvent, adding dichloromethane, washing, drying, filtering, decompressing, and separating and purifying by column chromatography to obtain the compound I.
In particular, the molar ratio of the compound III to the platinum compound is 1:1 to 1.2, preferably 1: (1.1), preferably 1:1, the platinum compound is platinum acetylacetonate, and the second solvent is dimethyl sulfoxide.
In the invention, the preparation method of the carborane-containing ligand II comprises the following steps:
s21 reaction of carborane [ NMe ]3H][CB11H12]Adding a third solvent for dissolving;
s22 addition of N-butyllithium in an ice bath under N2Under protection, adding cuprous iodide after reacting for 1.4-1.6h, and reacting for 40 min;
s23 adding palladium catalyst, phosphine ligand and compound IV in ice bath2Reacting for 20-24 h at room temperature under protection, wherein the structural formula of the compound IV is as follows:
Figure BDA0003277637620000092
R2is a halo group;
s24 filtering the product obtained in S23, washing, spinning dry the filtrate, balancing with a counter cation reagent which is tetraethylammonium bromide, and separating and purifying by column chromatography.
The carborane-containing ligand II needs to be N in the preparation process2The reaction was carried out under protection at room temperature, but the flask was ice-cooled for 5min in advance before each charge.
In particular, the third solvent is dried tetrahydrofuran, and the molar ratio of the compound IV to the carborane is 1:2 to 2.5, preferably 1: 2.2; the molar ratio of carborane to n-butyllithium is 1:1 (1-1.3), and preferably 1: and 1.2, the molar ratio of the cuprous iodide to the cuprous iodide is 1:1 to 1.3, and the preferable molar ratio is 1: 1.1.
in particular, the palladium catalyst is palladium acetate, and the molar ratio of the palladium catalyst to the cuprous iodide is 1: 10.
In particular, the phosphine ligand is tris (2-methoxyphenyl) phosphine at a molar ratio of 3: 10 to cuprous iodide.
The synthesis route for preparing the carborane-containing N-heterocyclic carbene metal organic platinum complex from the compounds I and II is as follows:
Figure BDA0003277637620000101
in order that the present invention may be more clearly understood, the present invention is further explained below in conjunction with specific embodiments, and descriptions of well-known functions and constructions are omitted for clarity and conciseness.
Example 1
This example provides a metal-organic platinum Complex C1The structural formula is as follows:
Figure BDA0003277637620000111
organometallic platinum complexes C1The synthetic route of (2) is as follows:
Figure BDA0003277637620000112
organometallic platinum complexes C1The preparation method comprises the following specific steps:
(i) platinum acetylacetonate (4.89mmol,1.9g) was charged into a 250mL two neck round bottom flask, followed by 4mL of dimethyl sulfoxide; a compound III1(4.44mmol,2g) was dissolved in a 50mL beaker containing 20mL of dimethyl sulfoxide, the beaker was slightly heated to promote dissolution, and then transferred to a 60mL constant pressure dropping funnel, which was inserted into the side port of the flask, and the opening of the piston was controlled to drop the solution dropwise into the flask within 3 hours to allow the two to react sufficiently. Refluxing for 24h at 110 ℃ under the protection of nitrogen. After the reaction is finished, the solvent is evaporated under reduced pressure, 50mL of dichloromethane is added into residual liquid, and the residual liquid is washed twice by 50mL of water; the organic phase was over anhydrous MgSO4Drying, filtering, concentrating the liquid under reduced pressure, and separating and purifying by column chromatography (eluent: dichloromethane/ethyl acetate-4/1) to obtain white solid I12.11g, 73.8% yield.
(ii) Reacting carborane [ NMe ]3H][CB11H12](2.96mmol,600mg) was dissolved in 20ml of tetrahydrofuran under a nitrogen atmosphereWhile stirring, 6ml of n-butyllithium was added under ice-bath, and after stirring and reacting for 1.5 hours, cuprous iodide (3.25mmol,620mg) was added under ice-bath, and after reacting for 40min, palladium acetate (0.33mmol,73mg), tris (2-methoxyphenyl) phosphine (0.99mmol,349mg), and compound IV were added under ice-bath1(1.33mmol,417mg) was stirred under nitrogen for 12 h. After the reaction is finished, filtering the mixture by diatomite, washing the mixture by dichloromethane for multiple times, spin-drying the filtrate, then adding 50ml of methyl tert-butyl ether for extraction, then washing the mixture by 20ml of 1mol/L hydrochloric acid, adding 20ml of water into an ether layer, spin-drying the ether layer, then adding a proper amount of sodium hydroxide solution into the water dropwise for neutralization until the aqueous solution is alkaline, adding tetraethylammonium bromide to form a whitish grey precipitate, performing suction filtration, and separating and purifying the precipitate by column chromatography (eluent: ethyl acetate/methanol: 100/1) to obtain a white solid II10.612g, yield 65.3%.
(iii) A compound I1(0.23mmol,150mg) and silver trifluoromethanesulfonate (0.58mmol,148mg) were placed in a sealed and light-proof 100ml bottle with a holder, and then vacuum-pumping and nitrogen-introducing were repeated. 20ml of degassed tetrahydrofuran is added into a reaction bottle, and then reflux is carried out for 1h at the temperature of 80 ℃ under the protection of nitrogen; after precipitation, compound II is added1(0.25mmol,177mg) was quickly charged into the reaction flask and the reaction was continued for 8 h. After the reaction, the mixture was filtered, the solvent was removed under reduced pressure, and the residue was separated and purified by column chromatography (eluent: dichloromethane) to obtain white solid C10.156g, 73.5% yield.
Example 2
This example provides a metal-organic complex C2The structural formula is as follows:
Figure BDA0003277637620000131
metal organic complexes C2The synthetic route of (2) is as follows:
Figure BDA0003277637620000132
metal organic complexes C2Detailed description of the inventionThe preparation method comprises the following steps:
(i) platinum acetylacetonate (2.80mmol,1.1g) was charged into a 250mL two neck round bottom flask, followed by 4mL of dimethyl sulfoxide; a compound III2(2.58mmol,2g) was dissolved in a 50mL beaker containing 20mL of dimethyl sulfoxide, the beaker was slightly heated to promote dissolution, and then transferred to a 60mL constant pressure dropping funnel, which was inserted into the side port of the flask, and the opening of the piston was controlled to drop the solution dropwise into the flask within 3 hours to allow the two to react sufficiently. Refluxing for 24h at 110 ℃ under the protection of nitrogen. After the reaction is finished, the solvent is evaporated under reduced pressure, 50mL of dichloromethane is added into residual liquid, and the residual liquid is washed twice by 50mL of water; the organic phase was over anhydrous MgSO4Drying, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography (eluent: dichloromethane) to obtain white solid I21.88g, yield 75.0%.
(ii) Reacting carborane [ NMe ]3H][CB11H12](2.96mmol,600mg) was dissolved in 20ml of tetrahydrofuran under nitrogen atmosphere, stirred, 6ml of n-butyllithium was added under ice bath, stirred to react for 1.5h, cuprous iodide (3.25mmol,620mg) was added under ice bath, palladium acetate (0.33mmol,73mg), tris (2-methoxyphenyl) phosphine (0.99mmol,349mg), and the compound IV were added under ice bath to react for 40min2(1.33mmol,417mg) was stirred under nitrogen for 12 h. After the reaction is finished, filtering the mixture by diatomite, washing the mixture by dichloromethane for multiple times, spin-drying the filtrate, then adding 50ml of methyl tert-butyl ether for extraction, then washing the mixture by 20ml of 1mol/L hydrochloric acid, adding 20ml of water into an ether layer, spin-drying the ether layer, then adding a proper amount of sodium hydroxide solution into the water dropwise for neutralization until the aqueous solution is alkaline, adding tetraethylammonium bromide to form a whitish grey precipitate, performing suction filtration, and separating and purifying the precipitate by column chromatography (eluent: ethyl acetate/methanol: 100/1) to obtain a white solid II20.581g, yield 62.0%.
(iii) A compound I2(0.13mmol,126mg) and silver trifluoromethanesulfonate (0.32mmol,83mg) were put in a sealed and light-proof 100ml eggplant-shaped bottle, and then vacuum-pumping and nitrogen-introducing were repeated. 20ml of degassed tetrahydrofuran is added into a reaction bottle, and then reflux is carried out for 1h at the temperature of 80 ℃ under the protection of nitrogen; after precipitation, compound II is added2(0.143mmol,100mg) was quickly charged into a reaction flask and the reaction was continued for 8 hours. After completion of the reaction, the reaction mixture was filtered, the solvent was removed under reduced pressure, and the residue was separated and purified by column chromatography (eluent: dichloromethane/n-hexane: 3/1) to obtain white solid C20.102 g, yield 63.0%.
Example 3
This example provides a metal-organic complex C3The structural formula is as follows:
Figure BDA0003277637620000141
metal organic complexes C3The synthetic route of (2) is as follows:
Figure BDA0003277637620000151
metal organic complexes C3The preparation method comprises the following specific steps:
(i) platinum acetylacetonate (3.26mmol,1.3g) was charged into a 250mL two neck round bottom flask, followed by 4mL of dimethyl sulfoxide; a compound III32.96mmol,2g) was dissolved in a 50mL beaker containing 20mL of dimethyl sulfoxide, the beaker was slightly heated to promote dissolution, and then transferred to a 60mL constant pressure dropping funnel, which was inserted into the side port of the flask, and the opening of the piston was controlled to drop the solution dropwise into the flask within 3 hours to allow the two to react sufficiently. Refluxing for 24h at 110 ℃ under the protection of nitrogen. After the reaction is finished, the solvent is evaporated under reduced pressure, 50mL of dichloromethane is added into residual liquid, and the residual liquid is washed twice by 50mL of water; the organic phase was over anhydrous MgSO4Drying, filtering, concentrating the liquid under reduced pressure, and separating and purifying by column chromatography (eluent: dichloromethane/ethyl acetate-4/1) to obtain white solid I31.85g, yield 72.0%.
(ii) The specific procedure is as in example 1 (ii).
(iii) A compound I3(0.13mmol,113mg) and silver trifluoromethanesulfonate (0.32mmol,83mg) were added to a sealed and light-proof 100ml bottle with a support, and then vacuum-pumping and nitrogen-introducing were repeatedAnd (4) qi. 20ml of degassed tetrahydrofuran is added into a reaction bottle, and then reflux is carried out for 1h at the temperature of 80 ℃ under the protection of nitrogen; after precipitation, compound II is added1(0.143mmol,100mg) was quickly charged into a reaction flask and the reaction was continued for 8 hours. After the reaction, the mixture was filtered, the solvent was removed under reduced pressure, and the residue was separated and purified by column chromatography (eluent: dichloromethane) to obtain white solid C30.112g, yield 75.5%.
In order to verify the feasibility of the organometallic complexes prepared by the process described in the present application, the following experiments are explained.
Experimental example 1
Metal organic complex C synthesized by the invention1、C2、C3The structural characterization data of (a) are as follows:
FIG. 1 shows a metal-organic complex C according to example 1 of the present invention1FIG. 2 is a view of a single crystal structure of (A), a metal organic complex C of example 2 of the present invention2FIG. 3 is a nuclear magnetic hydrogen spectrum (deuterated acetone as the deuterated reagent), FIG. 3 is a nuclear magnetic carbon spectrum (deuterated acetone as the deuterated reagent), FIG. 4 is a high-resolution mass spectrum, and FIG. 5 is a metal-organic complex C obtained in example 3 of the present invention3The nuclear magnetic hydrogen spectrum (deuterated reagent is deuterated acetone), the nuclear magnetic carbon spectrum (deuterated reagent is deuterated acetone) of the nuclear magnetic carbon spectrum, and the high-resolution mass spectrum of the nuclear magnetic carbon spectrum are shown in fig. 6 and 7.
Experimental example 2
FIG. 8 and FIG. 9 are respectively a metal organic complex C prepared by the present invention2And a metal-organic complex C3In the state of solution (metal organic complex C)2And a metal-organic complex C3Separately in dichloromethane) uv-visible absorption spectrum at 25 ℃.
Experimental example 3
FIG. 10 and FIG. 11 are respectively a metal organic complex C prepared by the present invention2And a metal-organic complex C3And the phosphorescence emission spectrum at 25 ℃ in a solid state has excitation wavelengths of 356nm and 328nm respectively. FIG. 12 and FIG. 13 are respectively a metal organic complex C prepared by the present invention2And a metal-organic complex C3Exciting phosphorescence emission pattern at 25 deg.C in PMMA film stateThe wavelengths were 356nm and 328nm, respectively. The PMMA film is prepared by a conventional method, for example, a metal organic complex sample and polymethyl methacrylate are dissolved in dichloromethane (ACS level) according to the mass ratio of 1: 49, the solution is dripped on the surface of quartz glass, and the solvent is volatilized.
FIG. 14 and FIG. 15 are respectively a metal organic complex C prepared by the present invention2And a metal-organic complex C3In the state of solution (metal organic complex C)2And a metal-organic complex C3Dissolved in dichloromethane respectively) at 25 ℃ with excitation wavelengths of 356nm and 328nm respectively.
The emission spectra in fig. 10 to 15 are normalized results, so that comparison is facilitated. The specific normalization method is a conventional normalization method, such as: the spectral data is simultaneously divided by the highest peak to make the highest peak become 1.
The following is for the organometallic complexes C obtained according to the invention2And a metal-organic complex C3The light-emitting properties in the different states are summarized, and are shown in table 1, wherein table 1 is a table of light-emitting properties of different metal organic complexes in different states.
TABLE 1
Figure BDA0003277637620000171
Figure BDA0003277637620000181

Claims (10)

1. A monocarbon borane-containing nitrogen heterocyclic carbene metal organic complex is characterized by having the following structural general formula:
Figure FDA0003277637610000011
wherein, -CB11H11As monocarboranes
Figure FDA0003277637610000012
Figure FDA0003277637610000013
Is BH, -R1Represents C4～12The linear alkyl group of (1) or (3), wherein X is a C element or an N element, the C element is a benzimidazole or imidazole ligand, and the N element is a triazole.
2. A method for preparing a monocarborane-containing N-heterocyclic carbene metal organic complex according to claim 1, which comprises the following steps:
s1 introduction of organometallic Complex I into N2Bubbling for 15min, adding silver trifluoromethanesulfonate, and adding2Under protection, adding a solvent to react for 1 hour in a dark place, and heating a reaction container to enable the reaction temperature to reach 80 ℃ in the dark place until precipitation is separated out;
s2, adding carborane-containing ligand II to carry out reflux reaction under the same condition;
s3, filtering, decompressing, removing the solvent, and separating and purifying by column chromatography to obtain the organic metal complex containing the carborane and the azacyclo-carbene;
wherein, the structural formula of the metal organic complex I is as follows:
Figure FDA0003277637610000014
the structural formula of the carborane-containing ligand II is as follows:
Figure FDA0003277637610000021
3. the organic machine tool containing monocarborane nitrogen heterocyclic carbene metal as claimed in claim 2The preparation method of the compound is characterized in that the solvent is acetonitrile or tetrahydrofuran, the molar ratio of the metal organic complex I to the silver trifluoromethanesulfonate is 1: 2.5-3, and the silver trifluoromethanesulfonate is slightly excessive, so that bromine in the complex I is completely precipitated in the form of silver bromide, the coordination reaction with the ligand II can be completely carried out in the next step, and the metal organic complex I and the silver trifluoromethanesulfonate can be subjected to a light-shielding reaction in the N-phase2The atmosphere is carried out under anhydrous and oxygen-free conditions, the molar ratio of the metal organic complex I to the carborane-containing ligand II is 1: 1.1-1.2, and the reflux reaction time is 6-8 h.
4. The preparation method of the organic complex containing the monocarborane nitrogen heterocyclic carbene metal as claimed in claim 2, characterized in that the preparation method of the compound I comprises the following steps:
s11, adding a platinum compound and a second solvent into a flask respectively;
s12 adding compound III into the second solvent, after dissolving, dropping into S11 flask at 110 deg.C under N2And refluxing for 24h under protection, wherein the structural formula of the compound III is as follows:
Figure FDA0003277637610000022
s13, decompressing, removing the second solvent, adding dichloromethane, washing, drying, filtering, decompressing, and separating and purifying by column chromatography to obtain the compound I.
5. The preparation method of the monocarborane-N-heterocyclic carbene metal organic complex as claimed in claim 4, wherein the molar ratio of the compound III to the platinum compound is 1:1 to 1.2, the platinum compound is platinum acetylacetonate, and the second solvent is dimethyl sulfoxide.
6. The preparation method of the carborane-containing N-heterocyclic carbene metal organic complex according to claim 2, wherein the preparation method of the carborane-containing ligand II comprises the following steps:
s21 reaction of carborane [ NMe ]3H][CB11H12]Adding a third solvent for dissolving;
s22 addition of N-butyllithium in an ice bath under N2Under protection, adding cuprous iodide after reacting for 1.4-1.6h, and reacting for 40 min;
s23 adding palladium catalyst, phosphine ligand and compound IV in ice bath, adding N2Reacting for 20-24 h at room temperature under protection, wherein the structural formula of the compound IV is as follows:
Figure FDA0003277637610000031
R2is a halo group;
s24 filtering and washing the product obtained in S23, spin-drying the filtrate, balancing with a counter cation reagent, and separating and purifying by column chromatography to obtain the carborane-containing ligand II.
7. The preparation method of the monocarborane azacyclo-carbene metal organic complex according to claim 6, wherein the third solvent is dried tetrahydrofuran, the molar ratio of the compound IV to the carborane is 1:2 to 2.5, the molar ratio of the carborane to n-butyllithium is 1:1 (1 to 1.3), and the molar ratio of the carborane to cuprous iodide is 1:1 (1 to 1.3).
8. The preparation method of the monocarborane-nitrogen heterocyclic carbene metal organic complex as claimed in claim 6, wherein the palladium catalyst is palladium acetate and the molar ratio of the palladium acetate to the cuprous iodide is 1: 10.
9. The method for preparing the monocarborane-nitrogen heterocyclic carbene metal organic complex according to claim 6, wherein the counter cation reagent is tetraethylammonium bromide.
10. The preparation method of the monocarborane azacyclo-carbene metal organic complex as claimed in claim 6, wherein the phosphine ligand is tris (2-methoxyphenyl) phosphine at a molar ratio of 3: 10 to cuprous iodide.
CN202111122875.5A 2021-09-24 2021-09-24 Monocarborane-containing nitrogen heterocyclic carbene metal organic complex and preparation method thereof Active CN113621002B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111122875.5A CN113621002B (en) 2021-09-24 2021-09-24 Monocarborane-containing nitrogen heterocyclic carbene metal organic complex and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111122875.5A CN113621002B (en) 2021-09-24 2021-09-24 Monocarborane-containing nitrogen heterocyclic carbene metal organic complex and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113621002A true CN113621002A (en) 2021-11-09
CN113621002B CN113621002B (en) 2023-11-28

Family

ID=78390565

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111122875.5A Active CN113621002B (en) 2021-09-24 2021-09-24 Monocarborane-containing nitrogen heterocyclic carbene metal organic complex and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113621002B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114181263A (en) * 2021-12-20 2022-03-15 广西民族大学 Monocarborane anion platinum complex-containing blue light material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928294A (en) * 2010-08-18 2010-12-29 天津师范大学 Nitrogen heterocyclic carbene silver complex on premise of substituted benzimidazole salt and application thereof
US20200181173A1 (en) * 2016-04-08 2020-06-11 Soochow University Method for preparing phenylboronic acid neopentyl glycol ester

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928294A (en) * 2010-08-18 2010-12-29 天津师范大学 Nitrogen heterocyclic carbene silver complex on premise of substituted benzimidazole salt and application thereof
US20200181173A1 (en) * 2016-04-08 2020-06-11 Soochow University Method for preparing phenylboronic acid neopentyl glycol ester

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114181263A (en) * 2021-12-20 2022-03-15 广西民族大学 Monocarborane anion platinum complex-containing blue light material and preparation method and application thereof
CN114181263B (en) * 2021-12-20 2023-11-24 广西民族大学 Blue light material containing monocarborane anion platinum complex, and preparation method and application thereof

Also Published As

Publication number Publication date
CN113621002B (en) 2023-11-28

Similar Documents

Publication Publication Date Title
JP5198856B2 (en) Metal complex
WO2014047616A1 (en) Metal compounds, methods, and uses thereof
WO2006095951A1 (en) Novel iridium complex and organic electroluminescence device using the same
Van der Heijden et al. Neutral monocyclopentadienyllutetium alkyls: in search of steric unsaturation
EP1944308A1 (en) Process for production of ortho-metallized 1:3 complex of iridium with homoligand
CN113621002A (en) Metal organic complex containing monocarborane and nitrogen heterocyclic carbene and preparation method thereof
CN111875634A (en) Benzimidazole bidentate ligand-based luminescent copper compound and preparation method thereof
Riesebeck et al. Cyclometalated Spirobifluorene Imidazolylidene Platinum (II) Complexes with Predominant 3LC Emissive Character and High Photoluminescence Quantum Yields
CN111925392B (en) Copper compound with photoluminescence performance and preparation method thereof
CN113292607B (en) Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof
CN111848676A (en) Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof
CN109535202B (en) Preparation method and application of iridium-4' -bromophenyl-terpyridine-containing crystal material
EP2646450A1 (en) Process for the synthesis of precursor complexes of titanium dioxide sensitization dyes based on ruthenium polypyridine complexes
CN111205333B (en) Cationic metal complex iridium-benzophenanthroline crystal material and preparation method and application thereof
CN113683646A (en) Monocarbon borane-containing metal platinum complex and preparation method and application thereof
Jiang et al. Self-Assembly of an Anionic [Cu5I8] 3–Supramolecular Cluster Driven by Ion-Pair Interaction and Catalytic Properties
US8859771B2 (en) Organic electroluminescent compound containing iridium, preparation method thereof and organic electroluminescent device
CN113563380B (en) Efficient light-emitting cuprous complex based on triazole phosphine derivatives and preparation method thereof
CN113072592B (en) Carbazole bridged binuclear metal platinum complex and preparation method and application thereof
CN108424765B (en) Yellow phosphorescent Cu (I) complex luminescent material and preparation method thereof
CN111892628B (en) Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof
CN109867634B (en) Strong fluorescence emission cage-shaped metal compound and synthetic method thereof
CN109232657B (en) Preparation method of dicyclic cationic complex metallic iridium-pyridazine crystal material
Constable et al. Metallostars containing {Ru (bpy) 3} motifs
CN115260248A (en) Binuclear cationic phosphorescent iridium compound and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant