CN117534708A - Copper complex based on benzothiazole phosphine derivative, preparation method and application - Google Patents
Copper complex based on benzothiazole phosphine derivative, preparation method and application Download PDFInfo
- Publication number
- CN117534708A CN117534708A CN202311161863.2A CN202311161863A CN117534708A CN 117534708 A CN117534708 A CN 117534708A CN 202311161863 A CN202311161863 A CN 202311161863A CN 117534708 A CN117534708 A CN 117534708A
- Authority
- CN
- China
- Prior art keywords
- cuprous complex
- solvent
- complex
- benzothiazole
- cuprous
- 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.)
- Pending
Links
- NCJZCJCCZMJSPI-UHFFFAOYSA-N P.S1C=NC2=CC=CC=C12 Chemical class P.S1C=NC2=CC=CC=C12 NCJZCJCCZMJSPI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000004699 copper complex Chemical class 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 35
- 239000003446 ligand Substances 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 20
- -1 diphenyl potassium phosphate Chemical compound 0.000 claims description 18
- NFRYVRNCDXULEX-UHFFFAOYSA-N (2-diphenylphosphanylphenyl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 NFRYVRNCDXULEX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical class FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 8
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 7
- 229910017888 Cu—P Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- AJZFEJQZIOIQSR-UHFFFAOYSA-M potassium;diphenyl phosphate Chemical compound [K+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 AJZFEJQZIOIQSR-UHFFFAOYSA-M 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 230000003335 steric effect Effects 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000013078 crystal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- RLQZDQWRKWNWPP-UHFFFAOYSA-N [K].P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O Chemical compound [K].P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O RLQZDQWRKWNWPP-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KFEHNXLFIGPWNB-UHFFFAOYSA-N 2-fluoro-4-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C(F)(F)F)=CC=C1C=O KFEHNXLFIGPWNB-UHFFFAOYSA-N 0.000 description 1
- UNWQNFJBBWXFBG-UHFFFAOYSA-N 2-fluoro-4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(F)=C1 UNWQNFJBBWXFBG-UHFFFAOYSA-N 0.000 description 1
- JDQDSEVNMTYMOC-UHFFFAOYSA-N 3-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1 JDQDSEVNMTYMOC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
Abstract
The embodiment of the application provides a cuprous complex based on a benzothiazole phosphine derivative, a preparation method and application thereof, wherein the chemical general formula of the cuprous complex is C 55 H 41 CuRNSP 3 BF 4 The structural formula is shown as the following formula:wherein Ph = phenyl; r is selected from H, OCH 3 Or CF (CF) 3 . The luminescent cuprous complex obtained by the method has excellent performance, can be applied to a luminescent layer of an organic electroluminescent device, can also be applied to an optical sensor, and has wide application prospect and important application value.
Description
Technical Field
The application relates to the technical field of synthesis of complex luminescent functional materials, in particular to a cuprous complex based on benzothiazole phosphine derivatives, a preparation method and application.
Background
Cuprous ion is d 10 The electronic configuration and the coordination mode are flexible, various structures can be formed, excellent photoelectric properties are shown, and the application of the cuprous luminous complex in intelligent response equipment, information storage and photosensitive devices is greatly expanded. Especially in the field of luminescence, the cuprous complex can realize a high-performance organic electroluminescent device and is considered as a good substitute for noble metal iridium and platinum phosphorescent materials; for the study of cuprous complexes, the method has important significance in the aspect of developing novel low-cost high-performance luminescent materials, and a large number of Cu (I) high-efficiency luminescent complexes are widely applied to the preparation of OLED devices. Therefore, the development of the cuprous complex luminescent functional material has important significance and economic value, but the existence of the copper atom orbit coupling effect restricts the improvement and optimization of the performance to a certain extent; obtaining cuprous complexes with excellent properties and high photoluminescence quantum yields is still a research hotspot for scientific researchers.
Disclosure of Invention
Aiming at the prior art, at least one technical problem is solved, and the application provides a cuprous complex based on a benzothiazole phosphine derivative, a preparation method and application thereof, wherein the cuprous complex of the benzothiazole phosphine derivative has excellent performance and high photoluminescence quantum yield, can be applied to a luminescent layer of an organic electroluminescent device, can also be applied to an optical sensor, and has wide application prospect and important application value.
According to a first aspect of the present application, a copper complex based on a benzothiazole phosphine derivative is proposed, having the chemical formula C 55 H 41 CuRNSP 3 BF 4 The structural formula is shown in the following formula
Wherein Ph = phenyl; r is selected from H, OCH 3 Or CF (CF) 3 。
In some embodiments, the cuprous complex is a luminescent material and uses benzothiazole phosphine compounds L1-L3 as main ligands, 1, 2-bis (diphenylphosphino) benzene L' as auxiliary ligands, and [ Cu (CH) 3 CN) 4 ]BF 4 Is a copper source; the center of the cuprous complex is soft acid metal ion Cu (I) and is coordinated with soft alkali coordination atoms P and hard alkali coordination atoms N in the ligands L and L' to form a four-coordination structure.
In some embodiments, the cuprous complex is a distorted tetrahedral structure, wherein the angle of N-Cu-P is similar to the angle of P-Cu-P, such that the two ligands have similar steric effects.
According to a second aspect of the present application, a method for preparing a luminescent material of a cuprous complex is provided, which comprises the following steps:
mixing a 2-fluorobenzaldehyde derivative, 2-amino thiophenol, a catalyst and absolute ethyl alcohol, heating an oil bath opening to boiling, cooling to remove a solvent, and recrystallizing to obtain intermediate compounds RL1-RL3;
after the RL1-RL3 is dissolved in the solvent, adding diphenyl potassium phosphate, and carrying out reflux reaction for 8-10 hours in an inert atmosphere; then cooling to remove the solvent and recrystallizing to obtain benzothiazole phosphine compounds L1-L3;
the benzothiazole phosphine compound L1-L3, 1, 2-bis (diphenylphosphino) benzene and [ Cu (CH) 3 CN) 4 ]BF 4 Adding the mixture into the mixed solvent, stirring and reacting for 1-2h, evaporating and concentrating the solvent, and filtering to obtain a target copper complex; wherein the mixed solvent comprises dichloromethane, methanol and acetonitrile in a volume ratio of 5:3:2.
In some embodiments, the molar ratio of the 2-fluorobenzaldehyde derivative, 2-aminothiophenol is 1:1; the catalyst is p-toluenesulfonic acid.
In some embodiments, the ratio of the molar ratio of the potassium diphenylphosphate to the RL1-RL3 is greater than 1.
In some embodiments, the solvent is tetrahydrofuran and the ratio of addition of the RL1-RL3 to the solvent is in the range of 0.4-0.65mmol/mL.
In some embodiments, removing the solvent is recovering the solvent using spin-steaming.
In some embodiments, the benzothiazole phosphine compounds L1-L3, the 1, 2-bis (diphenylphosphino) benzene, and the [ Cu (CH) 3 CN) 4 ]BF 4 The molar ratio of (2) is 1:1:1.
According to a third aspect of the present application there is provided the use of the cuprous complex as described in any one of the embodiments above in the preparation of an organic light emitting diode or optical sensor.
Compared with the prior art, the luminescent cuprous complex luminescent material of the benzothiazole phosphine derivative, the preparation method and the application have the following beneficial effects:
(1) The preparation method of the cuprous complex with excellent photoluminescence performance is simple, the total yield can reach 70%, the mass production is easy, the organic solvent used in the reaction can be recycled, and the pollution is small;
(2) At 298K, the luminescent cuprous complex of the benzothiazole phosphine derivative (1) C 55 H 42 CuNSP 3 BF 4 Cuprous complex (2) C 56 H 44 CuNSP 3 OBF 4 And cuprous complex (3) C 56 H 41 CuNSP 3 BF 7 The maximum emission wavelengths of (a) are 561nm, 537nm and 567nm respectively, which are respectively represented by yellow-green light emission, green light emission and yellow light emission; the luminous quantum efficiency of the solid powder at 298K reaches 58%, 65% and 56%, and the service lives thereof are 9.7 mu s, 51.3 mu s and 11.2 mu s respectively;
additional aspects and advantages of the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
fig. 1 is a schematic diagram of the crystal structure of the luminescent cuprous complex (1) in the present application;
fig. 2 is a schematic diagram of the crystal structure of the luminescent cuprous complex (2) in the present application;
FIG. 3 is a schematic view of the crystal structure of the luminescent cuprous complex (3) in the present application;
FIG. 4 a is an ultraviolet-visible absorption spectrum of the luminescent cuprous complex (1) in methylene chloride solution, b is an excitation and emission spectrum under 298K, wherein ex represents excitation spectrum and em represents emission spectrum;
FIG. 5 a is an ultraviolet-visible absorption spectrum of the luminescent cuprous complex (2) in methylene chloride solution, b is an excitation and emission spectrum under 298K, wherein ex represents excitation spectrum and em represents emission spectrum;
FIG. 6 a is an ultraviolet-visible absorption spectrum of the luminescent cuprous complex (3) in methylene chloride solution, b is an excitation and emission spectrum under 298K, wherein ex represents excitation spectrum and em represents emission spectrum;
FIG. 7 is a chromaticity Coordinate (CIE) diagram of light emitted by the luminescent cuprous complex (1) of the present application;
FIG. 8 is a chromaticity Coordinate (CIE) diagram of light emitted by the luminescent cuprous complex (2) of the present application;
fig. 9 is a chromaticity Coordinate (CIE) diagram of light emitted from the luminescent cuprous complex (3) in the present application.
Detailed Description
In order to better understand the embodiments of the present application, the following description will clearly and completely describe the embodiments of the present application with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments, and are not intended to limit the scope of the disclosure of the present application. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts disclosed herein. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, shall fall within the scope of the present application.
A schematic structural diagram according to an embodiment of the present disclosure is shown in the drawings. The figures are not drawn to scale, wherein certain details are exaggerated for clarity of presentation and may have been omitted. The shapes of the various regions, layers and their relative sizes, positional relationships shown in the drawings are merely exemplary, may in practice deviate due to manufacturing tolerances or technical limitations, and one skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions as actually required.
According to a first aspect of the present application, a copper complex based on a benzothiazole phosphine derivative is proposed, having the chemical formula C 55 H 41 CuRNSP 3 BF 4 The structural formula is shown in the following formula
Wherein Ph = phenyl; r is selected from H, OCH 3 Or CF (CF) 3 When R is selected from H, the cuprous complex is cuprous complex (1), and the crystal structure schematic diagram is shown in figure 1; when R is selected from OCH 3 When the cuprous complex is cuprous complex (2), the crystal structure of the cuprous complex is shown in figure 2; when R is selected from CF 3 The cuprous complex is cuprous complex (3), and the crystal structure of the cuprous complex is shown in figure 3.
The cuprous complex as luminescent material can be marked as CuLL' BF 4 Benzothiazole phosphine compound L1-L3 as main ligand and 1, 2-bis (diphenylphosphino) benzene L' as auxiliary ligand, and [ Cu (CH) 3 CN) 4 ]BF 4 Is a copper source; the center of the cuprous complex is soft acid metal ion Cu (I) and is coordinated with soft base coordination atoms P and hard base coordination atoms N in the ligands L and L' to form a four-coordination structure. The further cuprous complex is a distorted tetrahedral structure, wherein the angle of N-Cu-P is similar to the angle of P-Cu-P, so that the two ligands have similar spatial effects.
According to a second aspect of the present application, a method for preparing a cuprous complex luminescent material is provided, which comprises the following steps:
s1: mixing a 2-fluorobenzaldehyde derivative, 2-amino thiophenol, a catalyst and absolute ethyl alcohol, heating an oil bath opening to boiling, cooling to remove a solvent, and recrystallizing to obtain intermediate compounds RL1-RL3;
s2: after RL1-RL3 is dissolved in a solvent, adding diphenyl potassium phosphate, and carrying out reflux reaction for 8-10 hours in an inert atmosphere; then cooling to remove the solvent and recrystallizing to obtain benzothiazole phosphine compounds L1-L3;
s3: the benzothiazole phosphine compound L1-L3, 1, 2-bis (diphenylphosphino) benzene and [ Cu (CH) 3 CN) 4 ]BF 4 Adding the mixture into the mixed solvent, stirring and reacting for 1-2h, evaporating and concentrating the solvent, and filtering to obtain a target copper complex; wherein the mixed solvent comprises dichloromethane, methanol and acetonitrile with the volume ratio of 5-10:3:2.
In the S1, mixing a 2-fluorobenzaldehyde derivative and 2-aminothiophenol in a molar ratio of 1:1 with absolute ethyl alcohol serving as a solvent under the catalysis of p-toluenesulfonic acid, heating the mixture to boiling under the condition of oil bath, and continuously adding the absolute ethyl alcohol after evaporation in the reaction process, so as to react for 3-4 hours; after cooling to room temperature, performing reduced pressure distillation operation by using a rotary evaporation instrument to remove absolute ethyl alcohol and recovering the absolute ethyl alcohol to obtain a crude product; recrystallizing with absolute ethanol to obtain intermediate compounds RL1-RL3, wherein the structural formula of the intermediate compounds RL1-RL3 is
In the step, when the molar ratio of the 2-fluorobenzaldehyde derivative to the 2-amino thiophenol is not 1:1, the reaction yield is reduced to a certain extent, the residual raw materials influence the recrystallization, and the purity of the product is reduced; wherein, when other substances such as m-toluenesulfonic acid and the like are used as the catalyst, the yield is slightly reduced, when the catalyst is not used, the reaction yield is greatly reduced, and the amount of the catalyst is used to affect the reaction yield as well, preferably 0.001-0.002g of catalyst is added to 10mmol of raw materials for reaction, and the best combination cost factor is 0.001g; in addition, the reaction solvent in S1 is preferably absolute ethyl alcohol, and when absolute methyl alcohol is used as the solvent, the reaction is not greatly influenced, but the absolute ethyl alcohol is non-toxic and is more environment-friendly.
Wherein in S2, the synthetic route of the benzothiazole phosphine compound L1-L3 is as follows:
wherein, the intermediate compounds RL1-RL3 are dissolved in the solvent tetrahydrofuran, and the concentration of the RL1-RL3 is 0.4-0.65mmol/mL, preferably 0.50mmol/mL; post-adding potassium diphenylphosphate, wherein the ratio of the molar ratio of potassium diphenylphosphate to RL1-RL3 is greater than 1, wherein preferably the ratio of the molar ratio of potassium diphenylphosphate to RL1-RL3, in combination with a cost factor, is preferably 1.1; when the molar ratio of the diphenyl potassium phosphate to the intermediate compounds RL1-RL3 in the step is less than or equal to 1, the intermediate compounds RL1-RL3 remain, and the purity and the yield of the product during subsequent methanol recrystallization are affected. Reflux-reacting in inert atmosphere, such as nitrogen, for 8-10 hours after adding diphenyl potassium phosphate; then cooling to remove solvent and recrystallizing to obtain benzothiazole phosphine compound L1-L3, wherein the structural formula of the benzothiazole phosphine compound L1-L3 is
In S3, the synthetic route of the cuprous complex is as follows:
wherein, benzothiazole phosphine compound L1-L3, 1, 2-bis (diphenylphosphino) benzene and [ Cu (CH) with the mol ratio of 1:1:1 3 CN) 4 ]BF 4 Adding into the mixed solvent, stirring for reaction for 1-2h, evaporating and concentrating the solvent, and filtering to obtain CuLL' BF 4， CuLL’BF 4 The four-coordination structure is formed by coordination of a central soft acid metal ion Cu (I), a soft base coordination atom P and a hard base coordination atom N. Wherein the mixed solvent in the embodiment is dichloromethane with the volume ratio of 5:3:2,The volume ratio of the mixed solvent composed of methanol and acetonitrile, such as dichloromethane, methanol and acetonitrile, can be: 15mL-30mL:9mL:6mL, which is specific for CuLL' BF 4 The synthesis of (2) has no obvious influence, but the cost is slightly increased due to the increase of the using amount of the dichloromethane, so that the waste liquid amount is increased, and the volume ratio of the mixed solvent consisting of the dichloromethane, the methanol and the acetonitrile can be as follows: 15mL:9mL:6mL; meanwhile, the acetonitrile solution is replaced by other solvents such as trichloromethane, ethanol and the like, which cannot be synthesized. Thus, when benzothiazole phosphine compound L1-L3, 1, 2-bis (diphenylphosphino) benzene and [ Cu (CH) 3 CN) 4 ]BF 4 When the molar ratio of (C) is slightly more than 1:1:1, such as benzothiazole phosphine compounds L1-L3, 1, 2-bis (diphenylphosphino) benzene and [ Cu (CH) 3 CN) 4 ]BF 4 The molar ratio of the benzothiazole phosphine compounds L1-L3 is 1.05:1:1, the collection and purification of the final product are affected, the raw materials can be completely reacted only when the ratio of the raw materials is 1:1:1, and the product is purest and the yield is highest.
Example 1
(1) 2-fluorobenzaldehyde (1.24 g,10 mmol) and 60ml absolute ethanol are added into a 250ml round bottom flask, the mixture is heated to slight boiling in an open mouth, p-toluenesulfonic acid (0.001 g) is added, the temperature is increased and the solution is heated to boiling, the absolute ethanol is continuously evaporated and added during the period of time, and the reaction is carried out for 3 to 4 hours; cooling to room temperature after the reaction is finished, and evaporating to remove the solvent to obtain a crude product; recrystallisation twice from absolute ethanol gives 2.11g of intermediate compound RL1, calculated to be 92%.
(2) In a 100ml round-bottomed flask, ligand RL1 (2.29 g,10 mmol) prepared in step (1) was added and dissolved in 20ml of dehydrated tetrahydrofuran. After the solid is dissolved, 22ml (11 mmol) of potassium diphenylphosphonate is added by a syringe, and the mixture is reacted for 8 to 10 hours at 80 ℃ in argon atmosphere; after the reaction is finished, cooling to room temperature, removing the solvent by rotary evaporation to obtain a crude product, recrystallizing by using methanol to obtain 3.35g of ligand L1, and calculating the yield to be 85%; nuclear magnetic characterization of ligand L1: 1 H NMR(400MHz,CDCl 3 )δ7.90(d,J＝7.9Hz,2H),7.83(d,J＝7.7Hz,1H),7.49-7.38(m,2H),7.38-7.28(m,12H),7.12-7.06(m,1H). 31 PNMR(162MHz,CDCl 3 )δ-9.02(s)。
(3) Ligand L1 (0.7885 g,2 mmol) obtained in step (2), 1, 2-bis (diphenylphosphino) benzene (0.8969 g,2 mmol) and copper tetrafluoroborate tetraacetonitrile (0.6291 g,2 mmol) were added to a 100mL beaker, 15mL of methylene chloride solution, 9mL of methanol solution and 6mL of acetonitrile solution were added respectively, and after stirring and dissolution, the mixture was reacted in an argon atmosphere for 1.5 hours, and then the solvent was evaporated and concentrated and filtered to obtain 1.80g of copper complex (1), and the calculated yield was 91%. Nuclear magnetism characterization is carried out on the cuprous complex (1) 1 H NMR(400MHz,CDCl 3 )δ7.81(d,J＝8.0Hz,1H),7.72(dd,J＝7.0,4.1Hz,1H),7.68-7.59(m,4H),7.55-7.48(m,3H),7.37-7.27(m,7H),7.24(d,J＝8.3Hz,2H),7.15(td,J＝7.8,1.7Hz,6H),7.10-7.00(m,10H),6.97-6.85(m,8H). 31 P NMR(162MHz,CDCl 3 ) Delta-1.30(s), -7.41(s) elemental analysis C of cuprous Complex (1) 55 H 42 CuNSP 3 BF 4 Theoretical value (%): c,66.58; h,4.27; n,1.41. Experimental values (%): 66.54; h,4.29; n,1.43.
The solid product cuprous complex (1) is obtained by thermal evaporation, and the crystal structure diagram of the solid product cuprous complex is shown in figure 1. In addition, the mixed solvent for reaction can be recovered at the same time, and the filtered mother liquor can be further combined and concentrated to obtain more products; therefore, the yield of the product is further improved when the industrial production is performed.
Example 2
(1) 2-fluoro-4-methoxybenzaldehyde (1.54 g,10 mmol) and 60ml absolute ethanol are added into a 250ml round bottom flask, the mixture is heated to slight boiling, p-toluenesulfonic acid (0.001 g) is added, the temperature is increased to boiling, the absolute ethanol is continuously evaporated and added during the period of time, and the reaction is carried out for 3 to 4 hours; cooling to room temperature after the reaction is finished, and evaporating to remove the solvent to obtain a crude product; recrystallisation twice from absolute ethanol gives 2.46g of intermediate compound RL2, calculated to be 94%.
(2) In a 100ml round-bottomed flask, ligand RL2 (2.61 g,10 mmol) prepared in step (1) was added and dissolved in 20ml of dehydrated tetrahydrofuran. After the solid is dissolved, 22ml (11 mmol) of potassium diphenylphosphonate is added by a syringe, and the mixture is reacted for 8 to 10 hours at 80 ℃ in argon atmosphere; cooling to room temperature after the reaction is finished, removing the solvent by rotary evaporation to obtain a crude product,recrystallisation from methanol gives 3.75g of ligand L2, calculated yield 88%; nuclear magnetic characterization of ligand L2: 1 H NMR(400MHz,CDCl 3 )δ7.91-7.82(m,2H),7.79(d,J＝7.7Hz,1H),7.42-7.26(m,12H),6.96(dd,J＝8.6,2.6Hz,1H),6.60-6.54(m,1H),3.64(s,3H). 31 P NMR(162MHz,CDCl 3 )δ-7.75(s)。
(3) Ligand L2 (0.412 g,2 mmol) obtained in step (2), 1, 2-bis (diphenylphosphino) benzene (0.8969 g,2 mmol) and copper tetrafluoroborate tetraacetonitrile (0.6291 g,2 mmol) were added to a 100mL beaker, 15mL of methylene chloride solution, 9mL of methanol solution and 6mL of acetonitrile solution were added respectively, and after stirring and dissolution, the mixture was reacted in an argon atmosphere for 1.5 hours, and then the solvent was evaporated and concentrated and filtered to obtain 1.82g of copper complex (2), and the calculated yield was 89%. Nuclear magnetism characterization is carried out on the cuprous complex (2) 1 H NMR(400MHz,CDCl 3 )δ7.77-7.70(m,2H),7.69-7.63(m,2H),7.63-7.58(m,2H),7.36-7.28(m,7H),7.21(d,J＝8.3Hz,2H),7.18-7.12(m,7H),7.12-7.02(m,13H),6.94-6.83(m,6H),3.79(s,3H). 31 PNMR(162MHz,CDCl 3 ) Delta-0.70(s), -6.88(s). Anal. Calcd/%: found: elemental analysis C of cuprous Complex (2) 56 H 44 CuNSP 3 OBF 4 Theoretical value (%): c,65.80; h,4.34; n,1.37. Experimental values (%): c,65.82; h,4.35; n,1.35.
The solid product cuprous complex (2) is obtained by thermal evaporation, and the crystal structure diagram of the solid product cuprous complex is shown in figure 2. In addition, the mixed solvent for reaction can be recovered at the same time, and the filtered mother liquor can be further combined and concentrated to obtain more products; therefore, the yield of the product is further improved when the industrial production is performed.
Example 3
(1) 2-fluoro-4- (trifluoromethyl) benzaldehyde (1.92 g,10 mmol) and 60ml absolute ethyl alcohol are added into a 250ml round bottom flask, the mixture is heated to slight boiling, p-toluenesulfonic acid (0.001 g) is added, the temperature is increased to boiling, the absolute ethyl alcohol is continuously evaporated and added during the period of time, and the reaction is carried out for 3 to 4 hours; cooling to room temperature after the reaction is finished, and evaporating to remove the solvent to obtain a crude product; recrystallisation twice from absolute ethanol gives 2.66g of intermediate compound RL3, calculated as 89%.
(2) In a 100ml round-bottomed flask, ligand RL3 (2.99 g,10 mmol) prepared in step (1) was added and dissolved in 20ml of dehydrated tetrahydrofuran. After the solid is dissolved, 22ml (11 mmol) of potassium diphenylphosphonate is added by a syringe, and the mixture is reacted for 8 to 10 hours at 80 ℃ in argon atmosphere; after the reaction is finished, cooling to room temperature, removing the solvent by rotary evaporation to obtain a crude product, recrystallizing by using methanol to obtain 4.17g of ligand L3, and calculating the yield to be 90%; nuclear magnetic characterization of ligand L3: 1 H NMR(400MHz,CDCl 3 )δ8.01(dd,J＝8.0,3.4Hz,1H),7.92(d,J＝8.1Hz,1H),7.85(d,J＝7.7Hz,1H),7.69(d,J＝7.8Hz,1H),7.48-7.41(m,1H),7.40-7.28(m,12H). 31 P NMR(162MHz,CDCl 3 )δ-7.99(s)。
(3) Ligand L3 (0.9286 g,2 mmol), 1, 2-bis (diphenylphosphino) benzene (0.8969 g,2 mmol) and copper tetrafluoroborate tetraacetonitrile (0.6291 g,2 mmol) prepared in step (2) were added to a 100mL beaker, 15mL of methylene chloride solution, 9mL of methanol solution and 6mL of acetonitrile solution were added respectively, stirred and dissolved, and after adding and reacting for 1.5 hours in an argon atmosphere, the solvent was evaporated and concentrated and filtered to obtain 1.86g of copper complex (3), and the calculated yield was 88%. Performing nuclear magnetic characterization on the cuprous complex (3) 1 H NMR(400MHz,CDCl 3 )δ7.94-7.82(m,2H),7.69-7.60(m,3H),7.55-7.45(m,2H),7.42-7.33(m,6H),7.32-7.27(m,3H),7.20-7.13(m,7H),7.10-7.02(m,10H),6.97-6.91(m,4H),6.91 -6.79(m,4H). 31 P NMR(162MHz,CDCl 3 )δ-0.78(s),-6.71(s) . Elemental analysis C of the cuprous Complex (3) 56 H 41 CuNSP 3 BF 7 Theoretical value (%): c,63.44; h,3.90; n,1.32. Experimental values (%): 63.41; h,3.93; n,1.34.
The solid product cuprous complex (3) is obtained by thermal evaporation, and the crystal structure diagram of the solid product cuprous complex is shown in figure 3. In addition, the mixed solvent for reaction can be recovered at the same time, and the filtered mother liquor can be further combined and concentrated to obtain more products; therefore, the yield of the product is further improved when the industrial production is performed.
The structures of the cuprous complex (1) in example 1, the cuprous complex (2) in example 2 and the cuprous complex (3) in example 3 were measured using Bruker APEX-IICCD X-ray single crystal diffractometer,the partial parameters of the crystallography are shown in Table 1. Diffraction data using graphite monochromator Mo-K alpha rayThe collection was performed at 293K, absorption correction was performed using the sadbs program, and the resulting structural data was resolved and refined by ShelXT and ShelXS in OLEX2 package and the hydrogen atom positions were obtained by theoretical hydrogenation, wherein the crystallographic parameters of cuprous complex (1), cuprous complex (2) and cuprous complex (3) are shown in table 1.
Table 1 crystallographic parameters of cuprous complex (1), cuprous complex (2) and cuprous complex (3)
The crystallographic data of the above table test and analyze the single crystal structure of the cuprous complex (1) of example 1, the cuprous complex (2) of example 2, and the cuprous complex (3) of example 3, the cuprous complex (1), the cuprous complex (2), and the cuprous complex (3) being orthorhombic, P2 1 2 1 2 1 The spatial group, which is a distorted tetrahedral configuration, has some differences in parameters due to the substituents of the primary ligands used, which also determine their intrinsic properties, particularly in terms of emission wavelength, emission color, quantum efficiency, etc.
The cuprous complexes (1), (2) and (3) in this example are of distorted tetrahedral configuration, wherein each Cu (I) coordinates to the N atom, the P atom in the benzothiazole ligand and two P atoms in the ancillary ligand, BF 4 - Acting as counter anions, a four-coordinate distorted tetrahedral structure is formed. None of the single crystal structures contained solvent molecules. And the included angle of P-Cu-P is slightly larger than 120 degrees due to the steric hindrance effect, and the range is 131.30 (5) degrees-133.19 (6) degrees.
Experimental example
Photophysical property detection of cuprous complex (1), cuprous complex (2) and cuprous complex (3) in some embodiments,
(1) Ultraviolet-visible absorption spectrum
Under 298K, the liquid ultraviolet-visible absorption spectra of the cuprous complex (1), the cuprous complex (2) and the cuprous complex (3), the main ligand L and the auxiliary ligand L' are measured by a V-750 type ultraviolet-visible spectrophotometer, and are shown in figures 4-6. The absorption spectra of the cuprous complex (1), the cuprous complex (2) and the cuprous complex (3) have strong absorption (epsilon) near 228nm>8×10 4 L·mol -1 ·cm -1 ) A medium-intensity absorption occurs in the range 275-300 nm; it is obvious that the absorption spectra of the cuprous complex (1), the cuprous complex (2) and the cuprous complex (3) have very high similarity with the absorption of the ligand L and the auxiliary ligand L 'themselves, which means that the absorption of the cuprous complex (1), the cuprous complex (2) and the cuprous complex (3) mainly depends on the absorption properties of the ligands L and L'.
(2) Photoluminescent properties of cuprous complexes (1), 2) and 3)
Under the condition that the photoluminescence properties of the cuprous complex (1), the cuprous complex (2) and the cuprous complex (3) are 298K, the cuprous complex (1) C is measured by using a HORIBA Fluorolog-3 type fluorescence spectrometer, as shown in figures 4-6 55 H 42 CuNSP 3 BF 4 Cuprous complex (2) C 55 H 42 CuNSP 3 BF 4 And cuprous complex (3) C 56 H 41 CuNSP 3 BF 7 Maximum emission wavelengths under 298K are 561nm, 537nm and 567nm respectively, which are respectively shown as yellow-green light emission, green light emission and yellow light emission, as shown in figures 7-9; the fluorescent material is proved to be an excellent luminescent material and has certain application value in the fields of organic electroluminescence, anti-counterfeiting, luminescent coating and the like.
In some embodiments, the cuprous complex of any one of the above embodiments is provided for use in the preparation of an organic light emitting diode or optical sensor.
The solid powder of the cuprous complex has good luminescence property and high luminescence quantum efficiency; at 298K, the maximum emission wavelengths of the cuprous complex (1), the cuprous complex (2) and the cuprous complex (3) are 561nm, 537nm and 567nm respectively, which are respectively represented by yellow-green light emission, green light emission and yellow light emission; the solid powder has luminous quantum efficiency of 58%, 65% and 56% at 298K, and service life of 9.7 μs, 51.3 μs and 11.2 μs, respectively, and can be used for preparing organic light-emitting diode or optical sensor.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly defined otherwise.
While embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the application, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. Copper complexes based on benzothiazole phosphine derivatives, characterized in that the chemical formula is C 55 H 41 CuRNSP 3 BF 4 The structural formula is shown in the following formula
Wherein Ph = phenyl; r is selected from H, OCH 3 Or CF (CF) 3 。
2. A cuprous complex according to claim 1 wherein said cuprous complex is a luminescent material and comprises benzothiazole phosphine compounds L1-L3 as main ligands and 1, 2-bis (diphenylphosphino) benzene L' as auxiliary ligands and [ Cu (CH) 3 CN) 4 ]BF 4 Is a copper source; the center of the cuprous complex is soft acid metal ion Cu (I) and is coordinated with soft alkali coordination atoms P and hard alkali coordination atoms N in the ligands L and L' to form a four-coordination structure.
3. A cuprous complex as claimed in claim 2 wherein the cuprous complex has distorted tetrahedral structure wherein the angle of N-Cu-P is similar to the angle of P-Cu-P such that the two ligands have similar steric effects.
4. A method for preparing a cuprous complex luminescent material, characterized in that the preparation of the cuprous complex according to any one of claims 1-3 comprises the following steps:
mixing a 2-fluorobenzaldehyde derivative, 2-amino thiophenol, a catalyst and a first solvent, heating an oil bath opening to boiling, cooling to remove the first solvent, and recrystallizing to obtain intermediate compounds RL1-RL3;
after the RL1-RL3 is dissolved in the second solvent, adding diphenyl potassium phosphate, and carrying out reflux reaction for 8-10 hours in an inert atmosphere; cooling to remove the second solvent and recrystallizing to obtain benzothiazole phosphine compounds L1-L3;
the benzothiazole phosphine compound L1-L3, 1, 2-bis(diphenylphosphino) benzene and [ Cu (CH) 3 CN) 4 ]BF 4 Adding the copper complex into a mixed solvent, stirring and reacting for 1-2h, evaporating and concentrating the mixed solvent, and filtering to obtain a target copper complex; wherein the mixed solvent comprises dichloromethane, methanol and acetonitrile in a volume ratio of 5-10:3:2.
5. The process according to claim 4, wherein the molar ratio of the 2-fluorobenzaldehyde derivative to the 2-aminothiophenol is 1:1; the catalyst is p-toluenesulfonic acid.
6. The process of claim 4 wherein the molar ratio of potassium diphenylphosphate to RL1-RL3 is greater than 1.
7. The process according to claim 4, wherein the solvent is tetrahydrofuran, and the ratio of the RL1-RL3 to the solvent is 0.4-0.65mmol/mL.
8. The method according to claim 4, wherein the solvent is recovered by spin-evaporation.
9. The process according to claim 4, wherein the benzothiazole phosphine compound L1-L3, the 1, 2-bis (diphenylphosphino) benzene and the [ Cu (CH) 3 CN) 4 ]BF 4 The molar ratio of (2) is 1:1:1.
10. Use of a cuprous complex as claimed in any one of claims 1-3 in the preparation of organic light emitting diode or optical sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311161863.2A CN117534708A (en) | 2023-09-07 | 2023-09-07 | Copper complex based on benzothiazole phosphine derivative, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311161863.2A CN117534708A (en) | 2023-09-07 | 2023-09-07 | Copper complex based on benzothiazole phosphine derivative, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117534708A true CN117534708A (en) | 2024-02-09 |
Family
ID=89781356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311161863.2A Pending CN117534708A (en) | 2023-09-07 | 2023-09-07 | Copper complex based on benzothiazole phosphine derivative, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117534708A (en) |
-
2023
- 2023-09-07 CN CN202311161863.2A patent/CN117534708A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106459095B (en) | Metal Organic Framework (MOF) yellow phosphor and application thereof in white light emitting device | |
| CN105131942A (en) | Photo-induced yellow fluorescent zinc coordination polymer [Zn(HL)(HBPEB)] and method of synthesizing same | |
| JP2005255992A (en) | Ruthenium complex and its application | |
| CN111875634A (en) | Benzimidazole bidentate ligand-based luminescent copper compound and preparation method thereof | |
| Chen et al. | Binaphthanol-based organic fluorophores with color tunability and their optical properties | |
| Zhang et al. | Effects of counterions of colorful sandwich-type zinc (II) 4′-phenyl-terpyridine compounds on photoluminescent and thermal properties | |
| Du et al. | Syntheses, structures, and properties of three mixed-ligand complexes based on 3, 6-bis (imidazole-1-yl) pyridazine | |
| CN108752382B (en) | Terphenyl diphosphine three-coordination cuprous halide complex, and synthesis method and application thereof | |
| CN111925392B (en) | Copper compound with photoluminescence performance and preparation method thereof | |
| CN102030702B (en) | Hole-transporting material and synthesis method thereof | |
| CN117534708A (en) | Copper complex based on benzothiazole phosphine derivative, preparation method and application | |
| CN115010619B (en) | Organic luminescent material and application thereof | |
| CN113292607B (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN112209968B (en) | Cuprous halide cluster compound of furan diphosphine ligand, synthetic method, application, device, ligand and synthetic method thereof | |
| CN110272453B (en) | Tridentate phosphine ligand with dimethyl thiophene skeleton, synthetic method thereof, copper complex thereof, synthetic method of copper complex thereof and application of copper complex | |
| CN114437139A (en) | Luminescent material of tetradentate 6/5/6 cyclometalated platinum (II) complex based on azacarbazole-spirofluorene structure and application thereof | |
| JP2006193573A (en) | Metal complex phosphor for use in white, light emitting diode (led) | |
| CN117247407A (en) | Red luminous cuprous complex based on benzothiazole phosphine ligand and preparation method thereof | |
| CN113308129A (en) | Preparation and performance of homogeneous polycrystalline symmetrical bis (tetraphenylethylene) fluorescent dye | |
| CN105016988B (en) | Polyalkyloxy substituted 1,2-benzochrysene derivative and preparation method therefor | |
| CN109232169A (en) | A kind of polyaryl replaces fulvalene compound and its synthetic method | |
| CN104447874A (en) | Preparation method and application method of metal complex | |
| CN117964651B (en) | Narrow band circularly polarized luminescent molecule and preparation method and application thereof | |
| CN112538097B (en) | Metal organic complex, preparation method and application thereof | |
| RU2532642C1 (en) | Zinc and cadmium complexes of tetradentate azomethines of 2-tosylaminebenzaldehyde, possessing luminiscent activity |
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 |