CN112442090B - Iridium complex, platinum complex and nitrogen-containing tridentate ligand - Google Patents
Iridium complex, platinum complex and nitrogen-containing tridentate ligand Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 39
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 19
- 239000003446 ligand Substances 0.000 title claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 55
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 150000002503 iridium Chemical class 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-MICDWDOJSA-N 1-deuteriopropan-2-one Chemical compound [2H]CC(C)=O CSCPPACGZOOCGX-MICDWDOJSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- 238000004020 luminiscence type Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- -1 iridium Metal Complex Chemical class 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OFJQBVXEDYYHLP-UHFFFAOYSA-N FC(C1=NNC(=C1)C1=NC(=CC=C1)OC1=CC=C(C=C1)C(F)(F)F)(F)F Chemical compound FC(C1=NNC(=C1)C1=NC(=CC=C1)OC1=CC=C(C=C1)C(F)(F)F)(F)F OFJQBVXEDYYHLP-UHFFFAOYSA-N 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003057 platinum Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical group C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- HTMCTLFKKXRQNG-UHFFFAOYSA-N C(C)(C)(C)C1=CC(=NC(=C1)C1=CC(=NN1)C(F)(F)F)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(F)(F)F)C(F)(F)F Chemical compound C(C)(C)(C)C1=CC(=NC(=C1)C1=CC(=NN1)C(F)(F)F)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(F)(F)F)C(F)(F)F HTMCTLFKKXRQNG-UHFFFAOYSA-N 0.000 description 1
- WGZRLIRLHIGXQX-UHFFFAOYSA-N CC(C)(C)C1=CC(C2=CC(C(F)(F)F)=NN2)=NC(OC2=CC=C(C(F)(F)F)C=C2)=C1 Chemical compound CC(C)(C)C1=CC(C2=CC(C(F)(F)F)=NN2)=NC(OC2=CC=C(C(F)(F)F)C=C2)=C1 WGZRLIRLHIGXQX-UHFFFAOYSA-N 0.000 description 1
- QYSILJWYQHBZRG-UHFFFAOYSA-N FC(C=1C=C(C=C(C=1)CN1C=[N+](C=C1)C)N1C=[N+](C=C1)C)(F)F Chemical compound FC(C=1C=C(C=C(C=1)CN1C=[N+](C=C1)C)N1C=[N+](C=C1)C)(F)F QYSILJWYQHBZRG-UHFFFAOYSA-N 0.000 description 1
- DYYQNDFUNSSVND-UHFFFAOYSA-N FC(C=1C=CC=2N(C3=CC=C(C=C3C=2C=1)C(F)(F)F)C1=NC(=CC=C1)C1=CC(=NN1)C(F)(F)F)(F)F Chemical compound FC(C=1C=CC=2N(C3=CC=C(C=C3C=2C=1)C(F)(F)F)C1=NC(=CC=C1)C1=CC(=NN1)C(F)(F)F)(F)F DYYQNDFUNSSVND-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical group O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical group C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical group [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical group C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an iridium complex and a platinum complexCompounds and nitrogen-containing tridentate ligands, iridium complexes being represented by the general formula (I), wherein R 1 R is R 5 Each independently is a substituted or unsubstituted C 1 ‑C 12 Alkyl or substituted or unsubstituted C 6 ‑C 12 An aryl group; r is R 2 R is R 4 Each independently is hydrogen, C 1 ‑C 6 Alkyl, substituted or unsubstituted C 1 ‑C 12 Alkyl or substituted or unsubstituted C 6 ‑C 12 An aryl group; r is R 3 R is R 6 Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 ‑C 12 Alkyl, substituted or unsubstituted C 1 ‑C 6 Alkoxy, substituted or unsubstituted C 6 ‑C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; b is 0 or 1; when B is 1, B is-O-, -CH 2 -or-CR 2 -R is methyl, ethyl or propyl; c is-CH 2 -or-CR 2 -R is methyl, ethyl or propyl; a is that 1 Is a five-membered unsaturated ring or a six-membered unsaturated ring; a is that 2 Is C 6 ‑C 20 An aromatic ring of (a); x is as follows 1 、X 2 、X 3 、X 4 X is X 5 Each independently is carbon or nitrogen.
Description
Technical Field
The present invention relates to a metal complex, and more particularly, to an iridium complex and a platinum complex suitable for an organic light-emitting diode (OLED) and a nitrogen-containing tridentate ligand suitable for forming such iridium complex and platinum complex.
Background
Organic light emitting diode devices have been attracting attention in the display industry, particularly in the flat panel display industry, because they can operate at low driving voltages and can produce high luminous efficiency.
In order to develop a full-color flat panel display, development of a color light emitting material which is easy to synthesize and has high luminous efficiency is a main objective of research on OLEDs nowadays. Currently, tris-bidentate iridium complexes and platinum complexes are known to have suitable light emission characteristics, but their rigidity, stability and ease of synthesis are still lacking.
Disclosure of Invention
The invention provides an iridium complex and a platinum complex, which have sufficient rigidity and stability and are easy to synthesize.
The present invention also provides nitrogen-containing tridentate ligands suitable for use in forming such iridium complexes, platinum complexes.
The iridium complex of the present invention is represented by the general formula (I):
wherein the method comprises the steps of
R 1 R is R 5 Each independently is a substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group;
R 2 r is R 4 Each independently is hydrogen, C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group;
l and n are each independently integers from 1 to 2;
when l is equal to 2, R 2 May be the same or different, and two or more R' s 3 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
when n is equal to 2, R 4 May be the same or different, and two or more R' s 4 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
R 3 r is R 6 Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3;
m and p are each independently integers of 1 to 3;
when m is greater than or equal to 2, R 3 May be the same or different, and two or more R' s 3 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
when p is greater than or equal to 2, R 6 May be the same or different, and two or more R' s 6 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
b is 0 or 1;
when B is 1, B is-O-, -CH 2 -or-CR 2 -R is methyl, ethyl or propyl;
c is-CH 2 -or-CR 2 -R is methyl, ethyl or propyl;
A 1 is a five-membered unsaturated ring or a six-membered unsaturated ring;
A 2 is C 6 -C 20 An aromatic ring of (a); and
X 1 、X 2 、X 3 、X 4 x is X 5 Each independently is carbon or nitrogen.
The platinum complex of the present invention is represented by the general formula (II):
wherein the method comprises the steps of
R a Is chlorine, bromine, iodine, -C.ident.C-R, -NR 2 OR-OR, wherein R is a substituted OR unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 12 Aryl, or R a Has a structure represented by the following formula (1) or formula (2):
wherein R is b R is R c Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; p and q are integers of 1 to 4; when p is greater than or equal to 2, R b May be the same or different, and two or more R' s b Can be connected with each other to form C 3 -C 8 An aromatic ring of (a); and when q is greater than or equal to 2, R c May be the same or different, and two or more R' s c Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
R d is independently hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy or substituted or unsubstituted C 6 -C 12 An aryl group; r is an integer of 1 to 2; when r is equal to 2, R d May be the same or different, and two R' s d Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
R 1 r is R 5 Each independently is a substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group;
R 2 r is R 4 Each independently is hydrogen, C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group;
l and n are each independently integers from 1 to 2;
when l is equal to 2, R 2 May be the same or different, and two or more R' s 3 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
when n is equal to 2, R 4 May be the same or different, and two or more R' s 4 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
R 3 is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or C 1 -C 3 Fluoroalkyl (-C) x F 2x+1 X is an integer of 1 to 3);
m is an integer of 1 to 3;
when m is greater than or equal to 2, R 3 May be the same or different, and two or more R' s 3 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a);
c is-CH 2 -or-CR 2 -R is methyl, ethyl or propyl; and
X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 x is X 9 Each independently is carbon or nitrogen.
The nitrogen-containing tridentate ligands of the present invention are represented by the general formula (III):
wherein R is 1 ～R 5 、X 1 And l, m, n and C are as defined above for formula (I).
The iridium complex and the platinum complex coordinated by double three teeth have strong rigidity and high stability, so that the luminous efficiency is improved. The iridium complex and the platinum complex of the invention have simple synthesis, convenient purification and high yield, and are beneficial to commercial mass production.
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 shows absorption spectra and luminescence spectra of the compounds (I-3), (I-4), (I-8), (I-60) and (I-61) synthesized in examples 1, 2, 3, 4 and 5 of the present invention.
FIG. 2 shows the absorption spectrum and the emission spectrum of each of the compound (I-3) synthesized in the present invention and the control compound (Px-14).
FIG. 3 shows the absorption spectrum and the luminescence spectrum of each of the compound (I-61) synthesized in the present invention and the control compound (Cz-2).
FIG. 4 shows the results of the photostability test of the compounds (I-3), (I-4), (I-8), (I-60), (I-61), (Px-14), (Cz-2).
Detailed Description
The invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
In one embodiment, the iridium complex of the present invention has a structure represented by general formula (I):
wherein R is 1 R is R 5 Each independently is a substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group; r is R 2 R is R 4 Each independently is hydrogen, C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group; l and n are each independently integers from 1 to 2; r is R 3 R is R 6 Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; m and p are each independently integers of 1 to 3; b is 0 or 1; when B is 1, B is-O-, -CH 2 -or-CR 2 -R is methyl, ethyl or propyl; c is-CH 2 -or-CR 2 -R is methyl, ethyl or propyl; a is that 1 Is a five-membered unsaturated ring or a six-membered unsaturated ring; a is that 2 Is C 6 -C 20 An aromatic ring of (a); x is as follows 1 、X 2 、X 3 、X 4 X is X 5 Each independently is carbon or nitrogen.
In formula (I), when l is equal to 2, R2 may be the same or different, and two or more R3 may be linked to each other to form a C3-C8 aromatic ring. When n is equal to 2, R4 may be the same or different, and two or more R4 may be linked to each other to form a C3-C8 aromatic ring. When m is greater than or equal to 2, R3 may be the same or different, and two or more R3 may be linked to each other to form a C3-C8 aromatic ring. When p is greater than or equal to 2, R6 may be the same or different, and two or more R6 may be linked to each other to form a C3-C8 aromatic ring.
The above five-membered or six-membered unsaturated ring means that one or more double bonds are present in the ring system. In one embodiment, the five-membered or six-membered unsaturated ring may include a nitrogen-containing heterocyclic ring or a nitrogen-free heterocyclic ring. In one embodiment, the five-membered or six-membered unsaturated ring may include an aromatic ring.
The aromatic ring may include an aromatic hydrocarbon ring (aromatic hydrocarbon ring) or an aromatic heterocyclic ring (aromatic heterocyclic ring). Specific examples of the aromatic ring include benzene rings (benzone rings), pyridine rings (pyridine rings), pyrazine rings (pyrazine rings), pyrimidine rings (pyrimidine rings), pyridazine rings (pyridazine rings), triazine rings (triazine rings), pyrrole rings (pyrrrole rings), furan rings (furan rings), thiophene rings (thiophen rings), selenophene rings (selephene rings), tellurone rings (tellurophene ring), imidazole rings (imidozole rings), thiazole rings (thiazole rings), selenazol rings (seleazole rings), tellurozole rings (tetrazolium rings), thiadiazole rings (thiadiazole rings), oxadiazole rings (oxadiazole rings), and pyrazole rings (pyrazole rings).
In one embodiment, the iridium complex of the present invention has a structure represented by the general formula (I-a):
wherein R is 7 R is R 8 Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; q is an integer of 1 to 2; r is an integer of 1 to 4; x is as follows 6 、X 7 、X 8 、X 9 X is X 10 Each independently is carbon or nitrogen.
In formula (I-a), when q is equal to 2, R 7 May be the same or different, and two R' s 7 Can be connected with each other to form C 3 -C 8 Is a fragrance of (3). When r is greater than or equal to 2, R 8 May be the same or different, and two or more R' s 8 Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a).
In one embodiment, the iridium complexes of the present invention have a structure represented by any one of formulas (I-1) to (I-58):
in one embodiment, the iridium complexes of the present invention are represented by the general formula (I-b):
wherein R is 7 Is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; q is an integer of 1 to 2; r is R 9 R is R 10 Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; s and t are integers from 1 to 3; x is as follows 6 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 X is X 18 Each independently is carbon or nitrogen.
In formula (I-b), when q is equal to 2, R 7 May be the same or different, and two R' s 7 Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a). When s is greater than or equal to 2, R 9 May be the same or different, and two or more R' s 9 Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a). When t is greater than or equal to 2, R 10 May be the same or different, and two or more R' s 10 Can be connected with each other to form C 3 -C 8 Aromatic ring of (C)
In one embodiment, the iridium complexes of the present invention have a structure represented by any one of formulas (I-59) to (I-80):
the iridium complex has a double-three-tooth coordination mode, is high in rigidity and stability, and has high luminous efficiency. In addition, the iridium complex of the invention can modify the structure through simple reaction so as to have different valence numbers, thereby expanding the application range.
The invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention. Iridium complexes represented by the foregoing formulas (I-1), (I-2), (I-3.. The iridium complexes are hereinafter abbreviated as compounds (I-1), (I-2), (I-3.. Or complexes (I-1), (I-2), (I-3).
[ method for Forming iridium Metal Complex ]
In one embodiment, the iridium metal complex of the present invention may be prepared by the following reaction:
examples (example)
Example 1
Preparation of Compound (I-3):
IrCl is taken out 3 ·3H 2 O (130 mg,0.37 mmol), 2- (3- (trifluoromethyl) -1H-pyrazol-5-yl) -6- (4- (trifluoromethyl)) Phenoxy) pyridine (138 mg,0.37 mmol), 1- (3-tert-butyl) -5- ((3-methyl-1H-imidazol-3-ium-1-yl) methyl) phenyl) -3-methyl-1H-imidazol-3-ium hexafluorophosphate (221 mg,0.37 mmol) and potassium carbonate (1.02 g,7.38 mmol), dissolved in propionic acid (30 mL) at room temperature, heated to reflux and reacted for 12 hours. After the reaction was completed and cooled to room temperature, propionic acid was removed in vacuo, and then washed with water and ethyl acetate 3 times, and purified by column chromatography (ethyl acetate: hexane=1:3) to give a product in 28% yield.
Spectral data for compound (I-3): 1 H NMR(400MHz,acetone-d 6 ,298K):δ8.17(t,J＝7.7Hz,1H),7.82(d,J＝7.7Hz,1H),7.75(m,1H),7.41(d,J＝1.7Hz,1H),7.26(dd,J＝8.2,1.1Hz,1H),7.19(d,J＝1.9Hz,1H),7.11(d,J＝1.7Hz,1H),7.01(s,1H),6.96(d,J＝8.2Hz,1H),6.99～6.86(m,2H),6.69(d,J＝1.9Hz,1H),6.36(d,J＝2.2Hz,1H),6.08(d,J＝14.0Hz,1H),5.23(d,J＝14.0Hz,1H),2.97(s,3H),2.75(s,3H),1.40(s,9H). 19 F NMR(376MHz,acetone-d 6 ,298K):δ-60.19(s,3F),-62.10(s,3F).FD MS:m/z 871.2(M + ).
example 2
Preparation of Compound (I-4):
IrCl is taken out 3 ·3H 2 O (130 mg,0.37 mmol), 2- (3- (trifluoromethyl) -1H-pyrazol-5-yl) -6- (4- (trifluoromethyl) phenoxy) pyridine (138 mg,0.37 mmol), hexafluorophosphate salt of 3-methyl-1- (3- (3-methyl-1H-imidazol-3-ium-1-yl) -5- (trifluoromethyl) benzyl) -1H-imidazol-3-ium (226 mg,0.37 mmol) and potassium carbonate (1.02 g,7.38 mmol) were dissolved in propionic acid (30 mL) at room temperature, heated to reflux and reacted for 12 hours. After the reaction was completed and cooled to room temperature, propionic acid was removed in vacuo, and then washed with water and ethyl acetate 3 times, and purified by column chromatography (ethyl acetate: hexane=1:2) to give a product in 29% yield.
Spectral data for compound (I-4): 1 H NMR(400MHz,acetone-d 6 ,298K):δ8.25(t,J＝8.0Hz,1H),7.91(d,J＝2.3Hz,1H),7.87(d,J＝8.0Hz,1H),7.66(s,1H),7.37(s,1H),7.32(d,J＝8.0Hz,1H),7.26(d,J＝1.8Hz,1H),7.03(d,J＝7.2Hz,2H),7.00～6.90(m,2H),6.75(d,J＝1.8Hz,1H),6.29(d,J＝2.3Hz,1H),6.14(d,J＝14.4Hz,1H),5.41(d,J＝14.4Hz,1H),3.03(s,3H),2.77(s,3H). 19 F NMR(376MHz,acetone-d 6 ,298K):δ-60.36(s,3F),-61.50(s,3F),-62.21(s,3F).FD MS:m/z 883.0(M + ).
example 3
Preparation of Compound (I-8):
the synthesis procedure of compound (I-8) was similar to that of compound (I-4) except that 2- (3- (trifluoromethyl) -1H-pyrazol-5-yl) -6- (4- (trifluoromethyl) phenoxy) pyridine was changed to 4- (tert-butyl) -2- (3- (trifluoromethyl) -1H-pyrazol-5-yl) -6- (4- (trifluoromethyl) phenoxy) pyridine, and the yield was 33%.
Spectral data for compound (I-8): 1 H NMR(400MHz,acetone-d 6 ,298K):δ8.00(d,J＝1.7Hz,1H),7.90(d,J＝2.0Hz,1H),7.66(s,1H),7.37(s,1H),7.34(d,J＝1.7Hz,1H),7.26(d,J＝1.9Hz,1H),7.14(s,1H),7.03(d,J＝8.4Hz,1H),6.98～6.94(m,2H),6.75(d,J＝1.9Hz,1H),6.31(d,J＝2.0Hz,1H),6.15(d,J＝14.4Hz,1H),5.41(d,J＝14.4Hz,1H),3.04(s,3H),2.77(s,3H),1.52(s,9H). 19 F NMR(376MHz,acetone-d 6 ,298K):δ-60.31(s,3F),-61.47(s,3F),-62.17(s,3F).FD MS:m/z 939.3(M + ).
example 4
Preparation of Compound (I-60):
the synthesis procedure for compound (I-60) was similar to that of compound (I-4) except that 2- (3- (trifluoromethyl) -1H-pyrazol-5-yl) -6- (4- (trifluoromethyl) phenoxy) pyridine was changed to 3, 6-bis (trifluoromethyl) -9- (6- (3- (trifluoromethyl) -1H-pyrazol-5-yl) pyridin-2-yl) -9H-carbazole, and the yield was 31%.
Spectral data for compound (I-60): 1 H NMR(400MHz,acetone-d 6 ,298K):δ8.65(s,1H),8.56(d,J＝8.8Hz,1H),8.36(t,J＝8.0Hz,1H),8.29(dd,J＝8.0,1.0Hz,1H),8.03(dd,J＝8.0,1.0Hz,1H),7.93～7.90(m,1H),7.88(dd,J＝8.8,1.6Hz,1H),7.82(d,J＝2.1Hz,1H),7.64(s,1H),7.40(s,1H),7.28(d,J＝1.8Hz,1H),7.15(s,1H),6.81(d,J＝2.1Hz,1H),6.74(d,J＝1.8Hz,1H),6.36(d,J＝1.8Hz,1H),6.06(d,J＝14.4Hz,1H),5.43(d,J＝14.4Hz,1H),3.14(s,3H),2.52(s,3H). 19 F NMR(376MHz,acetone-d 6 ,298K):δ-60.34(s,3F),-61.42(s,3F),-61.50(s,3F),-61.56(s,3F).FD MS:m/z 1024.3(M + ).
example 5
Preparation of Compound (I-61):
the synthesis procedure of compound (I-61) was similar to that of compound (I-4) except that 2- (3- (trifluoromethyl) -1H-pyrazol-5-yl) -6- (4- (trifluoromethyl) phenoxy) pyridine was changed to 9- (4- (tert-butyl) -6- (3- (trifluoromethyl) -1H-pyrazol-5-yl) pyridin-2-yl) -3, 6-bis (trifluoromethyl) -9H-carbazole, with a yield of 30%.
Spectral data for compound (I-61): 1 H NMR(400MHz,acetone-d 6 ,298K):δ8.64(s,1H),8.53(d,J＝8.8Hz,1H),8.24(d,J＝1.6Hz,1H),8.11(d,J＝1.6Hz,1H),7.91(dd,J＝8.8,1.8Hz,2H),7.80(d,J＝2.0Hz,1H)7.63(s,1H),7.37(s,1H),7.26(d,J＝1.8Hz,1H),7.23(s,1H),6.79(d,J＝2.0Hz,1H),6.71(d,J＝1.8Hz,1H),6.36(d,J＝1.8Hz,1H),6.04(d,J＝14.4Hz,1H),5.41(d,J＝14.4Hz,1H),3.11(s,3H),2.50(s,3H),1.57(s,9H). 19 F NMR(376MHz,acetone-d 6 ,298K):δ-60.28(s,3F),-61.36(s,3F),-61.46(s,3F),-61.49(s,3F).FD MS:m/z 1080.1(M + ).
the absorption spectra and the luminescence spectra of the compounds (I-3), (I-4), (I-8), (I-60), (I-61) synthesized in examples 1, 2, 3, 4 and 5 are shown in FIG. 1, and the absorption peak position (abs lambda) max ) Emission peak Position (PL), quantum yield (Q.Y%), luminescence lifetime (τ) obs ) Half-life (τ) of radiation luminescence rad ) Thermal decomposition temperature (T) d ) Listed in table 1 below. Wherein the radiation luminescence half-life refers to the real luminescence half-life (tau) under the radiation light-emitting proportion rad ＝τ obs /q.y.); the thermal decomposition temperature was measured by heating the compound under nitrogen at 10℃per minute, continuously heating the temperature from 30℃to 600℃and recording the temperature at which the weight loss of the compound was 5%.
TABLE 1
a All spectra are in CH 2 Cl 2 Is measured at a concentration of 10 -5 M；
b The luminescence spectrum is measured in a degassing solution; coumarin (C102) (q.y. =80%, λ) in methanol max =480 nm) as standard;
c the thermal decomposition temperature refers to the temperature at which the compound loses 5% by weight.
As can be seen from FIG. 1 and Table 1, the compounds (I-3), (I-4), (I-8), (I-60) and (I-61) have excellent luminous efficiency due to their high rigidity; meanwhile, the organic light emitting diode has good thermal stability and is suitable for manufacturing OLED elements. And the compounds (I-3), (I-4), (I-8), (I-60) and (I-61) are simple and easy to synthesize and convenient to purify, and are beneficial to commercial mass production.
To better demonstrate the advantages of the six-pentacyclic unconjugated dual-carbene iridium metal complex, it was compared with the five-pentacyclic conjugated dual-carbene iridium metal complex (Px-14) and (Cz-2) published in the prior literature, reference: (1) H. -h.kuo, l. -y.hsu, j. -y.tso, w. -y.hung, s. -h.liu, p. -t.chou, k. -t.wong, z. -l.zhu, c. -S.Lee, A.K.Y.Jen, Y.Chi, J.Mater.Chem.C 2018,6,10486; (2) H. -h.kuo, z. -l.zhu, c. -s.lee, y. -k.chen, s. -h.liu, p. -t.chou, a.k. -Y.Jen, Y.Chi, adv.Sci.2018,5,1800846.
The structures of the five-ring conjugated double-carbene iridium metal complexes (Px-14) and (Cz-2) and the corresponding structures of the six-five-ring unconjugated double-carbene iridium metal complexes (I-3) and (I-61) are shown as follows:
the "five-five ring" in the five-ring conjugated double-carbene iridium metal complex (Px-14) and (Cz-2) refers to a ring form composed of a nitrogen-containing tridentate ligand on the right side and a central metal, wherein there are two five-membered rings. The "six-five ring" in the six-five ring nonconjugated double-carbene iridium metal complex (I-3) and (I-61) refers to a ring form composed of a nitrogen-containing tridentate ligand on the right side and a central metal, wherein the ring form has one six-membered ring and one five-membered ring.
The absorption spectra and the luminescence spectra of the compounds (Px-14), (I-3), (Cz-2), (I-61) are shown in FIGS. 2 and 3, and the absorption peak position (abs lambda) max ) Emission peak Position (PL), quantum yield (Q.Y%), luminescence lifetime (τ) obs ) Half-life (τ) of radiation luminescence rad ) Thermal decomposition temperature (T) d ) Listed in table 2 below.
TABLE 2
a All spectra are in CH 2 Cl 2 Is measured at a concentration of 10 -5 M；
b The luminescence spectrum is measured in a degassing solution; coumarin (C102) (q.y. =80%, λ) in methanol max =480 nm) as standard;
c the thermal decomposition temperature refers to the temperature at which the compound loses 5% by weight.
As can be seen from tables 1 and 2, the thermal decomposition temperatures of the compounds (I-3), (I-4), (I-8), (I-60), (I-61), (Px-14) and (Cz-2) are all greater than 350 degrees, showing that the iridium metal compounds of this type have good thermal stability. However, the thermal decomposition temperature cannot truly evaluate the stability of the compound under long-term operation in an OLED element, and thus, the compound is dissolved in anhydrous oxygen-freeIn the toluene solution of (2), the solution was continuously irradiated with a light source of pseudo-sunlight, and the compound was tested for photostability. Before illumination, the initial maximum intensity of radiation was measured (A 0 ) The method comprises the steps of carrying out a first treatment on the surface of the After illumination, the strongest radiation intensity after degradation was measured (A t ) Using the first order reaction rate equation: ln (A) t /A 0 ) The rate constants (k) were plotted and the relative photostability of the compounds was compared with the rate constants.
As can be seen from FIGS. 2, 3 and Table 2, the six-pentacyclic unconjugated double-carbene iridium metal complexes (I-3) and (I-61) have almost the same emission peak positions and quantum yields, but have a shorter half-life of radiation emission than the corresponding pentacyclic conjugated double-carbene iridium metal complexes (Px-14) and (Cz-2). The carbene ligand of the broken conjugation type is utilized to form coordination with metal by a five-membered ring and a six-membered ring, so that the bonding angle is more close to 180 degrees of theory, further the acting force between the ligand and the metal is increased, and the promotion of 3 The MC excited state energy level is farther away from the light emission energy level and enriches the electron density of the central metal, so that the light emission half life is effectively reduced.
The results of the photo-stability test for the compounds (I-3), (I-4), (I-8), (I-60), (I-61), (Px-14), (Cz-2) are shown in FIG. 4, and the photo-degradation rate constant (k), the relative photo-stability (setting Px-14 photo-stability to 100) are shown in Table 3 below.
| Compounds of formula (I) | Photodegradation Rate constant (hr) -1 ) | Stability to light |
| (Px-14) | 4.3x 10 -3 | 100 |
| (I-3) | 3.5x 10 -3 | 123 |
| (I-4) | 2.1x 10 -3 | 205 |
| (I-8) | 2.0x 10 -3 | 215 |
| (Cz-2) | 4.3x 10 -3 | 153 |
| (I-60) | 1.2x 10 -3 | 358 |
| (I-61) | 1.1x 10 -3 | 391 |
As can be seen from FIG. 4 and Table 3, the compounds (I-3), (I-4) and (I-8) have better photostability than (Px-14); meanwhile, the compounds (I-60) and (I-61) have better photostability than (Cz-2). The comprehensive results show that the prepared six-five-ring unconjugated double-carbene iridium metal complex using the disconnected conjugated carbene has excellent luminous efficiency and short half-life of radiation luminescence. Most importantly, the novel compound has better long-acting light stability, and has great significance on the development of blue phosphorescence luminescent materials.
In one embodiment, the nitrogen-containing tridentate ligands of the present invention (e.g., six-pentacyclic unconjugated biscarbines) are represented by the general formula (III):
wherein R is 1 ～R 5 、X 1 And l, m, n and C are as defined above for formula (I).
The above-described six-pentacyclic unconjugated biscarbines can be used to form other metal complexes, such as platinum complexes, in addition to iridium complexes.
In one embodiment, the platinum complexes of the invention have the structure represented by the general formula (II):
wherein R is a Is chlorine, bromine, iodine, -C.ident.C-R, -NR 2 OR-OR, wherein R is a substituted OR unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 12 Aryl, or R a Has a structure represented by the following formula (1) or formula (2):
wherein R is b R is R c Each independently is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy, substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; p and q are integers of 1 to 4;
R d is independently hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted or unsubstituted C 1 -C 6 Alkoxy or substituted orUnsubstituted C 6 -C 12 An aryl group; r is an integer of 1 to 2; and
R 1 r is R 5 Each independently is a substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group; r is R 2 R is R 4 Each independently is hydrogen, C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 12 Alkyl or substituted or unsubstituted C 6 -C 12 An aryl group; l and n are each independently integers from 1 to 2; r is R 3 Is hydrogen, fluorine, substituted or unsubstituted C 1 -C 12 Alkyl, substituted, unsubstituted C 1 -C 6 Alkoxy or substituted or unsubstituted C 6 -C 12 Aryl or-C x F 2x+1 X is an integer of 1 to 3; m is an integer of 1 to 3; c is-CH 2 -or-CR 2 -R is methyl, ethyl or propyl; x is as follows 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 X is X 9 Each independently is carbon or nitrogen.
In the general formula (1), when p is greater than or equal to 2, R b May be the same or different, and two or more R' s b Can be connected with each other to form C 3 -C 8 An aromatic ring of (a); and when q is greater than or equal to 2, R c May be the same or different, and two or more R' s c Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a).
In the general formula (2), when r is equal to 2, R d May be the same or different, and two R' s d Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a).
In formula (II), when l is equal to 2, R 2 May be the same or different, and two or more R' s 3 Can be connected with each other to form C 3 -C 8 An aromatic ring of (a); when n is equal to 2, R 4 May be the same or different, and two or more R' s 4 Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a). When m is greater than or equal to 2, R 3 May be the same or different, and two or more R' s 3 Can be connected with each other to form C 3 -C 8 Is an aromatic ring of (a).
In one embodiment, the platinum complex of the present invention has a structure represented by any one of the formulas (II-1) to (II-30):
the present invention will be further illustrated by the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The platinum complex represented by the aforementioned formula (II-1), (II-2), (II-3.) is hereinafter abbreviated as compound (II-1), (II-2), (II-3.) or complex (II-1), (II-2), (II-3).
[ method for Forming platinum Metal Complex ]
In one embodiment, the platinum metal complexes of the present invention may be prepared by the reaction described below:
examples (example)
Example 6
Preparation of Compound (II-1):
taking Pt (cod) Cl 2 (100 mg,0.27 mmol), 1- (3-tert-butyl) -5- ((3-methyl-1H-imidazol-3-ium-1-yl) methyl) phenyl) -3-methyl-1H-imidazol-3-ium hexafluorophosphate (177 mg,0.29 mmol) and potassium acetate (525 mg,5.34 mmol), dissolved in propionic acid (10 mL) at room temperature, heated to reflux and reacted for 4 to 6 hours. After the reaction was completed and cooled to room temperature, propionic acid was removed in vacuo, and then washed with water and ethyl acetate 3 times, and purified by column chromatography (ethyl acetate: hexane=1:1) to give a product in 38% yield.
Spectroscopic data for compound (II-1): 1 H NMR(400MHz,acetone-d 6 ,298K):δ7.85(d,J＝2.0Hz,1H),7.38(d,J＝1.8Hz,1H),7.28(d,J＝1.8Hz,1H),7.21(d,J＝1.8Hz,1H),7.16(d,J＝1.8Hz,1H),6.94(d,J＝2.0Hz,1H),5.08(s,2H),4.28(s,3H),4.15(s,3H),1.31(s,9H).
example 7
Preparation of Compound (II-3):
the synthesis procedure for compound (II-3) was similar to that of compound (II-1) except that the hexafluorophosphate salt of 1- (3-tert-butyl) -5- ((3-methyl-1H-imidazol-3-ium-1-yl) methyl) phenyl) -3-methyl-1H-imidazol-3-ium was changed to that of 3-methyl-1- (3-methyl-1H-imidazol-3-yl) -5- (trifluoromethyl) benzyl) -1H-imidazol-3-ium in 51% yield.
Spectroscopic data for compound (II-3): 1 H NMR(400MHz,acetone-d 6 ,298K):δ7.97(d,J＝2.0Hz,1H),7.52(t,J＝6.9Hz,1H),7.45～7.41(m,1H),7.31(d,J＝2.0Hz,1H),7.22(d,J＝1.8Hz,2H),5.19(s,2H),4.32(s,3H),4.16(s,3H). 19 F NMR(376MHz,acetone-d 6 ,298K):δ-62.14(s,3F).
example 8
Preparation of Compound (II-4):
the synthesis procedure for compound (II-4) was similar to that of compound (II-1) except that the hexafluorophosphate salt of 1- (3-tert-butyl) -5- ((3-methyl-1H-imidazol-3-ium-1-yl) methyl) phenyl) -3-methyl-1H-imidazol-3-ium was changed to that of 3-isopropyl-1- (3- (3-isopropyl-1H-imidazol-3-yl) -5- (trifluoromethyl) benzyl) -1H-imidazol-3-ium in 25% yield.
Spectroscopic data for compound (II-4): 1 H NMR(400MHz,acetone-d 6 ,298K):δ8.01(d,J＝2.2Hz,1H),7.55～7.51(m,2H),7.47(d,J＝2.0Hz,1H),7.42(d,J＝1.8Hz,1H),7.22(t,J＝8.4Hz,1H),6.61～6.52(m,1H),6.33～6.25(m,1H),5.15(s,2H),1.51(d,J＝6.8Hz,6H),1.41(d,J＝6.8Hz,6H).
the iridium complex and the platinum complex can be applied to OLED. In one embodiment, the organic light emitting diode comprises two electrodes and a light emitting layer disposed between the two electrodes, and the light emitting layer contains at least one iridium complex, platinum complex or a combination thereof. For example, the iridium complex and platinum complex of the present invention are doped as dopants into a host material of the light-emitting layer.
In one embodiment, the present invention provides an OLED comprising two electrodes and a light emitting layer disposed between the two electrodes, wherein the light emitting layer comprises an iridium complex, a platinum complex, or a combination thereof. The iridium complex and/or platinum complex can be used as a dopant of a host material of the light-emitting layer. The material of each of the two electrodes may be selected from materials commonly used in the art, and other functional layers such as an electron-transport layer (electron-transport layer), a hole-injection layer (hole-transport layer), a hole-blocking layer (hole-blocking layer), etc. may be disposed between each electrode and the light emitting layer by the prior art. The OLED may be fabricated on a flat substrate, such as a conductive glass or plastic substrate.
In conclusion, the iridium complex and the platinum complex coordinated by double three teeth have high rigidity and high stability, so that the luminous efficiency is improved. The iridium complex provided by the invention is simple and easy to synthesize, convenient to purify and high in yield, and is beneficial to commercial mass production. In addition, the iridium complex of the present invention can also be modified in its structure by a simple reaction so as to have different valence numbers. The iridium complex with neutral valence can be used for OLED, the complex with positive or negative valence has water solubility, can modify biological functional groups, and is applied to the medical field, so that the application field of the iridium complex is very wide.
Although the invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather may be modified and practiced by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (7)
1. An iridium complex represented by the general formula (I-a):
wherein the method comprises the steps of
R 1 R is R 5 Each independently is unsubstituted C 1 -C 12 An alkyl group;
R 2 r is R 4 Each independently is hydrogen or unsubstituted C 1 -C 12 An alkyl group;
l and n are each independently integers from 1 to 2;
when l is equal to 2, R 2 May be the same or different;
when n is equal to 2, R 4 May be the same or different;
R 3 r is R 6 Each independently hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
m and p are each independently integers of 1 to 3;
when m is greater than or equal to 2, R 3 May be the same or different;
when p is greater than or equal to 2, R 6 May be the same or different;
b is 0 or 1;
when B is 1, B is-O-, -CH 2 -or-CR 2 -R is methyl, ethyl or propyl;
c is-CH 2 -；
R 7 R is R 8 Each independently hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
q is an integer of 1 to 2;
r is an integer of 1 to 4;
when q is equal to 2, R 7 May be the same or different;
when r is greater than or equal to 2, R 8 May be the same or different;
X 1 is carbon; and
X 3 、X 4 、X 6 、X 7 、X 8 、X 9 x is X 10 Each independently is carbon or nitrogen.
2. The iridium complex according to claim 1, which has a structure represented by any one of the formulae (I-1) to (I-58):
3. an iridium complex represented by the general formula (I-b):
wherein the method comprises the steps of
R 1 R is R 5 Each independently is unsubstituted C 1 -C 12 An alkyl group;
R 2 r is R 4 Each independently is hydrogen or unsubstituted C 1 -C 12 An alkyl group;
l and n are each independently integers from 1 to 2;
when l is equal to 2, R 2 May be the same or different;
when n is equal to 2, R 4 May be the same or different;
R 3 r is R 6 Each independently hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
m and p are each independently integers of 1 to 3;
when m is greater than or equal to 2, R 3 May be the same or different;
when p is greater than or equal to 2, R 6 May be the same or different;
c is-CH 2 -；
R 7 Is hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
q is an integer of 1 to 2;
when q is equal to 2, R 7 May be the same or different;
R 9 r is R 10 Each independently hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
s and t are integers from 1 to 3;
when s is greater than or equal to 2, R 9 May be the same or different;
when t is greater than or equal to 2, R 10 May be the same or different;
X 1 is carbon; x is as follows 3 、X 4 、X 6 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 X is X 18 Each independently is carbon or nitrogen.
4. The iridium complex according to claim 3, which has a structure represented by any one of the formulae (I-59) to (I-80):
5. a platinum complex represented by the general formula (II):
wherein the method comprises the steps of
R a Is chlorine, bromine, iodine, -C.ident.C-R, -NR 2 OR-OR, wherein R is unsubstituted C 1 -C 12 Alkyl, unsubstituted C 6 -C 12 Aryl, or R a Has a structure represented by the following formula (1) or formula (2):
wherein R is b R is R c Each independently hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3; p and q are integers of 1 to 4; when p is greater than or equal to 2, R b May be the same or different; and when q is greater than or equal to 2, R c May be the same or different;
R d is independently hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl or unsubstituted C 1 -C 6 An alkoxy group; r is an integer of 1 to 2; when r is equal to 2, R d May be the same or different;
R 1 r is R 5 Each independently is unsubstituted C 1 -C 12 An alkyl group;
R 2 r is R 4 Each independently is hydrogen or unsubstituted C 1 -C 12 An alkyl group;
l and n are each independently integers from 1 to 2;
when l is equal to 2, R 2 May be the same or different;
when n is equal to 2, R 4 May be the same or different;
R 3 is hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
m is an integer of 1 to 3;
when m is greater than or equal to 2, R 3 May be the same or different;
c is-CH 2 -；
X 1 Is carbon; and
X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 x is X 9 Each independently is carbon or nitrogen.
6. The platinum complex according to claim 5, which has a structure represented by any one of the formulas (II-1) to (II-30):
7. a nitrogen-containing tridentate ligand represented by the general formula (III):
wherein the method comprises the steps of
R 1 R is R 5 Each independently is unsubstituted C 1 -C 12 An alkyl group;
R 2 r is R 4 Each independently is hydrogen or unsubstituted C 1 -C 12 An alkyl group;
l and n are each independently integers from 1 to 2;
when l is equal to 2, R 2 May be the same or different;
when n is equal to 2, R 4 May be the same or different;
R 3 is hydrogen, fluorine, unsubstituted C 1 -C 12 Alkyl, unsubstituted C 1 -C 6 Alkoxy or-C x F 2x+1 X is an integer of 1 to 3;
m is an integer of 1 to 3;
when m is greater than or equal to 2, R 3 May be the same or different;
c is-CH 2 -; and
X 1 is carbon.
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