CN107200755A - The platinum complex of four-coordination deuterated ligand coordination - Google Patents

Abstract

The present invention's is that, on a kind of platinum complex for being adapted to be used as the multiple tooth coordination of phosphorescence or delayed fluorescence or phosphorescent emitters in showing and illuminating application, the phosphorescent emitters or the platinum complex as delayed fluorescence or phosphorescent emitters of being suitable as have one of following structure：

Description

The platinum complex of four-coordination deuterated ligand coordination

Technical field

The disclosure be on one kind be adapted to show and illuminate application in be used as phosphorescence or delayed fluorescence or The platinum complex of the multiple tooth coordination of phosphorescent emitters.

Background technology

The compound that can be absorbed and/or light is applicable to various optics and photoelectric device, includes but is not limited to such as Solar energy, photosensitive such light absorption device, Organic Light Emitting Diode (OLED), light emitting devices or existing light absorbs have light again The device of emissivities and the related application for biomarker.In order to find for the organic of optics and electroluminescent device And organo metallic material, specially made much to study.In general, the research mesh village in this field is to realize multinomial target, Absorption and luminous efficiency including improving device, improve the stability of device, and improve resolution ratio etc..

Although exclusively for optics and photoelectric material (for example, red and green phosphorescent organo metallic material is on sale on the market And Organic Light Emitting Diode (OLED), illumination and advanced display in be used as phosphor) studies conducted achieve it is aobvious The progress of work, but many currently available materials show many shortcomings, including combination property is general, transmitting or incomplete absorption And stability is not ideal enough etc..

Excellent BLUE EMITTER is especially rare, and its a major challenge faced is the stability of blue device.With it is red and The minimum triplet excited state energy of green phosphor is compared, and the minimum triplet excited state energy of blue phosphor is very high, this meaning The minimum triplet excited state energy for the material of main part of blue device even can be higher.Therefore, one of problem is that blue device can Dopant material is limited.Accordingly, it is desirable to the new of more dominance energy can be shown in optical emitting and absorption application Material.

In the present disclosure of the invention, deuterium is introduced to the part of platinum complex.Because D-atom is than hydrogen atom weight, with C- H keys are compared, and the vibration of carbon-deuterium (C-D) key can be reduced.Therefore, the shuttle belt of emission spectrum will be reduced or weakened, and whole light Spectrum can narrow.This is possible to promote transmitting performance that is photochromic and improving device.More particularly, the CIE coordinates of complex compound will It is tuned to more meet the demand of flat panel TV.

The content of the invention

The present invention relates to the gold as emitter being adapted in Organic Light Emitting Diode (OLED), display and illumination application Belong to complex compound.

Disclosed herein is 1 type molecular formula complex compound：

R^aRepresent single, double, triple or the substitution of four bases, R^aIt is independent deuterium, CDH₂, CD₂H, CD₃, CD R¹R², CD₂R¹, or other Alkyl virtue, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, monosubstituted amino, two hydrocarbon containing deuterium Base amino, mono amino, diaryl amine, alkoxy, aryloxy group, halogeno-group, aralkyl, ester, alkoxy carbonyl group, amide groups, alkoxy Carbonylamino, alkoxy carbonyl base amino, aryloxycarbonyl base amino, aralkyl, sulfonamides, carbamoyl, alkylthio group, urea Base, phosphamide, silicyl, polymer；Or its any conjugate or compound.

R^b、R^c、R^dAnd R^eOr in each be all self-existent or non-existent；If exist, then R^b、 R^c、R^dAnd R^eIn each represent the substitution of single or double base, R respectively^b,R^dAnd R^eCan also be the substitution of three bases, R^bCan be four bases Substitution, and wherein R^b、R^c、R^dAnd R^eIn each be independent deuterium, it is halogen, hydroxyl, sulfydryl, nitro, cyano group, nitrile, different Nitrile, sulfinyl, sulfydryl, sulfo group, carboxyl, diazanyl；It is substituted or unsubstituted：Aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl Base, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkoxy, virtue The oxygen-containing carbonylamino of epoxide, haloalkyl, aralkyl, ester, alkoxy carbonyl, acyl amino, alkoxycarbonyl amino, aryl, Sulfamido, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or change Compound, R^aAnd R^bOptionally connection forms ring, R^dAnd R^eOptionally connection forms ring.

R¹And R²In each be all independent hydrogen, deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, Sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl-alkyl, cycloalkenyl group cyclenes Base, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, diaryl Amino, alkoxy, oxygen aryl, alkylhalide group, aralkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl Amino, sulfamido, sulfonamides, carbamyl, sulfanyl, urea groups, phosphamide, silicyl, polymer；Or its any combination Thing or compound.

On the one hand, the platinum complex has molecular formula 2, molecular formula 3, molecular formula 4, molecular formula 5, molecular formula 6 or molecular formula 7 Structure.On the other hand, they can not also obtain Specific details at this comprising it other structures or part, the present invention is not Should be confined to its those obtain Specific details herein structure or part.

R^b、R^c、R^dAnd R^eOr in each be all self-existent or non-existent, if exist, then R^b、 R^c、R^dAnd R^eIn each represent the substitution of single or double base, R respectively^b,R^dAnd R^eCan also be the substitution of three bases, R^bCan be four bases Substitution, and wherein R^b、R^c、R^dAnd R^eIn each be independent deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, Isonitrile, sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；Substitute or do not substitute：Aryl, cycloalkyl-alkyl, cycloalkenyl group cyclenes Base, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, diaryl Amino, alkoxy, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl ammonia Base, sulfamido, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or Compound, R^aAnd R^bOptionally connection forms fusion ring, R^dAnd R^eOptionally connection forms fusion ring.

R¹And R²In each be all independent hydrogen, deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, Sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl-alkyl, cycloalkenyl group cyclenes Base, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, diaryl Amino, alkoxy, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl ammonia Base, sulfamido, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or Compound.

There is disclosed herein the composition for being included herein disclosed one or more compounds.

There is disclosed herein the device for being included herein disclosed one or more compounds, such as organic light-emitting diodes Pipe.

Brief description of the drawings

Fig. 1 describes a device for including metal complex disclosed herein.In one embodiment, the compound It can be used in Organic Light Emitting Diode.

Fig. 2 shows that compound 1 is in CH at room temperature₂Cl₂With the emission spectrum in PMMA.

Fig. 3 is shown⁶Compound containing deuterium 3 and without deuterium compound in d-DMSO solvents¹H NMR spectras compare.

Fig. 4 shows that compound 3 is in CH at room temperature₂Cl₂With the emission spectrum in PMMA.

Fig. 5 shows that compound 3 is in CH at room temperature₂Cl₂In compound containing deuterium and the ratio without deuterium compound emission spectrum Compared with.

Fig. 6 shows containing deuterium compound of the compound 2 in PMMA and the ratio without deuterium compound emission spectrum at room temperature Compared with.

Fig. 7 shows that compound 7 is in CH at room temperature₂Cl₂In compound containing deuterium and the ratio without deuterium compound emission spectrum Compared with.

The other side of picture is also described in picture description after picture.Advantage is by claim In the element that particularly points out and combination and realize and obtain.It is pointed out that general remark above and following detailed Illustrate all to be exemplary and explanatory, without limited.

Embodiment

By reference to example that is described further below and wherein including, the present invention can be more easily understood.

Before the compounds of this invention, device and/or method are disclosed and described, it is noted that unless otherwise saying Bright, otherwise they are not limited to specific synthetic method, or unless otherwise stated, they are not limited to particular agent, because These methods or reagent are it is of course possible to changing.It is also noted that be a bit, term used herein be intended merely to description it is specific Aspect, rather than in order to limit.Although any method of or identical similar with those described herein method or material Or material can be used in practice or test, but will now be described is illustrative methods and material.

Other clear stipulaties, otherwise illustrate and the singulative used in accessory claim unless the context otherwise " one ", " one " and it is " a certain " include plural reference.Thus, for example, when mentioning " a kind of composition " include two or more into The mixing divided.

Term " optional " used herein or " alternatively " refer to that the event or situation that then describe may be sent out It is raw or may not occur, and specific embodiment and the event or situation of the description when including the event or situation generation Specific embodiment when not occurring.

It disclosed herein is the combination for preparing composition described herein and to be used in method disclosed herein The composition of thing in itself.These and other materials obtain herein disclosure, it is noted that when the combination of these materials, subgroup, When interaction, class are disclosed, although each different independent and collective combinations of these compounds and the specific reference of arrangement Can not clearly it be disclosed, but each compound is all especially considered and described herein.If a for example, specific chemical combination A variety of modifications that thing is disclosed and discussed and can made for multiple molecules comprising the compound are discussed, unless Illustrated on the contrary, otherwise each combination and permutation of the compound and possible modification can all be considered. Therefore, if belonging to of a sort molecule A, B and C and belonging to showing for of a sort molecule D, E and F and a kind of combination molecule Example obtains disclosure, then A-D is disclosed, then like this, each even if not being that each molecule is all individually described in detail Molecule is all obtained individually and the meaning of groupthink is still, A-E, A-F, B-D, B-E, B-F, C-D, and C-E and C-F combination are all It is considered as being disclosed.Equally, the subset of these molecules or combination are recognized as being disclosed.Therefore, such as, A-E, B- F and C-E subgroup can be considered as being disclosed.This concept is applied to all aspects of the application, includes, but not limited to Prepare and using the step in the method for said composition.Therefore, it is right if there is the various additional steps being able to carry out This is it is to be understood that these extra steps can be performed with any certain specific embodiments or the specific embodiment combination of these methods Each in rapid.

As mentioned above, a connection atom or group can connect two atoms, such as, a nitrogen-atoms With a carbon atom.On the one hand one connection atom or group are disclosed as X, Y, Y herein¹, Y², and/or Z.If chemical combination If valency allows, the being also an option that property of connection atom possesses other chemical groups of attachment.For example, on the one hand, because if Chemical valence is once incorporated on two groups (for example, nitrogen and carbon-based group), it will saturation, so an oxygen atom do not have appoint Other chemical groups of what attachment.On the other hand, can be that carbon atom adheres to two additionally when carbon atom is the connection atomic time Chemical group.Suitable chemical group includes amine, acid amides, mercaptan, aryl, heteroaryl, cycloalkyl-alkyl and heterocyclyl groups.

Term " loop structure " or similar terms include but is not limited to context means that any cyclic chemical structure, Aryl, heteroaryl, cycloalkyl-alkyl, cycloalkenyl group, heterocyclic radical, carbene and N- heterocyclic radical carbenes.

" replacement " one word used herein is envisioned for including all of organic compound allowing substituent.One In individual extensive aspect, substituent can be allowed to include the acyclic and cyclic of organic compound, side chain and unbranched, carbocyclic ring With heterocycle, the substituent of aromatic series and non-aromatic.Illustrative substituent includes, for example, those described below takes Dai Ji.For suitable organic compound, can allow substituent can be it is one or more, can be with identical or different.In order to The purpose of the present invention is realized, hetero atom, such as nitro can possess the organic compound described herein for meeting hetero atom chemical valence The hydrogen substituent of thing and/or any admissible substituent.The present invention will not be permitted by organic compound in any way Perhaps the limitation of substituent.In addition, term " substitution " or " with ... substitution " Implicit Conditions for including are, such substitution and substitution Atom and substituent allow chemical valence consistent, and this substitution can bring a kind of compound of stabilization, such as, a kind of Will not the spontaneous compound changed by modes such as rearrangement, cyclisation, eliminations.The imagination that we also make is, in some sides Face, unless there are clearly opposite explanation, single substituent can be replaced (that is, being further substituted with or not by further selectivity Substitution).

In order to define it is different belong to, " A1 ", " A2 ", " A3 ", " A4 " are used for as representing various specific take herein Dai Ji general symbol(s).These symbols can be any substituent, be not limited to those and obtain disclosed substituent herein, such as Really they are defined as specified substituent in one embodiment, and Ta Menneng in another specific embodiment, is defined as one A little other substituents.

Term " alkyl " used herein is a kind of side chain or the unbranched saturated carbon being made up of 1 to 24 carbon atoms Hydrogen compound group, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, dibutyl, the tert-butyl group, n-pentyl, Isopentyl, diamyl, neopentyl, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, palmityl, 20 bases, two Tetradecyl etc..Groups can be ring-type or non-annularity.Groups can be side chain or unbranched.Groups can also It is commutable or do not replace.Such as, groups can be replaced with one or more groups, be included but is not limited to, herein Described alkyl, cycloalkyl-alkyl, alkoxy, amino, or, halide, hydroxyl, nitro, silicyl, sulphur epoxide or sulphur Alcohol.A kind of " low alkyl " group is a kind of groups included from the individual carbon atom not waited of 1 to 6 (such as from 1 to 4).

In this paper description in the whole text, " alkyl " generally refers to both unsubstituted alkyl group and substitution alkyl group；However, Herein, also by the special special substituent confirmed in alkyl group, substitution alkyl group is mentioned.For example, term " alkyl halide " or " halogen Substituted alkyl " refers specifically to a kind of by one or more halide, such as fluorine, chlorine, the alkyl group of bromine or iodine substitution.Term " alkoxy alkane Base " refers specifically to a kind of groups replaced by one or more alkoxy grps as described below.Term " alkyl amino " is specific Refer to a kind of groups replaced by one or more alkylamino groups as described below etc..When using in a specific embodiment " alkyl ", and in another specific embodiment use such as " alkyl alcohol " etc particular term when, it is not intended to this be Imply, what " alkyl " this term did not referred to is also such as " alkyl alcohol " or the like particular term.

This way is also applied for other base groups as described herein.It is, such as " cycloalkyl " an etc term refers to Be both non-substituted and substituted cycloalkylalkyl group, in addition, substituted group can also be obtained specifically in article It is determined that；For example, a kind of special substituted cycloalkyl can to the north of be referred to as, such as, and a kind of " cycloalkyl ".Equally, a kind of substituted Alkoxy can be specially referred to as, for example, a kind of " halogenated alkoxy ", special substituted alkenyl can be referred to as, for example, " alkene Base ethanol ", or similar term.Again, using such as " cycloalkyl " etc general terms and such as " alkyl-cycloalkyl " etc Particular term is not meant to that general terms is not to include particular term yet.

Term " cycloalkyl " used herein is a kind of non-aromatic carbon-based ring being at least made up of three carbon atoms.Ring The example of alkyl-alkyl group includes, but not limited to cyclopropane, cyclobutane, pentamethylene, cyclohexyl, norborny, and similar Material.Term " Heterocyclylalkyl " is a kind of naphthene group as defined above, and be included in " among the implication of cycloalkyl " ", In this implication, at least one carbon atom on ring is replaced by a hetero atom, and this hetero atom includes, but not limited to Nitrogen, oxygen, sulphur or phosphorus.Cycloalkyl group and Heterocyclylalkyl group can be substituted or non-substituted property.Cycloalkyl group and heterocycle alkane Base group can be replaced by one or more base groups, include, but not limited to alkyl described herein, cycloalkyl, alkoxy, ammonia Base, ether, halogen, hydroxyl, nitro, silicyl, sulphur epoxide, or mercaptan.

Term " poly- alkylene group " used herein is a kind of base for having two or more CH2 groups being connected with each other Group.Poly- alkylene group can be by molecular formula-(CH₂)_a- represent, wherein one " a " represents one from 2 to 500 integer.

Term " alkoxy " used herein refers to a kind of alkyl being connected by an ehter bond with " alkoxy " Or cycloalkyl group；It is, a kind of " alkoxy " group can be defined as-OA¹, wherein A¹It is alkyl defined above or cycloalkanes Base." alkoxy " also includes the polymer of the alkoxy group just described；It is, a kind of alkoxy can be it is a kind of such as- OA¹—OA²Or-OA¹—(OA²)_a—OA³Etc polymer, wherein " a " is one from 1 to 200 integer, and A¹、A²And A³ It is alkyl and/or cycloalkyl group.

Term as used herein " alkenyl " is a kind of hydrocarbon group for including 2 to 24 carbon atoms, its knot Structure molecular formula is at least containing a carbon-carbon double bond.Such as (A¹A²) C=C (A³A⁴) etc unsymmetric structure be intended to include E and Z Two kinds of isomers.This can be estimated from structural formula, in structural formula, there is a kind of asymmetric alkene, or It can also be explicitly indicated that with C=C keysyms.Alkenyl group can use one or more substituent groups, include but is not limited to, herein Described alkyl, cycloalkyl-alkyl, alkoxy, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, iso-aryl, acetaldehyde, amino, Carboxylic acid, ester, ether, halide, hydroxyl, ketone, azide, nitro, silicyl, sulphur epoxide or mercaptan.

Term " cycloalkenyl group " used herein is a kind of non-aromatic carbocyclic ring being made up of at least three carbon atoms, and extremely Less containing a carbon-carbon double bond, i.e. C=C.The example of cycloalkenyl group group includes, but not limited to cyclopropanyl, cyclobutane base, ring penta Alkenyl, cyclopentadecylene base, cyclohexene, cyclohexadienyl, ENB, and similar compound.Term " heterocycloalkenyl " is one Class cycloalkenyl group group defined above, and be included in the implication of term " cycloalkenyl group ", at least one carbon in its middle ring is former Son is replaced by a hetero atom, and the hetero atom includes but is not limited to, nitrogen, oxygen, sulphur, phosphorus.Cycloalkenyl group group and heterocycloalkenyl group can be with It is substituted and non-substituted property.Cycloalkenyl group group and heterocycloalkenyl group can be replaced by one or more group, including but not limit In, alkyl described herein, cycloalkyl, alkoxy, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, heteroaryl, acetaldehyde, Amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, nitrine, nitro, silicyl, sulphur epoxide or mercaptan.

Term as used herein " alkynyl " is a kind of hydrocarbon group for including 2 to 24 carbon atoms, its knot Structure molecular formula is at least containing a triple carbon-carbon bonds.Ethynylene group can use one or more substituent groups, include but is not limited to, herein Described alkyl, cycloalkyl-alkyl, alkoxy, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, iso-aryl, acetaldehyde, amino, Carboxylic acid, ester, ether, halide, hydroxyl, ketone, azide, nitro, silicyl, sulphur epoxide or mercaptan.

Term " cycloalkynyl radical " used herein is a kind of non-aromatic carbocyclic ring being made up of at least seven carbon atoms, and extremely Less containing a triple carbon-carbon bonds.The example of cycloalkynyl radical group include, but not limited to cycloheptyl alkynyl, cyclo-octene base, Cyclonontynyl, and similar compound.Term " heterocycle alkynyl " is class cycloalkynyl radical group defined above, and is wrapped Include in the implication of term " cycloalkynyl radical ", at least one carbon atom in its middle ring is replaced by a hetero atom, the hetero atom bag Include but be not limited to, nitrogen, oxygen, sulphur or phosphorus.Cycloalkynyl radical group and heterocycle alkynyl group can be substituted and non-substituted property.Cycloalkynyl radical Group and heterocycle alkynyl group can be replaced by one or more group, include but is not limited to, alkyl described herein, cycloalkyl, alkane Epoxide, it is alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, folded Nitrogen, nitro, silicyl, sulphur epoxide or mercaptan.

Term as used herein " aryl " is a kind of group for including any carbon-based fragrance group, is included but is not limited to, benzene, Naphthalene, phenyl, biphenyl, phenoxy group benzene, and similar compound.Term " aryl " also includes " heteroaryl ", and " heteroaryl " is defined as One include aromatic group group, the group at least one be included in aromatic group ring in hetero atom.Heteroatomic example Son includes but is not limited to nitrogen, oxygen, sulphur and phosphorus.Equally, the term " non-heteroaryl " being also contained in term " aryl " defines one It is individual to include with the group of aromatic group, and the aromatic group does not include hetero atom.Aryl group can be substituted and non-substituted Property.Aryl group can be replaced by one or more group, include but is not limited to, alkyl described herein, cycloalkyl, alcoxyl Base, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, heteroaryl, acetaldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, nitrine, Nitro, silicyl, sulphur epoxide or mercaptan.Term " biaryl " is a kind of certain types of aryl group, and is included in " virtue In the definition of base ".Biaryl refers to the two kinds of aryl groups connected together by a condensed cyclic structure structure, as naphthalene that Sample, or, it is attached together by one or more carbon-carbon bonds, as biphenyl.

Term " aldehyde " used herein is represented by molecular formula-C (O) H.In this paper whole description, " C (O) " It is a kind of shorthand notation of carbonyl group, it is, C=O

Term as used herein " amine " or " amino " are by molecular formula-NA¹A²Represent, wherein A¹And A²Can be, it is independent , hydrogen or alkyl described herein, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, or heteroaryl group

Term as used herein " alkyl amino " is represented by molecular formula-NH (- alkyl), and wherein alkyl is herein Have been described.Representational example includes, but not limited to methylamino group, ethylamino group, propylcarbamic group, isopropyl Base amino group, butylamino group, isobutylamino group, (sec-butyl) amino group, (tert-butyl group) amino group, penta (alkane) base amino Group, c group, (tertiary pentyl) amino group, hexylamino group, and similar compound.

Term as used herein " dialkyl amido " is by molecular formula-N (- alkyl)₂Represented, wherein alkyl is herein In have been described.Representational example includes, but not limited to dimethylamino group, diethylamino group, dipropylamino Group, diisopropylaminoethyl group, dibutylamino group, diisobutylamino group, two (sec-butyl) amino groups, two (tert-butyl group) amino Group, diamyl (alkane) base amino group, diisoamyl amino group, two (tertiary pentyl) amino groups, dihexyl amino group, N- ethyl-N- first Base amino group, N- methyl-N-propylaminos group, N- ethyl-N- propylcarbamic groups, and similar compound.

Term as used herein " carboxylic acid " represented by molecular formula-C (O) OH

Term as used herein " ester " is by molecular formula OC (O) A¹Or-C (O) OA¹It is represented, wherein A¹Can be, herein Described alkyl, cycloalkyl-alkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, heteroaryl group.Term as used herein " polyester " is by molecular formula-(A¹O(O)C-A²-C(O)O)_a- or-(A¹O(O)C-A²-OC(O))_a- represented, wherein it is possible to A¹And A²Be, it is independent, a kind of alkyl described herein, cycloalkyl-alkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl or Heteroaryl group, and " a " be one from 1 to 500 integer." polyester " is used to describe by possessing at least two carboxylic acids as term Group compound and possess at least two hydroxyl groups compound reacted produced by a kind of group.

Term as used herein " ether " is by molecular formula OC (O) A¹It is represented, wherein A¹And A²Can be, it is as described herein Alkyl, cycloalkyl-alkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, heteroaryl group.Term as used herein " polyethers " By molecular formula-(A¹O-A²O)_a-, represented, wherein A¹And A²Can be, independent, alkyl as described herein, cycloalkyl, alkene Base, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl, heteroaryl group, and " a " be one from 1 to 500 integer.The example of polyethers group Including polyethylene oxide, polypropylene oxide and polybutylene oxide thing.

Term " polymerization " includes poly- alkylene, polyethers, polyester and other groups containing repeat unit, including but does not limit In-(CH₂O)_n-CH₃、-(CH₂CH₂O)_n-CH₃、-[CH₂CH(CH₃)]_n-CH₃、-[CH₂CH(COOCH₃)]_n-CH₃、-[CH₂CH (COO CH₂CH₃)]_n-CH₃With-[CH₂CH(COO^tBu)]_n-CH₃, wherein n is integer (such as a, n>1 or n>2).

Term " halide " used herein refers to halogen fluorine, chlorine, bromine and iodine.

Term " heterocyclic radical " used herein refers to single and polycyclic non-aromatic ring system, and used herein " miscellaneous Aryl " refers to that at least one loop system is not the list and polycyclic non-aromatic ring system of carbon.These terms include azetidine, Dioxane, furans, thiazole, imidazoles, isoxazole, morpholine, oxazole, pyrazoles, including 1,2,3-oxadiazoles, 1,2,5- oxadiazoles and 1,3,4- oxadiazoles, piperazine, piperidines, pyrazine, pyrazoles, pyridazine, pyridine, pyrimidine, pyrroles, pyrrolidones, tetrahydrofuran, tetrahydrochysene furan Mutter, tetrazine, including 1,2,4,5- tetrazines, tetrazolium, including 1,2,3,4- tetrazoliums and 1,2,4,5- tetrazoliums, thiadiazole, including, 1,2, 3- thiadiazoles, 1,2,5- thiadiazoles and 1,3,4- thiadiazoles, thiazoles, thiophene-based, triazine, including 1,3,5-triazines and 1,2,4- Triazine, triazole, including 1,2,3-triazoles, 1,3,4- triazoles and similar compound.

Term as used herein " hydroxyl " is represented by molecular formula-OH.

Term as used herein " ketone " is by molecular formula A¹C(O)A²It is represented, wherein A¹And A²Can be, it is independent, this A kind of alkyl, cycloalkyl-alkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl or heteroaryl group described by text.

Term as used herein " azide " is by molecular formula-N₃It is represented.

Term as used herein " nitro " is by molecular formula-NO₂It is represented.

Term as used herein " nitrile " is represented by molecular formula-CN.

Term as used herein " silicyl " is by molecular formula-SiA¹A²A³It is represented, wherein A¹、A²And A³Can be, Independent, a kind of alkyl described herein, cycloalkyl-alkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl or heteroaryl Group.

Term as used herein " oxygen sulfo group " is by molecular formula-S (O) A¹,-S (O)₂A¹,-OS (O)₂A¹, or-OS (O)₂OA¹It is represented, wherein A¹Can be a kind of alkyl described herein, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, Aryl or heteroaryl group.In description herein, the shorthand that " S (O) " is S=O is write a Chinese character in simplified form.Terms used herein " sulfonyl " refers to It is oxygen sulfo group, it is by by molecular formula-S (O)₂A¹It is represented, wherein A¹Can be a kind of alkyl described herein, cycloalkyl, Alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl or heteroaryl group.Term as used herein " sulfone " is by molecular formula A¹S(O)₂A²Institute Represent, wherein A¹And A²Can be, independent, a kind of alkyl described herein, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkyne Base, aryl or heteroaryl group.Term as used herein " sulfoxide " is by molecular formula A¹S(O)A²It is represented, wherein A¹And A²Can be with It is, independent, a kind of alkyl described herein, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, cycloalkynyl radical, aryl or heteroaryl group.

Term as used herein " mercaptan " is represented by molecular formula-SH.

" R used herein¹”、“R²”、“R³" and " Rⁿ" (wherein n is an integer), it can independently possess institute above One or more groups listed.If for example, R¹It is an alternative in a straight chain alkyl groups, the hydrogen atom of alkyl group Ground is replaced by a hydroxyl group, an alkoxy group, an alkyl group, monohalide and similar substance.According to selected group, One group may be embodied in second group, or, second of selection is that first group can be suspended to and (be attached to) on second group.For example, According to a kind of " alkyl group being made up of amino group " this saying, amino group can be covered in the backbone of alkyl group.Another choosing Selecting is, amino group can be attached on the backbone of alkyl group.The property (S) of selected group will determine that first group is embedded or attached To second group.

Compound described herein may contain " selectivity substitution " composition.In general, regardless of whether being attached with before " selectivity " this term, " substitution " this term means the one or more hydrogen for specifying composition by a suitable substituent Replaced.Unless otherwise indicated, " selectivity substitution " group may possess one suitably in each alternative position of group Substituent, if there is substitution of the number that multiple positions can be selected from specific group more than one in any given structure Base is replaced, then the substituent can be identical or different in each position.The substituent of group is preferably capable of drawing Act those substituents for forming stable or chemically feasible compound.Also allow for, in some aspects, unless there are clear and definite phase Anti- explanation, single substituent can replace (that is, further substituteding or unsubstituted) by further selectivity.

In some respects, a kind of structure of compound can be represented with following molecular formula：

This molecular formula is understood to identical with following molecular formula：

Wherein n typically represents an integer.That is, RⁿIt is understood to represent five kinds of independent substituents, R^n(a), R^{n (b)}, R^n(c), R^n(d), R^n(e)." independent substituent " means that each R substituent can be defined as an independent.If for example, R in one specific embodiment^n(a)It is halogen, then R^n(b)Halogen is not necessarily in that specific embodiment.

To R in chemical constitution disclosed and illustrated herein and composition, R¹, R², R³, R⁴, R⁵, R⁶Etc. refer to several times. To R in detailed description, R¹, R², R³, R⁴, R⁵, R⁶Any description Deng progress is suitable for each to R, R¹, R², R³, R⁴, R⁵, R⁶Deng Any structure or composition being described.

Just become to be becoming increasingly popular using the phototube device of organic material, and they it is welcome the reason for have a lot. Many materials for manufacturing this device are relatively cheap, thus organic electro-optic device relative to inorganic device have it is potential into This advantage.In addition, the inherent characteristic of organic material, such as its pliability, may make them be very suitable for some special applications, such as Processing in flexible substrate.The example of organic photoelectric device device includes organic luminescent device (OLED), organic transistor, You Jitai Positive energy battery and organic photodetector.For OLED, organic material may have the advantage in performance compared to traditional material. For example, the luminous wavelength of organic luminous layer can generally be easy to be adjusted with appropriate dopant.

Decay of the exciton from singlet excited to ground state produces cold light, i.e. fluorescence.Exciton is from triplet excited state to ground state Decay produces cold light, i.e. phosphorescence.Because the strong spin-orbit coupling energy of heavy metal atom effectively strengthens singlet excited Intersect (ISC) between system between triplet excited state, phosphorescent metal complex, such as platinum complex have shown that they are harvested Both substance and triplet excited state and the potentiality for reaching 100% internal quantum.Therefore, phosphorescent metal complex is conduct The fine candidate material of organic luminescent device (OLED) light emitting layer dopant, it is very more all to obtain in academic and industrial circle Attention.And in the past ten years, people achieve necessarily on the commercialized road of technological direction high profit Achievement, for example, OLED is applied in the advanced display of smart mobile phone, television set and digital camera.

However, up to the present, blue electroluminescent devices are still the most field of challenge, reason in this technology At least partly it is the unstability of blue device.It is generally believed that the selection of host material is the one of the blue device stability of influence Individual factor.But, the minimum triplet excitation state (T of blue fluorescent material₁) energy it is very high, this generally means that blue device Host material minimum triplet excitation state (T₁) energy should be higher.This just brings to the blue device substrate material of exploitation It is difficult.

The present invention provides a kind of design of material route by the way that D-atom (s) to be introduced to the part of platinum complex.Due to deuterium Atomic ratio hydrogen atom weight, compared with c h bond, the vibration of carbon-deuterium (C-D) key can be reduced.Therefore, the shuttle belt of emission spectrum will Reduce or weaken, and whole spectrum can narrow.This is possible to promote transmitting performance that is photochromic and improving device.

Metal complex described herein can be customized or be adapted to need the spy of particular transmission or absorption characteristic Fixed application.The optical property of metal complex in the present invention can be by changing the structure of the part around metal center or leading to Cross the structure of fluorescent illuminant (s) on change part and be adjusted.For example, being inhaled with carrying electron donating substituents or electronics Receiving the metal complex of the part of substituent generally has different optical properties, including transmitting and absorption spectrum.Metal complex The color of thing can be adjusted by changing the conjugation group in fluorescent illuminant and part.

The transmitting of this compound can pass through, such as, the structure of modification part or fluorescent illuminant, and adjust (for example, From ultraviolet to near-infrared).Fluorescent illuminant is one group of atom in an organic molecule, and the atom can absorb energy to produce Singlet excited.The singlet excitons can produce decay to produce timely cold light rapidly.On the one hand, the complex compound can be big Lighted on partial visible spectrum.In specific example, complex compound described herein can be from 400 nanometers to 700 nanometers In the range of light.On the other hand, complex compound improves the stability and efficiency of legacy transmission complex compound.Another further aspect, it is described Complex compound can be used as, such as, biologic applications, anticancer, the transmitter in Organic Light Emitting Diode (OLED) or its combination, Luminous label.Last aspect, complex compound can be used for luminescent device, for example, compact fluorescent lamp (CFL), light emitting diode And incandescent lamp etc. (LED).

Disclosed herein is the compound or compound complex containing platinum, palladium or gold.Term compound, compound complex It is used alternatingly herein with complex compound.On the one hand, compound disclosed herein has neutral charge.

Compound disclosed by the invention can show preferable property, and with can by select appropriate part come The transmitting of adjustment and/or absorption spectrum.On the other hand, their compound, structure or the portion being particularly described herein Point any one or any number of may be left out.

Compounds as disclosed herein be applied to various optics and photoelectric device, include, but not limited to such as solar energy and Photo sensitive device etc light absorption device, Organic Light Emitting Diode (OLED), light emitting devices or existing light absorbs have light hair again Penetrate the device of ability and the mark for biologic applications.

As underdrawed above, disclosed compound is platinum complex.On the one hand, compound disclosed herein can be used Make OLED applications, such as full-color display, host material.

Compound disclosed herein has use value in various applications.As luminescent material, these compounds can use In Organic Light Emitting Diode (OLED), luminescent device and display and other luminescent devices.

On the other hand, these compounds can be in illuminating device, for example, there is provided than traditional material in organic luminescent device More preferable efficiency and/or service life.

Compound described herein can use a variety of methods to be made, and include, but not limited to described in example Those.

Compound disclosed herein includes delayed fluorescence emitter, phosphorescent emitters or combinations thereof.On the one hand, herein Disclosed compound is delayed fluorescence transmitter.On the other hand, compound disclosed herein is phosphorescent emitters.Yet another side Face a, compound disclosed herein is both a delayed fluorescence emitter and a phosphorescent emitters.

Disclosed herein is 1 type molecular formula complex compound：

R^aRepresent single, double, triple or the substitution of four bases, R^aIt is independent deuterium, CDH₂, CD₂H, CD₃, CD R¹R², CD₂R¹, or other Alkyl virtue, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, monosubstituted amino, two hydrocarbon containing deuterium Base amino, mono amino, diaryl amine, alkoxy, aryloxy group, halogeno-group, aralkyl, ester, alkoxy carbonyl group, amide groups, alkoxy Carbonylamino, alkoxy carbonyl base amino, aryloxycarbonyl base amino, aralkyl, sulfonamides, carbamoyl, alkylthio group, urea Base, phosphamide, silicyl, polymer；Or its any conjugate or compound.

R^b、R^c、R^dAnd R^eOr in each be all self-existent or non-existent, if exist, then R^b、 R^c、R^dAnd R^eIn each represent the substitution of single or double base, R respectively^b,R^dAnd R^eCan also be the substitution of three bases, R^bCan be four bases Substitution, and wherein R^b、R^c、R^dAnd R^eIn each be independent deuterium, it is halogen, hydroxyl, sulfydryl, nitro, cyano group, nitrile, different Nitrile, sulfinyl, sulfydryl, sulfo group, carboxyl, diazanyl；It is substituted or unsubstituted：Aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl Base, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkoxy, virtue The oxygen-containing carbonylamino of epoxide, haloalkyl, aralkyl, ester, alkoxy carbonyl, acyl amino, alkoxycarbonyl amino, aryl, Sulfamido, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or change Compound, R^aAnd R^bOptionally connection forms fusion ring, R^dAnd R^eOptionally connection forms fusion ring.

R¹And R²In each be all independent hydrogen, deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, Sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl-alkyl, cycloalkenyl group cyclenes Base, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, diaryl Amino, alkoxy, oxygen aryl, alkylhalide group, aralkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl Amino, sulfamido, sulfonamides, carbamyl, sulfanyl, urea groups, phosphamide, silicyl, polymer；Or its any combination Thing or compound.

On the one hand, the platinum complex has molecular formula 2, molecular formula 3, molecular formula 4, molecular formula 5, molecular formula 6 or molecular formula 7 Structure.On the other hand, they can not also obtain other structures or the part of Specific details, the present invention here comprising it Should not be limited to its those obtain Specific details herein structure or part.

R^b、R^c、R^dAnd R^eOr in each be all self-existent or non-existent, if exist, then R^b、 R^c、R^dAnd R^eIn each represent the substitution of single or double base, R respectively^b,R^dAnd R^eCan also be the substitution of three bases, R^bCan be four bases Substitution, and wherein R^b、R^c、R^dAnd R^eIn each be independent deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, Isonitrile, sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；Substitute or do not substitute：Aryl, cycloalkyl-alkyl, cycloalkenyl group cyclenes Base, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, diaryl Amino, alkoxy, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl ammonia Base, sulfamido, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or Compound, R^aAnd R^bOptionally connection forms fusion ring, R^dAnd R^eOptionally connection forms fusion ring.

R¹And R²In each be all independent hydrogen, deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, Sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl, ring cycloalkenyl group, heterocycle Base, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkane Epoxide, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, sulfonyl ammonia Base, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound.

For molecular formula 1 to 4 described herein, its realm may be defined in the following description.

On the one hand, R^aIt is monosubstituted.On the other hand, R^aIt is disubstituted.Yet another aspect, R^aIt is three substitutions.Last side Face, R^aIt is four substitutions.

On the one hand, R^aIt is independent deuterium, CDH₂, CD₂H, CD₃, CD R¹R², CD₂R¹, or other alkaryls containing deuterium, cycloalkyl alkane Base, cycloalkenyl group cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, double alkyl aminos, Dan Fang Base amino, double arylaminos, alkoxy, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxy carbonyl ammonia Base, aryloxycarbonylamino, sulfamido, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization； Or its any conjugate or compound.

On the one hand, a kind of R^bIt is present.On the other hand, R^bIt is non-existent.

On the one hand, R^bIt is monosubstituted.On the other hand, R^bIt is disubstituted.Yet another aspect, R^bIt is three substitutions.Last side Face, R^bIt is four substitutions.

On the one hand, it is each^KindR^bAll it is independent deuterium, halogen^Element, hydroxyl, mercaptan, nitro,^CyanogenBase, nitrile, isonitrile, sulfinyl 、^HydrogenSulfenyl, sulfo group, carboxyl, diazanyl；Can^GenerationIt is replacing or not section replace：Aryl, cycloalkyl, ring cycloalkenyl group, heterocyclic radical, heteroaryl, Alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, arylamino, alkoxy, aryloxy group, Alkylhalide group, alkyl, ester, alkoxy carbonyl, acyl amino, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamido, ammonia Sulphonyl, carbamyl, sulfanyl, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound.

On the one hand, a kind of Rc is present.On the other hand, Rc is non-existent.

On the one hand, Rc is monosubstituted.On the other hand, Rc is disubstituted.

On the one hand, each R^cAll it is independent deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, sulfurous Acyl group, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl Base, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkoxy, virtue Epoxide, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, sulfamido, ammonia sulphur Acyl, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound.

On the one hand, a kind of R^dIt is present.On the other hand, R^dIt is non-existent.

On the one hand, R^dIt is monosubstituted.On the other hand, R^dIt is disubstituted.Yet another aspect, R^dIt is three substitutions.

On the one hand, each R^dAll it is independent deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, sulfurous Acyl group, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl Base, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkoxy, virtue Epoxide, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, sulfamido, ammonia sulphur Acyl, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound.

On the one hand, a kind of R^eIt is present.On the other hand, R^eIt is non-existent.

On the one hand, R^eIt is monosubstituted.On the other hand, R^eIt is disubstituted.Yet another aspect, R^eIt is three substitutions.

On the one hand, each R^eAll it is independent deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, sulfurous Acyl group, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：Aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl Base, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkoxy, virtue Epoxide, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, sulfamido, ammonia sulphur Acyl, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound.

On the one hand, each in R, R1 and R2 be all independent hydrogen, halogen, hydroxyl, mercaptan, nitro, cyano group, Nitrile, isonitrile, sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl, aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, Alkenyl, alkynyl, amino, alkyl monosubstituted amino, double alkyl aminos, single arylamino, double arylaminos, alkoxy, aryloxy group, alkyl halide Base, alkyl, ester, alkoxy carbonyl, acyl amino, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamido, sulfonamides, Carbamyl, sulfanyl, urea groups, phosphamide, alternative silicyl, polymerization, or, or its any conjugate or compound.Zero On the one hand, each in R, R1 and R2 be all independent hydrogen, aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, Each in alkenyl, alkynyl, halogen, hydroxyl, mercaptan, nitro, cyano group or amino another further aspect, R, R1 and R2 is all Independent hydrogen, aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, alkenyl or alkynyl.

On the one hand, for any molecular formula disclosed herein,It is independent one in having structure Kind.On the other hand, they can also include their other structures not described specifically herein or part, and this Invention is not intended to be only limitted to structure or the part that they those are especially described.

2nd, exemplary compounds

On the one hand, the metal complex illustrated by the disclosure can include one or more following structures.It is another Aspect, they also can be comprising the other structures not yet explicitly addressed herein or the part of these structures, and is not intended to the present invention Disclosure be limited to clearly to address this etc. structure or part thereof.

There is disclosed herein including the device of one or more in compound disclosed herein.

Compounds as disclosed herein be applied to various optics and photoelectric device, include, but not limited to such as solar energy and Light absorption device, Organic Light Emitting Diode (OLED), light emitting devices or existing light absorbs have light again as photo sensitive device The device of emissivities and the mark for biologic applications.

Compound illustrated herein can be used in a kind of such as OLED etc luminescent device.Fig. 1 illustrates OLED 1000 sectional drawing.OLED 1000 includes matrix 1002, positive level 1004, hole mobile material (HTL) 1006, light processing material 1008th, the metal cathode layer 1012 of electron transport material (ETL) 1010 and one.Anode 1004 is usually transparent material, for example, aoxidize Indium tin.Light processing material 1008 can include an emitter and the luminescent material (EML) of a main body.

Fig. 1 shows OLED 1000 sectional drawing, and it includes：Matrix 1002 with an anode 1004, usually transparent material Material, such as tin indium oxide,；One hole transport material (HTL) 1006；One lighting function material 1008, such as including a transmitting The luminescent material of body and a main body；The metal cathode layer 1012 of one electron transport material (ETL) 1010 and one.On the one hand, such as OLED etc luminescent device can include one layer or more.In all senses, this one or this etc. any layer of multilayer can include oxygen Change indium tin (ITO), MoO₃、Ni₂O₃, poly- (3,4- ethene dioxythiophenes) (PEDOT), kayexalate (PSS), 4,4', 4 "-((E of 1E, 1'E, 1 ")-cyclopropane -1,2,3- trimethylenes three (Cyano-methyl subunit)) three (2,3,5,6- tetrafluoros cyanophenyl) (NHT-49), 2,2'- (perfluorodecalin -2,6- diyls) malononitrile (NHT-51), 2,3,5,6- tetrafluoros-paraquinones bismethane (F4-TCNQ), N, N '-two -1- naphthyls-N, N '-biphenyl -1,1 '-biphenyl -4,4 ' diamines (NPD), 1,1- are along ((two -4- are to first Phenylamino) phenyl) hexamethylene (TAPC), 2,6- is along (N- carbazyls)-pyridine (mCpy), 2,8- along (diphenyl phosphate azide) two Benzothiophene (PO15), LiF, LiQ, Cs₂CO₃、CaCO₃, Al or its composition.In this embodiment, light processing material The bed of material 1008 can include one or more compounds of the present invention, optionally a related material of main part.ETL layers 1010 and 1006 Can also comprising one or more compounds and with the hand-to-hand another implanted layer of electricity.The material of implanted layer may include (electron injection Layer) EIL, (hole injection layer) HIL and CPL (cap rock), its form can be simple layer or be dispersed in transmission material.Main body material Material can be any suitable material of main part known in the art.OLED glow color handles the luminous of material 1008 by light Energy (optical energy gap) is determined, can be tuned as described above by the electronic structure of tuning emitting compound and/or material of main part Light handles the luminous energy (optical energy gap) of material 1008.The electricity in hole mobile material and ETL layers 1010 in htl layer 1006 Sub- transmission material can include any suitable hole transporter known in the art.This selection is belonged to and is familiar with this technology person Extent of competence.

Obviously, phosphorescence can be presented in compound of the invention.Phosphorescent OLED (that is, the OLED with phosphorescent emitters) typically has There is the device efficiency higher than such as fluorescence OLED etc other OLED.《It is natural》The 151-154 pages of 395 phase in 1998 is said Understand the luminescent device based on electroluminescent phosphorescence emitter, because of its instruction content on OLED especially with respect to fluorescence OLED, It is herein incorporated by reference in this.

In all senses, any layer in the one layer or more illustrated by Fig. 1 may each comprise tin indium oxide (ITO), MoO3, Ni2O3, poly- (3,4- ethene dioxythiophenes) (PEDOT), kayexalate (PSS), N, N '-two -1- naphthyls-N, N '-connection Benzene -1,1 '-biphenyl -4,4 ' diamines (NPD), 1,1- are suitable along ((two -4- p-totuidines bases) phenyl) hexamethylene (TAPC), 2,6- (N- carbazyls)-pyridine (mCpy), 2,8- are along (diphenyl phosphate azide) dibenzothiophenes (PO15), LiF, Al or its combination Thing.

Light process layer 1008 may include one or more compounds of the present invention, optionally a related material of main part.It is main Body material can be any suitable material of main part known in the art.OLED glow color handles material 1008 by light Luminous energy (optical energy gap) decision, can be by tuning the electronic structure of emitting compound, material of main part or both come tuned light Handle the luminous energy (optical energy gap) of material 1008.The electronics in hole mobile material and ETL layers 1010 in htl layer 1006 Transmission material may include any suitable hole transporter known in the art.

Phosphorescence can be presented in compound illustrated herein.Phosphorescent OLED (that is, the OLED with phosphorescent emitters) typically has There is the device efficiency higher than such as fluorescence OLED etc other OLED.It is illustrated in greater detail in WO2000/070655 Based on the luminescent device of electroluminescent phosphorescence emitter, because of its instruction content on OLED especially with respect to fluorescence OLED, to draw Mode is incorporated into this.

Being proposed to of the example below intactly discloses and illustrated to want for this paper to those skilled in the art Ask how compound, constituent, object, device and/or the method for protection make and assess, and intention is pure to be exemplary And not make scope limitation.The accuracy (for example, quantity, temperature etc.) in terms of numeral has been tried to make sure that, but for some Error and deviation should take in.It is outer except as otherwise indicating, part be by weight in part, temperature be by DEG C in units of or It is environment temperature, and pressure is at or approximately at atmospheric pressure.

The various preparation methods of compound illustrated herein are told about with example.These methods provided are to be used for Illustrate various preparation methods, but its intention not limits any method as described herein.Correspondingly, in disclosure of the invention Appearance gathers around seised those skilled in the art and can easily change methods described or employ different approach to prepare herein One or more in illustrated compound.Following aspect is only as an example, and its intention not makees scope limitation.Temperature, urge Agent, concentration, reactant composition and other process conditions can change, and seised is gathered around to the disclosure Art personnel can easily select appropriate reactant and condition by complex compound for needed for.

In CDCl₃Or DMSO-d₆In solution, recorded by Varian liquid NMR¹H NMR (hydrogen nuclear magnetic resonance) With¹³C NMR (nuclear magnetic resonance of carbon) spectrum is 300,400 or 500MHz, and chemical shift is using remaining protonated solvent as base It is accurate.If using CDCl₃As solvent, then recorded using tetramethylsilane (δ=0.00ppm) as interior reference¹H NMR (hydrogen Nuclear magnetic resonance) spectrum；Using CDCl₃(δ=77.00ppm) is recorded as interior reference¹³C NMR (nuclear magnetic resonance of carbon) spectrum.Such as Fruit uses DMSO-d⁶As solvent, then using remaining H₂O (δ=3.33ppm) is recorded as interior reference¹H NMR (proton magnetic Resonance) spectrum；Using DMSO-d⁶(δ=39.52ppm) is recorded as interior reference¹³C NMR (nuclear magnetic resonance of carbon) spectrum.Below Abbreviation (or combinations thereof) is to be used to explain¹H NMR (hydrogen nuclear magnetic resonance) diversity：S=singlets, d=two-wire states, t= Triplet state, the line states of q=tetra-, the line states of p=five, the multi-thread states of m=, br=is wide.

Platinum complex 1 is prepared according to following scheme：

The synthesis of the bromo- 4-D- pyridines of 2-：To 100mL flask addition 2,6- dibromo pyridines (2.36g, 10mmol), It is dissolved at room temperature in the tetrahydrofuran of fresh distillation (THF).Then it is added dropwise i-PrMgBr's (8mL, 12.8mmol) Hexane solution.After one hour of the stirring, D is added₂O(5mL).After about 0.5 hour, with DCM (dichloromethane) extraction mixture, And each organic phase is combined, cleaned with bittern, use Mg₂SO₄Dry.Remove solvent, obtain a mixture (dark brown oil, 497mg), crude product is directly used in next step：

The synthesis of the 2-D- parts of complex compound 1：1- methylimidazoles (16mg, 0.2mmol) are added to a 15mL seal pipe, 2- (3- (1H- pyrazol-1-yls) phenoxy group) -9H- carbazoles (130mg, 0.4mmol), the bromo- 4-D- pyridines (346mg, 2mmol) of 2-, K₂CO₃(111mg, 0.8mmol), toluene (2mL) and CuI (15mg, 0.08mmol).Bubbled 10 minutes by mixture with nitrogen, and Stirred 3 days at 120 DEG C.After the cooling period, addition water and ethyl acetate (EA), and filtered to mixture.Using ethyl acetate Aqueous phase is extracted, and combines each organic phase, is cleaned with bittern, uses Na₂SO₄Dry.Using PE/EA=10:1 as elutriant, leads to Cross silica gel column chromatography to purify obtained solution, produce target product (brown solid, 160mg, 99% yield).¹H NMR (500MHz,DMSO-d⁶):δ 8.55 (d, J=2.6Hz, 1H), 8.33 (d, J=8.4Hz, 1H), 8.28 (d, J=7.9Hz, 1H), 8.13 (t, J=7.8Hz, 1H), 7.84 (s, 1H), 7.82 (s, 1H), 7.73 (d, J=1.7Hz, 1H), 7.64 (d, J= 8.5Hz, 1H), 7.60-7.56 (m, 2H), 7.54-7.47 (m, 3H), 7.39 (t, J=7.5Hz, 1H), 7.14 (dd, J=8.4, 2.2Hz, 1H), 6.99 (dd, J=8.1,2.4Hz, 1H), 6.56 (s, 1H).MS(ESI):404.2[M+H⁺], 426.1 [M+Na⁺]

The synthesis of complex compound 1：Into glove-box 15mL seal pipe addition 2-D- parts (20mg, 0.05mmol), potassium chloroplatinite (23mg, 0.055mmol) and acetic acid (1mL), and after being bubbled 15 minutes by mixture with nitrogen, 110 DEG C are heated the mixture to, three days when being.After cooling to room temperature, produced solution is handled with water, and precipitated Go out a small amount of solid.Collection takes solution, and using DCM (dichloromethane) as elutriant, by silica gel column chromatography come purified solution, produces Target product (yellow solid, 14mg, 47% yield).¹H NMR(300MHz,CDCl₃):δ 8.26 (d, J=8.6Hz, 1H), 8.13 (d, J=2.7Hz, 1H), 8.02 (d, J=7.1Hz, 1H), 7.98-7.88 (m, 2H), 7.84 (s, 1H), 7.79 (d, J= 8.3Hz, 1H), 7.44-7.29 (m, 3H), 7.21 (d, J=8.0Hz, 1H), 7.16-7.06 (m, 3H), 6.67 (s, 1H).Room temperature CIE (0.156,0.124) in lower PMMA (polymethyl methacrylate).

Platinum complex 1 is prepared according to following scheme：

Into glove box a 15mL seal pipe addition part (30mg, 0.075mmol), potassium chloroplatinite (31mg, 0.075mmol) with acetic acid (1mL), and after allowing mixture to bubble 15 minutes, mixture is heated at 110 DEG C, when being Three days.After cooling to room temperature, produced solution is handled with water (10mL), and is settled out a small amount of solid.Collection takes molten Liquid, and use PE/DCM=1:2 as elutriant, by silica gel column chromatography come purified solution, produce target product (yellow solid, 22mg, 49% yield).¹H NMR(500MHz,DMSO-d⁶):δ 9.30 (s, 1H), 8.92 (d, J=2.7Hz, 1H), 8.31 (d, J =8.6Hz, 1H), 8.25 (dd, J=8.7,1.8Hz, 1H), 8.20 (d, J=2.2Hz, 1H), 8.18 (d, J=7.5Hz, 1H), 8.11 (d, J=8.2Hz, 1H), 7.90 (d, J=8.2Hz, 1H), 7.53 (d, J=7.6Hz, 1H), 7.50 (t, J=7.6Hz, 1H), 7.43 (t, J=7.5Hz, 1H), 7.25 (d, J=7.9Hz, 1H), 7.24-7.22 (m, 1H), 7.00 (d, J=8.0Hz, 1H), 6.93 (t, J=3.0Hz, 1H).

Platinum complex 3 is prepared according to following scheme：

The synthesis of 2- (benzyloxy bromide)-(4-D- pyridine -2- bases) -9H- carbazoles：2- (benzyls are added to a 15mL seal pipe Epoxide) -9- (4- bromopyridine -2- bases) -9H- carbazoles (107mg, 0.25mmol).Then iPrMgBr is added dropwise at room temperature Tetrahydrofuran (THF) solution of (1.5mL, 1M).After one hour of the stirring, D is added₂O(0.6mL).After 30 minutes, Na is used₂SO₄It is right Mixture is dried.Using PE/EA=15:1, as elutriant, produced solution is purified by silica gel column chromatography, is produced The reactant (white solid, 13mg) and target product (brown solid, 75mg, 85% yield) of recycling.¹H NMR (300MHz,DMSO-d⁶):δ 8.77 (d, J=4.9Hz, 1H), 8.16 (d, J=8.4Hz, 2H), 7.78 (d, J=8.9Hz, 2H), 7.52 (d, J=6.2Hz, 3H), 7.40-7.36 (m, 5H), 7.32 (t, J=7.4Hz, 1H), 7.07 (dd, J=8.1, 1.2Hz, 1H), 5.22 (s, 2H) .MS (ESI):351.2[M+H⁺], 373.1 [M+Na⁺]。

The synthesis of 9- (4-D- pyridine -2- bases) -9H- carbazole -2- propyl alcohol：2- (benzyloxy) -9- is added to an autoclave (4-D- pyridine -2- bases) -9H- carbazoles (331mg, 0.9mmol), Pd/C (38mg) and EA (25mL).Mixture is emptied, then used Nitrogen is refilled, and is operated three times, and is stirred 24 hours at 0.8MPa and 65 DEG C.After cooling down, mixture was carried out Filter and use Na₂SO₄Filtered fluid is dried.Using PE/EA=10:1,2:1, as elutriant, is purified by silica gel column chromatography The solution obtained, produces the reactant (brown solid, 6mg) and target product (white solid, 231mg, 98% of recycling Yield).¹H NMR(300MHz,DMSO-d⁶):δ 9.60 (s, 1H), 8.76 (d, J=4.9Hz, 1H), 8.13-8.06 (m, 1H), 8.03 (d, J=8.4Hz, 1H), 7.78 (s, 1H), 7.73 (d, J=8.1Hz, 1H), 7.51 (d, J=4.7Hz, 1H), 7.41- 7.32 (t, J=7.7Hz, 1H), 7.29 (t, J=7.7Hz, 1H), 7.21 (d, J=2.1Hz, 1H), 6.82 (dd, J=8.4, 2.1Hz,1H)。MS(ESI):262.1[M+H⁺].

The synthesis of the 4-D- parts of complex compound 1：3- methylimidazoles (16mg, 0.2mmol) are added to a 15mL seal pipe, 4- (3- (1H- pyrazol-1-yls) phenoxy group) -9H- carbazoles (130mg, 0.4mmol), the bromo- 4-D- pyridines of 2- (235mg, 0.9mmol), K₂CO₃(880mg, 2.7mmol), toluene (2mL) and CuI (0.18mmol, 10m).With nitrogen by mixture foaming 10 Minute, and stirred 3 days at 120 DEG C.After the cooling period, addition water and ethyl acetate (EA), and filtered to mixture.Using Ethyl acetate extracts aqueous phase, and combines each organic phase, is cleaned with bittern, uses Na₂SO₄Dry.Using PE/EA=10:1 conduct Elutriant, obtained solution is purified by silica gel column chromatography, produces target product (brown solid, 75mg, 99% yield) 。¹H NMR(500MHz,DMSO-d⁶):δ 8.72 (d, J=4.9Hz, 1H), 8.54 (d, J=8.4Hz, 1H), 8.28 (d, J= 7.9Hz, 1H), 7.13 (t, J=7.8Hz, 1H), 7.84 (s, 1H), 7.82 (s, 1H), 7.73 (d, J=1.7Hz, 1H), 7.64 (d, J=8.5Hz, 1H), 7.60-7.56 (m, 2H), 7.54-7.47 (m, 3H), 7.39 (t, J=7.5Hz, 1H), 7.14 (dd, J =8.4,2.2Hz, 1H), 7.59 (dd, J=8.1,2.4Hz, 1H), 6.55 (s, 1H).MS(ESI):404.2[M+H⁺], 426.1 [M+Na⁺]。

The synthesis of complex compound 3：4-D- parts (20mg, 0.05mmol), potassium chloroplatinite are added to a 15mL seal pipe (23mg, 0.055mmol) and acetic acid (1mL), and after being bubbled 15 minutes by mixture with nitrogen, 110 DEG C are heated the mixture to, For when three days.After cooling to room temperature, produced solution is handled with water, and is settled out a small amount of solid.Collection takes solution, And using DCM (dichloromethane) as elutriant, by silica gel column chromatography come purified solution, produce target product (yellow solid, 9mg, 47% yield).¹H NMR(500MHz,DMSO-d⁶):δ 9.31 (d, J=5.9Hz, 1H), 8.94 (d, J=2.7Hz, 1H), 8.32 (s, 1H), 8.21 (d, J=2.2Hz, 1H), 8.19 (d, J=6.8Hz, 1H), 8.12 (d, J=8.5Hz, 1H), 7.91 (d, J=8.3Hz, 1H), 7.55 (d, J=7.7Hz, 1H), 7.51 (t, J=7.7Hz, 1H), 7.47-7.42 (m, 2H), 7.28- 7.23 (m, 2H), 7.01 (d, J=8.0Hz, 1H), 6.94 (t, J=2.5Hz, 1H).PMMA (poly-methyl methacrylates at room temperature Ester) in CIE (0.155,0.117).

Platinum complex 4 is prepared according to following scheme：

The synthesis of the 5-D- parts of complex compound 4：To 48mL seal pipe add the bromo- 9- of 2- (3-D- pyridine -2- bases) - 9H- carbazoles (196mg, 0.6mmol), N- (3- hydroxyphenyls) pyrazoles (80mg, 0.5mmol), DMG (15mg, 0.15mmol), Cs₂CO₃489mg, 1.5mmol), CuI (14mg, 0.075mmol) and Isosorbide-5-Nitrae-dioxane (5mL).Allowed with nitrogen Mixture bubbles 10 minutes, and is stirred 3 days at 120 DEG C.After the cooling period, solvent is removed.With water and ethyl acetate (EA) to mixed Compound is handled, and it is filtered.Aqueous phase is extracted using ethyl acetate, and combines each organic phase, is cleaned with bittern, Use Na₂SO₄Dry.Using PE/EA=10:1 as elutriant, and obtained solution is purified by silica gel column chromatography, produces target Product (brown solid, 144mg, 71% yield).¹H NMR(500MHz,DMSO-d⁶):δ 8.72 (dd, J=4.8,2.0Hz, 1H), 8.54 (d, J=2.6Hz, 1H), 8.32 (d, J=8.4Hz, 1H), 8.27 (d, J=7.7Hz, 1H), 8.12 (dd, J= 7.4,1.9Hz, 1H), 7.83 (d, J=8.3Hz, 1H), 7.73 (d, J=1.7Hz, 1H), 7.63 (dd, J=8.1,2.1Hz, 1H), 7.59 (d, J=2.2Hz, 1H), 7.57 (t, J=2.2Hz, 1H), 7.53-7.47 (m, 3H), 7.39 (t, J=7.4Hz, 1H), 7.13 (dd, J=8.5,2.2Hz, 1H), 6.99 (dd, J=7.9,2.4Hz, 1H), 6.55 (t, J=2.2Hz, 1H).

The synthesis of complex compound 4：5-D- parts (40mg, 0.1mmol), potassium chloroplatinite are added to a 15mL seal pipe (46mg, 0.11mmol) and acetic acid (1mL), and with N₂Allow mixture bubble 10 minutes after, at 110 DEG C to mixture carry out Heating, three days when being.After cooling to room temperature, produced solution is handled with water, and is settled out a small amount of solid.Collection takes Solution, and use PE/DCM=1:1 as elutriant, by silica gel column chromatography come purified solution, and producing target product, (yellow is solid Body, 8mg, 13% yield).¹H NMR(300MHz,DMSO-d⁶):δ 9.31 (d, J=5.3Hz, 1H), 8.94 (d, J=2.7Hz, 1H), 8.27 (dd, J=6.9,1.2Hz, 1H), 8.24-8.16 (m, 2H), 8.12 (d, J=8.1Hz, 1H), 7.91 (d, J= 8.3Hz, 1H), 7.54 (t, J=7.3Hz, 2H), 7.50-7.40 (m, 2H), 7.31-7.19 (m, 2H), 7.01 (d, J= 8.0Hz, 1H), 6.94 (t, J=2.4Hz, 1H).CIE (0.146,0.109) in PMMA (polymethyl methacrylate) at room temperature.

Platinum complex 3 is prepared according to following scheme：

The synthesis of ligand complex 7：4-CH is added to a 15mL seal pipe₃- part (42mg, 0.1mmol), CH₃CH₂ONa (14mg, 0.2mmol) and CH₃CH₂OD(1mL).After being bubbled 10 minutes by mixture with nitrogen, and mixture is allowed to flow back 3 days.After cooling to room temperature, solution is extracted with ethyl acetate, and combines each organic phase, is cleaned with bittern, uses Na₂SO₄It is dry It is dry.Using PE/EA=5:1, as elutriant, produced solution is purified by silica gel column chromatography, produces target product (white Solid, 42mg 4-³D- parts, 100% yield).¹H NMR(300MHz,CDCl₃):δ 8.55 (d, J=4.8Hz, 1H), 8.08 (s, 1H), 8.05 (s, 1H), 7.77 (d, J=8.5Hz, 1H), 7.68 (s, 1H), 7.54 (s, 1H), 7.49-7.31 (m, 7H), 7.14 (s, 1H), 7.05 (d, J=8.4Hz, 1H), 6.95 (d, J=7.8Hz, 1H), 6.43 (s, 1H).

The synthesis of complex compound 7：4-CD is added to a 15mL seal pipe₃- part (42mg, 0.1mmol), potassium chloroplatinite (46mg, 0.11mmol) and acetic acid (1mL).Bubbled 10 minutes by mixture with nitrogen, and heat the mixture to 110 DEG C, when being Three days.After cooling to room temperature, produced solution is handled with water, and is settled out a small amount of solid.Collection takes solution, and adopts Use PE/DCM=1:2 as elutriant, by silica gel column chromatography come purified solution, produce target product (yellow solid, 23mg, 38% yield).¹H NMR(300MHz,CDCl₃):δ 9.10 (d, J=5.7Hz, 1H), 8.08-7.99 (m, 2H), 7.92 (d, J= 8.0Hz, 1H), 7.82 (s, 1H), 7.78 (d, J=8.2Hz, 1H), 7.35 (m, 4H), 7.20 (m, 1H), 7.11 (m, 2H), 6.94 (d, J=6.2Hz, 1H), 6.66 (d, J=1.8Hz, 1H).

When emission spectrum is shown in aglucon addition D-atom, triplet state energy gap is almost identical.

The representative data of emitter excitation is to use 5%PMMA (polymethyl methacrylate) chloroform molten from it Film emission spectrum prepared by liquid is obtained.CIE index coordinates in PMMA (polymethyl methacrylate) are non-deuterate complex compounds (0.163,0.131), complex compound 1 (0.156,0.124), complex compound 2 (0.160,0.119), complex compound 3 (0.155,0.117) With complex compound 4 (0.146,0.109).Excitation can be improved by deuterate.In the methyl substituted complex compound 7 of deuterate shown in Fig. 7 In the case of, compared with its CIE coordinate for the non-deuterate complex compound 7 of (0.147,0.100), DCM (dichloromethane) is molten at room temperature Emission spectrum in liquid shows more preferably CIE coordinates (0.145,0.093) in navy blue region.

One of ordinary skill in the art is based on this specification, would appreciate that other modifications and substitutions of each side are specifically real Apply mode.Therefore, this specification only may be interpreted as being illustrative.It should be understood that illustrated herein and explanation form should be made For the example of embodiment.Explain herein and expositor can be substituted with other elements and material, part and program can With reverse, it is possible to the specific feature of independent utility, for all these, one of ordinary skill in the art is from this specification It would appreciate that after middle benefit.Herein described element can be changed, without departing from the spirit described in claims below And scope.

Claims (10)

1. a kind of platinum compounds, it is characterised in that with following molecular formula：

Wherein R^aRepresent single, double, triple or the substitution of four bases, R^aIt is independent deuterium, R^aIt is independent to constitute CDH₂, CD₂H, CD₃, CD R¹R², CD₂R¹, or other alkyl virtues containing deuterium, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkyl, alkenyl, alkynyl, amino, singly take For amino, Dialkylamino, mono amino, diaryl amine, alkoxy, aryloxy group, halogeno-group, aralkyl, ester, alkoxy carbonyl group, acyl Amido, alkoxycarbonyl amino, alkoxy carbonyl base amino, aryloxycarbonyl base amino, aralkyl, sulfonamides, carbamyl Base, alkylthio group, urea groups, phosphamide, silicyl, polymer；Or its any conjugate or compound；

R^b、R^c、R^dAnd R^eOr in each be all self-existent or non-existent, if exist, then R^b、R^c、R^d And R^eIn each represent the substitution of single or double base, R respectively^b,R^dAnd R^eCan also be the substitution of three bases, R^bCan be the substitution of four bases, And wherein R^b、R^c、R^dAnd R^eIn each be independent deuterium, halogen, hydroxyl, sulfydryl, nitro, cyano group, nitrile, isonitrile, sub- sulphur Acyl group, sulfydryl, sulfo group, carboxyl, diazanyl；It is substituted or unsubstituted：Aryl, cycloalkyl, cycloalkenyl group, heterocyclic radical, heteroaryl, alkane Base, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, The oxygen-containing carbonylamino of haloalkyl, aralkyl, ester, alkoxy carbonyl, acyl amino, alkoxycarbonyl amino, aryl, sulfonyl ammonia Base, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound, R^a And R^bOptionally connection forms fusion ring, R^dAnd R^eOptionally connection forms fusion ring；

R¹And R²In each be all independent hydrogen, deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, sulfurous Acyl group, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：It is aryl, cycloalkyl-alkyl, cycloalkenyl group cycloalkenyl group, miscellaneous Ring group, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, Alkoxy, oxygen aryl, alkylhalide group, aralkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, Sulfamido, sulfonamides, carbamyl, sulfanyl, urea groups, phosphamide, silicyl, polymer；Or its any conjugate or Compound.

2. platinum compounds according to claim 1, it is characterised in that：The compound also has molecular formula two, molecular formula 3rd, the structure of molecular formula four, molecular formula five, molecular formula six or molecular formula seven；

R^b、R^c、R^dAnd R^eOr in each be all self-existent or non-existent, if exist, then R^b、R^c、R^d And R^eIn each represent the substitution of single or double base, R respectively^b,R^dAnd R^eCan also be the substitution of three bases, R^bCan be the substitution of four bases, And wherein R^b、R^c、R^dAnd R^eIn each be independent deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, Sulfinyl, sulfhydryl, sulfo group, carboxyl, diazanyl；Substitute or do not substitute：It is aryl, cycloalkyl-alkyl, cycloalkenyl group cycloalkenyl group, miscellaneous Ring group, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, Alkoxy, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, sulfonyl Amino, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound, R^aAnd R^bOptionally connection forms fusion ring, R^dAnd R^eOptionally connection forms fusion ring.

R¹And R²In each be all independent hydrogen, deuterium, halogen, hydroxyl, mercaptan, nitro, cyano group, nitrile, isonitrile, sulfurous Acyl group, sulfhydryl, sulfo group, carboxyl, diazanyl；It is alternative or irreplaceable：It is aryl, cycloalkyl-alkyl, cycloalkenyl group cycloalkenyl group, miscellaneous Ring group, heteroaryl, alkyl, alkenyl, alkynyl, amino, alkyl monosubstituted amino, dialkyl amido, single arylamino, ammonia diaryl base, Alkoxy, aryloxy group, alkylhalide group, alkyl, ester, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, fragrant oxygen carbonyl amino, sulfonyl Amino, sulfonamides, carbamyl, alkylthio group, urea groups, phosphamide, silicyl, polymerization；Or its any conjugate or compound.

3. platinum compounds according to claim 1, it is characterised in that：WhereinR^dAnd R^eConnection forms fusion Ring simultaneously can be selected from following structure：

4. the platinum compounds according to any one in claim 1-3, it is characterised in that：The platinum compounds has neutrality Electric charge.

5. the platinum compounds according to any one in claim 1-3, it is characterised in that：The platinum compounds is from by being complexed Selected in the group that thing 1 is constituted to complex compound 312：

6. a kind of emitter, it is characterised in that：The emitter is a delayed fluorescence emitter and/or phosphorescent emitters, including Platinum compounds described in claim 1.

7. emitter according to claim 6, it is characterised in that：The chosen compound is to have in device environment 100% internal quantum.

8. emitter according to claim 8, it is characterised in that：The emitter is Organic Light Emitting Diode.

9. platinum compounds according to claim 1, it is characterised in that：Polymerization includes poly- alkyl, gathered in the platinum compounds Ester or polyethers.

10. platinum compounds according to claim 9, it is characterised in that：Polymerization includes-(CH₂O)_n-CH₃、-(CH₂CH₂O)_n- CH₃、-[CH₂CH(CH₃)]_n-CH₃、-[CH₂CH(COOCH₃)]_n-CH₃、-[CH₂CH(COOCH₂CH₃)]_n-CH₃Or-[CH₂CH (COO^tBu)]_n-CH₃, wherein n is an integer.