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CN113698523A - High molecular compound containing space charge transfer polymer sensitizer and resonance structure condensed ring unit and organic electroluminescent device - Google Patents

High molecular compound containing space charge transfer polymer sensitizer and resonance structure condensed ring unit and organic electroluminescent device Download PDF

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CN113698523A
CN113698523A CN202111033368.4A CN202111033368A CN113698523A CN 113698523 A CN113698523 A CN 113698523A CN 202111033368 A CN202111033368 A CN 202111033368A CN 113698523 A CN113698523 A CN 113698523A
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CN113698523B (en
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王利祥
邵世洋
胡军
王一诺
赵磊
王兴东
吕剑虹
王淑萌
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Changchun Institute of Applied Chemistry of CAS
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
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Abstract

本发明提供了一种含有空间电荷转移聚合物敏化剂和共振结构稠环单元的高分子化合物，所述高分子发光材料具有式(I)和/或式(II)所示的结构。与现有技术相比，该高分子化合物具体以下优点：一方面，空间电荷转移高分子的给体和受体之间采用非共轭结构连接，其电子云重叠程度较小，产生TADF效应，三线态激子可以反系间窜越到单线态，接着通过

Figure DDA0003246045830000012
传递过程将能量转移至共振稠环单元MR发光，实现对三线态激子的利用；另一方面，得益于共振稠环单元MR的刚性骨架，非辐射跃迁受到抑制，光致荧光量子效率高；同时，由于刚性结构可抑制分子激发态振动弛豫，重组能小，表现出窄光谱发射和高色纯度的特点。
Figure DDA0003246045830000011
The present invention provides a polymer compound containing a space charge transfer polymer sensitizer and a resonance structure condensed ring unit, and the polymer light-emitting material has a structure represented by formula (I) and/or formula (II). Compared with the prior art, the polymer compound has the following advantages: on the one hand, the donor and the acceptor of the space charge transfer polymer are connected by a non-conjugated structure, and the degree of overlap of the electron clouds is small, resulting in a TADF effect, Triplet excitons can cross between antisystems to singlet states, and then pass through
Figure DDA0003246045830000012
The transfer process transfers energy to the resonant condensed ring unit MR to emit light, realizing the utilization of triplet excitons; on the other hand, thanks to the rigid skeleton of the resonant condensed ring unit MR, non-radiative transitions are suppressed, and the photoluminescence quantum efficiency is high At the same time, because the rigid structure can suppress the vibrational relaxation of molecular excited states, the recombination energy is small, and it exhibits the characteristics of narrow spectral emission and high color purity.
Figure DDA0003246045830000011

Description

High molecular compound containing space charge transfer polymer sensitizer and resonance structure condensed ring unit and organic electroluminescent device
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a macromolecular compound containing a space charge transfer polymer sensitizer and a resonance structure condensed ring unit and an organic electroluminescent device.
Background
High molecular light emitting materials are the basis for the fabrication of low cost and large area Organic Light Emitting Diodes (OLEDs) based on solution processing. Depending on the light emitting mechanism, the polymer light emitting materials can be classified into three types: fluorescent polymers, phosphorescent polymers, and Thermally Activated Delayed Fluorescence (TADF) polymers. Among them, the fluorescent polymer is limited by the spin statistic theory, and the fluorescent unit can only utilize singlet excitons accounting for 25% of the total number of excitons, so the luminous efficiency is low. The phosphorescent polymer can emit light by utilizing singlet excitons and triplet excitons simultaneously due to the spin-orbit coupling effect of heavy metals, and the exciton utilization rate can reach 100%. However, the phosphorescent polymer needs expensive heavy metal, which increases material cost, and the stability of the blue phosphorescent metal complex is poor, which limits practical application of the phosphorescent polymer.
The thermally activated delayed fluorescence polymer has the energy level difference (delta E) between the singlet state and the triplet stateST) Small characteristic, can utilize the crossing process between the reverse systems to convert the triplet exciton into the singlet exciton for radiation transition luminescence, and has the advantages of realizing the radiation transition luminescence without introducing heavy metalThe utilization of triplet excitons reaches the maximum exciton utilization rate of 100 percent, so the method has the advantages of low material cost and high efficiency and has wide development prospect.
Currently, TADF polymers are generally designed such that an electron donor and an electron acceptor are connected by a conjugated structure, and the light-emitting nature thereof is derived from donor-to-acceptor chemical bond charge transfer (TBCT). In order to satisfy an efficient separation of the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) to obtain a small Δ ESTA larger twist angle between the donor and acceptor units is generally required to reduce the degree of overlap of their electron clouds. The introduction of larger twist angles tends to result in a decrease in fluorescence quantum yield (PLQY). On the other hand, the electron cloud delocalization degree is often larger due to the adoption of the conjugated structure connection between the donor and the acceptor, so that the red shift of the emission spectrum is easily caused, and the blue light emission is not favorably realized. Therefore, how to design a more suitable polymer material to solve the above-mentioned defects in material design and light-emitting performance has become one of the problems to be solved by many prospective researchers in the field.
Disclosure of Invention
In view of the above, the present invention provides a polymer compound and an organic electroluminescent device having a higher quantum yield and containing a space charge transfer polymer sensitizer and a condensed ring unit with a resonant structure.
The invention provides a high molecular compound containing a space charge transfer polymer sensitizer and a condensed ring unit with a resonance structure, and the high molecular compound has a structure shown in a formula (I) and/or a formula (II):
Figure BDA0003246045820000011
wherein x and y are each independently any number from 0.0001 to 0.999, and x + y is less than 1; n is an integer of 2-9999;
Figure BDA0003246045820000021
is an electron donor selected from one or more of the groups of formulae (D1-1) to (D7-9) lacking one H:
Figure BDA0003246045820000022
Figure BDA0003246045820000031
Figure BDA0003246045820000032
is an electron acceptor selected from one or more of the groups formed by formula (A1-1) to formula (A13-2) lacking one H:
Figure BDA0003246045820000033
Figure BDA0003246045820000041
wherein R in the formulae (D1-1) to (D7-9) and the formulae (A1-1) to (A13-2)1～R8Each independently selected from H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups;
or R1～R8Are connected by chemical bonds to form a bridging structure;
Figure BDA0003246045820000051
is a condensed ring unit of resonant structure selected from the group consisting of formula (F-1) _ cFormula (F-11) lacks one or more of the groups formed by one H;
Figure BDA0003246045820000052
wherein, X1～X3Each independently selected from B, N, P, P ═ O or P ═ S;
Y1～Y6each independently selected from B-R ', N-R', C-O, S-O, O-S-O, O, S, Se or Te; the B-R ' and R ' in N-R ' are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted alkyl; or the B-R ' and the R ' of the N-R ' are adjacent to each other through a connecting group or a single bond
Figure BDA0003246045820000053
One or both of which are bonded.
Z1～Z3Each independently selected from B, N, P, P ═ O or P ═ S;
Figure BDA0003246045820000054
each independently selected from an aryl ring of C6-C60 or a heteroaryl ring of C3-C60;
sp is selected from a linear alkylene group of C1-C20, a branched alkylene group of C1-C20, an ether oxygen group of C1-C20 or a cycloalkylene group of C3-C20;
or at least one hydrogen in the structures shown in formula (I) and/or formula (II) is replaced by halogen and/or heavy hydrogen.
The invention also provides an organic electroluminescent device which comprises the macromolecular compound containing the space charge transfer polymer sensitizer and the condensed ring unit with the resonance structure.
The invention provides a high molecular compound containing a space charge transfer polymer sensitizer and a condensed ring unit with a resonance structure, wherein a high molecular luminescent material has a structure shown in a formula (I) and/or a formula (II). Compared with the prior art, the macromolecular compound provided by the invention has noncoordination of polystyreneA yoke main chain structure having an electron donor Ar in a side chain1Electron acceptor Ar2And a resonance structure condensed ring luminescent unit MR, wherein Ar1And Ar2Linked by a non-conjugated main chain, and adjacent Ar1And Ar2Can generate space-charge transfer (TSCT) effect and generate heat-activated delayed fluorescence which can further pass through
Figure BDA0003246045820000063
The energy is transferred to the resonance condensed ring unit MR for luminescence by the transfer process, so that the macromolecular compound has the following advantages: on one hand, the donor and the acceptor of the space charge transfer macromolecule are connected by adopting a non-conjugated structure, and the electron cloud overlapping degree is smaller, so that small delta E can be obtainedSTGenerating the TADF effect, triplet excitons can be converted from intersystem crossing to singlet states and then pass through
Figure BDA0003246045820000064
In the transfer process, energy is transferred to the resonance condensed ring unit MR for luminescence, so that the utilization of triplet excitons is realized; on the other hand, due to the rigid skeleton of the resonance condensed ring unit MR, the nonradiative transition is suppressed, and the photoluminescence quantum efficiency is high. Meanwhile, the rigid structure can inhibit the vibration relaxation of the molecular excited state, has small recombination energy and shows narrow spectrum emission (FWHM)<50nm) and high color purity. Therefore, a device prepared by using the high molecular compound provided by the invention can realize high luminous efficiency and high color purity at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high molecular compound containing a space charge transfer polymer sensitizer and a condensed ring unit with a resonance structure, and the high molecular compound has a structure shown in a formula (I) and/or a formula (II):
Figure BDA0003246045820000061
wherein x and y are each independently any number from 0.0001 to 0.999, and x + y is less than 1.
In the invention, preferably, x is any value of 0.001 to 0.5, more preferably, x is any value of 0.001 to 0.2, and still more preferably, x is any value of 0.01 to 0.1; in the embodiment provided by the present invention, x is specifically 0.05.
In the present invention, preferably, y is any value of 0.0001 to 0.1, more preferably, y is any value of 0.0001 to 0.05, still more preferably, y is any value of 0.0001 to 0.02, still more preferably, y is any value of 0.0001 to 0.01, and most preferably, y is any value of 0.001 to 0.01; in the examples provided by the present invention, y is specifically 0.002 or 0.004.
n is an integer of 2 to 9999, preferably an integer of 10 to 5000, more preferably an integer of 20 to 3000, and still more preferably an integer of 20 to 1000.
Figure BDA0003246045820000062
As electron donors, one or more of the groups formed by formula (D1-1) to formula (D7-9) lacking one H:
Figure BDA0003246045820000071
Figure BDA0003246045820000081
r in the formulae (D1-1) to (D7-9)1～R8Each independently is H,Halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups; preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C16 straight-chain alkyl, substituted or unsubstituted C1-C16 branched-chain alkyl, substituted or unsubstituted C3-C16 cycloalkyl, substituted or unsubstituted C1-C16 alkoxy chain, substituted or unsubstituted C6-C16 aryl, substituted or unsubstituted C3-C16 heteroaryl, a combination of the above groups, or a mixture of the above groups; more preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C8 heteroaryl, a combination of the above groups, or a mixture of the above groups; most preferably each independently H, halogen, -CN, -NO2Substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C4 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C6 heteroaryl, a combination of the above groups, or a fused group of the above groups. The heteroatoms in the heteroaryl group are preferably one or more of N, S, Si, O and P.
According to the invention, the substituent of the substituted C1-C22 straight-chain alkyl, substituted C1-C22 branched-chain alkyl, substituted C1-C22 cycloalkyl, substituted C1-C22 alkoxy chain, substituted C6-C20 aryl and substituted C3-C20 heteroaryl is that one or more nonadjacent carbon atoms are replaced by O, S, Si, -CO-O-, and/or one or more hydrogen atoms can be replaced by F.
Or R1～R8Which are connected by chemical bonds to form a bridging structure.
In the present invention, most preferably, the
Figure BDA0003246045820000091
One or more of the following groups formed by the formulas (d1-1) to (d2-9), the formulas (d3-6) to (d6-11) lack one H and the formulas (d2-10) to (d 3-5):
Figure BDA0003246045820000092
Figure BDA0003246045820000101
Figure BDA0003246045820000102
is an electron acceptor, which is one or more of the groups formed by formulas (A1-1) to (A13-2) lacking one H:
Figure BDA0003246045820000103
Figure BDA0003246045820000111
Figure BDA0003246045820000121
r in the formulae (A1-1) to (A13-2)1～R8Each independently of the others being H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups; preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C16 straight-chain alkyl, substituted or unsubstituted C1-C16 branched-chain alkyl, substituted or unsubstituted C3-C16 cycloalkyl, substituted or unsubstituted C1-C16 alkoxy chain, substituted or unsubstituted C6-C16 aryl, substituted or unsubstituted C3-C16 heteroaryl, a combination of the above groups, or a mixture of the above groups; more preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6EAn aryl group of C10, a substituted or unsubstituted heteroaryl group of C3-C10, a combination of the above groups, or a fused group of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C8 heteroaryl, a combination of the above groups, or a mixture of the above groups; most preferably each independently H, halogen, -CN, -NO2Substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C4 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C6 heteroaryl, a combination of the above groups, or a fused group of the above groups. The hetero atom in the heteroaryl group is preferably one or more of N, S, Si, O and P
According to the invention, the substituent of the substituted C1-C22 straight-chain alkyl, substituted C1-C22 branched-chain alkyl, substituted C1-C22 cycloalkyl, substituted C1-C22 alkoxy chain, substituted C6-C20 aryl and substituted C3-C20 heteroaryl is that one or more nonadjacent carbon atoms are replaced by O, S, Si, -CO-O-, and/or one or more hydrogen atoms can be replaced by F.
Or R1～R8Which are connected by chemical bonds to form a bridging structure.
In the present invention, most preferably, the
Figure BDA0003246045820000122
One or more of a group formed by lacking one H and a group represented by formula (a7-5) to formula (a7-9) for formula (a1-1) to formula (a7-4) below:
Figure BDA0003246045820000131
Figure BDA0003246045820000141
Figure BDA0003246045820000151
Figure BDA0003246045820000161
Figure BDA0003246045820000162
is a condensed ring unit with a resonance structure, and is one or more of groups formed by formula (F-1) to formula (F-11) lacking one H:
Figure BDA0003246045820000163
wherein, X1～X3Each independently B, N, P, P ═ O or P ═ S;
Y1～Y6each independently is B-R ', N-R', C-O, S-O, O-S-O, O, S, Se or Te; r ' in the B-R ' and the N-R ' are respectively and independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted alkyl, preferably substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl and substituted or unsubstituted C1-C22 alkyl, more preferably substituted or unsubstituted C6-C16 aryl, substituted or unsubstituted C3-C16 heteroaryl, substituted or unsubstituted C1-C16 alkyl, more preferably substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, substituted or unsubstituted C1-C10 alkyl, more preferably substituted or unsubstituted C6-C867 aryl, substituted or unsubstituted C3-C8 heteroaryl, substituted or unsubstituted C8-C8 alkyl, most preferably substituted or unsubstituted C8 aryl or substituted or unsubstituted C8 aryl, GetSubstituted or unsubstituted C3-C6 heteroaryl, substituted or unsubstituted C1-C4 alkyl; or the B-R ' and the R ' of the N-R ' are adjacent to each other through a connecting group or a single bond
Figure BDA0003246045820000171
Figure BDA0003246045820000172
One or both of which are bonded. The substituents in the substituted aryl, substituted heteroaryl and substituted alkyl groups are such that one or more nonadjacent carbon atoms are replaced by O, S, Si, -CO-O-and/or one or more hydrogen atoms may be replaced by F.
Z1～Z3Each independently B, N, P, P ═ O or P ═ S;
Figure BDA0003246045820000173
independently represent an aryl ring of C6-C60 or a heteroaryl ring of C3-C60, preferably independently represent an aryl ring of C6-C40 or a heteroaryl ring of C3-C40, more preferably represent an aryl ring of C6-C20 or a heteroaryl ring of C3-C20, still more preferably represent an aryl ring of C6-C15 or a heteroaryl ring of C3-C15, and most preferably represent an aryl ring of C6-C12 or a heteroaryl ring of C3-C12; the hetero atoms in the heteroaryl ring are preferably one or more of Si, Ge, N, P, O, S and Se; in the present invention, more preferably, the total number of carbon atoms and heteroatoms in the heteroaryl ring is 5 or more.
Preferably, the
Figure BDA0003246045820000174
In (1)
Figure BDA0003246045820000175
Each independently is one of the groups shown in the formulas (1) to (15):
Figure BDA0003246045820000176
wherein, formula(1) L in the formula (15)1～L3Each independently of the others being H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups; preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C16 straight-chain alkyl, substituted or unsubstituted C1-C16 branched-chain alkyl, substituted or unsubstituted C3-C16 cycloalkyl, substituted or unsubstituted C1-C16 alkoxy chain, substituted or unsubstituted C6-C16 aryl, substituted or unsubstituted C3-C16 heteroaryl, a combination of the above groups, or a mixture of the above groups; more preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C8 heteroaryl, a combination of the above groups, or a fused form of the above groupsA group of (A) or (B); most preferably each independently H, halogen, -CN, -NO2Substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C4 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C6 heteroaryl, a combination of the above groups, or a fused group of the above groups. The heteroatoms in the heteroaryl group are preferably one or more of N, S, Si, O and P.
According to the invention, the substituent of the substituted C1-C22 straight-chain alkyl, substituted C1-C22 branched-chain alkyl, substituted C1-C22 cycloalkyl, substituted C1-C22 alkoxy chain, substituted C6-C20 aryl and substituted C3-C20 heteroaryl is that one or more nonadjacent carbon atoms are replaced by O, S, Si, -CO-O-, and/or one or more hydrogen atoms can be replaced by F.
Or L1～L3Which are connected by chemical bonds to form a bridging structure.
According to the invention, more preferably, said
Figure BDA0003246045820000181
One or more selected from the group consisting of formula (F1-1) to formula (F11-12) lacking a H:
Figure BDA0003246045820000182
Figure BDA0003246045820000191
Figure BDA0003246045820000201
Figure BDA0003246045820000211
Figure BDA0003246045820000221
wherein R in the formulas (F1-1) to (F11-12)1～R12Each independently of the others being H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or a combination of the above groups, or a fused group of the above groups; preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C16 straight-chain alkyl, substituted or unsubstituted C1-C16 branched-chain alkyl, substituted or unsubstituted C3-C16 cycloalkyl, substituted or unsubstituted C1-C16 alkoxy chain, substituted or unsubstituted C6-C16 aryl, substituted or unsubstituted C3-C16 heteroaryl, a combination of the above groups, or a mixture of the above groups; more preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, a combination of the above groups, or a mixture of the above groups; further preferably each independently of the others is H, halogen, -CN, -NO2Substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1EA C6 branched alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy chain, a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted C3-C8 heteroaryl group, a group formed by combining the above groups, or a group formed by fusing the above groups; most preferably each independently H, halogen, -CN, -NO2Substituted or unsubstituted C1-C4 straight-chain alkyl, substituted or unsubstituted C1-C4 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C4 alkoxy chain, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C6 heteroaryl, a combination of the above groups, or a fused group of the above groups. The heteroatoms in the heteroaryl group are preferably one or more of N, S, Si, O and P.
According to the invention, the substituent of the substituted C1-C22 straight-chain alkyl, substituted C1-C22 branched-chain alkyl, substituted C1-C22 cycloalkyl, substituted C1-C22 alkoxy chain, substituted C6-C20 aryl and substituted C3-C20 heteroaryl is that one or more nonadjacent carbon atoms are replaced by O, S, Si, -CO-O-, and/or one or more hydrogen atoms can be replaced by F.
Or R1～R4Which are connected by chemical bonds to form a bridging structure.
In the present invention, most preferably, the
Figure BDA0003246045820000231
One or more selected from the group consisting of formula (f1-1) to formula (f11-7) lacking a H:
Figure BDA0003246045820000232
Figure BDA0003246045820000241
Figure BDA0003246045820000251
Figure BDA0003246045820000261
sp is C1-C20 branched chain alkylene, C1-C20 branched chain alkylene, C1-C20 ether oxygen or C3-C20 cycloalkylene; preferably C1-C15 branched alkylene, C1-C15 branched alkylene, C1-C15 ether oxygen or C3-C15 cycloalkylene; more preferably a branched alkylene group of C3 to C15, a branched alkylene group of C3 to C15, an ether oxy group of C3 to C15, or a cycloalkylene group of C3 to C15; more preferably a branched alkylene group of C5-C15, a branched alkylene group of C5-C15, an ether oxygen group of C5-C15, or a cycloalkylene group of C5-C15; more preferably a branched alkylene group of C6-C10, a branched alkylene group of C6-C10, an ether oxygen group of C6-C10, or a cycloalkylene group of C6-C10; most preferred is a branched alkylene group having 6 to 8 carbon atoms, a branched alkylene group having 6 to 8 carbon atoms, an ether oxygen group having 6 to 8 carbon atoms, or a cycloalkylene group having 6 to 8 carbon atoms.
In the present invention, it is most preferable that the polymer compound has one or more of the structures represented by the formulae (I-1) to (I-41) and the formulae (II-1) to (II-50):
Figure BDA0003246045820000271
Figure BDA0003246045820000281
Figure BDA0003246045820000291
Figure BDA0003246045820000301
Figure BDA0003246045820000311
Figure BDA0003246045820000321
the macromolecular compound provided by the invention has a non-conjugated main chain structure of polystyrene and an electron donor Ar at a side chain1Electron acceptor Ar2And a resonance structure condensed ring luminescent unit MR, wherein Ar1And Ar2Linked by a non-conjugated main chain, and adjacent Ar1And Ar2Can generate space-charge transfer (TSCT) effect and generate heat-activated delayed fluorescence which can further pass through
Figure BDA0003246045820000324
The energy is transferred to the resonance condensed ring unit MR for luminescence by the transfer process, so that the macromolecular compound has the following advantages: on one hand, the donor and the acceptor of the space charge transfer macromolecule are connected by adopting a non-conjugated structure, and the electron cloud overlapping degree is smaller, so that small delta E can be obtainedSTGenerating the TADF effect, triplet excitons can be converted from intersystem crossing to singlet states and then pass through
Figure BDA0003246045820000325
In the transfer process, energy is transferred to the resonance condensed ring unit MR for luminescence, so that the utilization of triplet excitons is realized; on the other hand, due to the rigid skeleton of the resonance condensed ring unit MR, the nonradiative transition is suppressed, and the photoluminescence quantum efficiency is high. Meanwhile, the rigid structure can inhibit the vibration relaxation of the molecular excited state, has small recombination energy and shows narrow spectrum emission (FWHM)<50nm) and high color purity. Therefore, a device prepared by using the high molecular compound provided by the invention can realize high luminous efficiency and high color purity at the same time.
The invention also provides a preparation method of the macromolecular compound containing the space charge transfer polymer sensitizer and the resonance structure condensed ring unit, which comprises the following steps: in a protective atmosphere, initiating a monomer shown in a formula (III), a monomer shown in a formula (IV) and a monomer shown in a formula (V) and/or a monomer shown in a formula (VI) in a first solvent by an initiator to react to obtain a macromolecular compound; the molar ratio of the monomer shown in the formula (III), the monomer shown in the formula (IV) to the monomer shown in the formula (V) and/or the monomer shown in the formula (VI) is (1-x-y): x: y;
Figure BDA0003246045820000322
wherein x, y,
Figure BDA0003246045820000323
The same as Sp, and are not repeated herein.
In a protective atmosphere, initiating a monomer shown in a formula (III), a monomer shown in a formula (IV) and a monomer shown in a formula (V) and/or a monomer shown in a formula (VI) in a first solvent by an initiator to react; the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and nitrogen and/or argon is preferable in the present invention; the initiator is preferably one or more of azobisisobutyronitrile, dibenzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxybenzoate; the molar quantity of the initiator is preferably 1 to 10 percent of the total molar quantity of all monomers, more preferably 1 to 5 percent, and still more preferably 2 to 3 percent; the first solvent is preferably one or more of toluene, xylene, tert-butyl benzene, tetrahydrofuran, dioxane and N, N-dimethylformamide; the amount of the first solvent is preferably such that the concentration of the total monomers in the initial reaction system is 0.05-1 mol/L, more preferably 0.1-0.5 mol/L; the reaction temperature is preferably 40-120 ℃, more preferably 40-100 ℃, and further preferably 50-80 ℃; the reaction time is preferably 8-72 h, more preferably 15-60 h, still more preferably 20-50 h, and most preferably 32-48 h.
Preferably settling in a second solvent after the reaction; the second solvent is preferably one or more of methanol, acetone, diethyl ether, n-hexane and cyclohexane; after settling, drying to obtain the macromolecular compound.
The invention also provides an organic electroluminescent device which comprises the macromolecular compound containing the space charge transfer polymer sensitizer and the condensed ring unit with the resonance structure.
Preferably, the macromolecular compound containing the space charge transfer polymer sensitizer and the condensed ring unit with the resonance structure is used as a luminescent material in an organic electroluminescent device.
Further preferably, the organic electroluminescent device includes an anode, a cathode, and an organic compound layer disposed between the anode and the cathode; the number of the organic compound layers is preferably 1 or more, and at least one layer is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more of the high molecular compounds containing the space charge transfer polymer sensitizer and the condensed ring unit with the resonance structure.
Further preferably, the organic electroluminescent device includes a substrate; an anode disposed on the substrate; an organic compound layer disposed on the anode; the number of the organic compound layers is preferably 1 or more, and at least one layer is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more of the high molecular compounds containing the space charge transfer polymer sensitizer and the condensed ring unit with the resonance structure; a cathode disposed on the organic compound layer.
The kind of the substrate is not particularly limited in the present invention, and glass or plastic is preferable in the present invention; the thickness of the substrate is preferably 0.3-0.7 mm.
An anode is arranged on the substrate; the anode is a material which facilitates hole injection, and in the present invention, a conductive metal or a conductive metal oxide is preferable, and indium tin oxide is more preferable.
An organic compound layer is arranged on the anode; the organic compound layer may be one layer or a plurality of layers, and at least one layer of the organic compound layer is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more high molecular compounds containing a space charge transfer polymer sensitizer and a condensed ring unit with a resonance structure. In the present invention, it is preferable that the polymer compound containing a space charge transfer polymer sensitizer and a condensed ring unit of a resonance structure directly constitutes an organic electroluminescent layer as a light-emitting material.
A cathode is arranged on the organic compound layer; the cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, the organic compound layer between the anode and the organic electroluminescent layer preferably further comprises a hole injection layer, a hole transport layer and an electron blocking layer; the organic layer between the organic electroluminescent layer and the cathode preferably further comprises a hole blocking layer and an electron injection/transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, and the electron injection/transport layer are not particularly limited in the present invention and may be selected according to materials and thicknesses well known to those skilled in the art.
The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method: forming an anode on the substrate; forming one or more organic compound layers including an organic electroluminescent layer on the anode; forming a cathode on the organic compound layer; the organic electroluminescent layer comprises one or more of the macromolecular compounds containing the space charge transfer polymer sensitizer and the condensed ring unit with the resonance structure.
In the process of preparing the organic electroluminescent device, the anode is first formed on the substrate, and the present invention does not specifically limit the formation manner of the anode, and may be performed according to a method well known to those skilled in the art.
After the anode is obtained, an organic compound layer is formed on the anode. The organic electroluminescent layer in the organic compound layer comprises one or more high-molecular luminescent materials taking the space charge transfer polymer as a sensitizer. The present invention is not particularly limited in the manner of forming the organic electroluminescent layer in the organic compound layer and the mail compound layer between the organic electroluminescent layer and the anode, and may be formed on the anode by solution spin coating, inkjet printing, offset printing or stereolithography. After the organic electroluminescent layer is formed, a hole blocking layer and an electron injection/transmission layer can be formed on the surface of the organic electroluminescent layer by vacuum evaporation or spin coating.
After the organic compound layer is prepared, a cathode is prepared on the surface thereof, and the cathode is preferably formed by a method known to those skilled in the art, including but not limited to vacuum deposition, without being particularly limited thereto.
In order to further illustrate the present invention, the following will describe in detail a polymer compound and an organic electroluminescent device containing a space charge transfer polymer sensitizer and a condensed ring unit with a resonance structure, provided by the present invention, with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
Figure BDA0003246045820000341
Under argon atmosphere, 0.948mmol of MD1, 0.050mmol of MA1, 0.002 mmol of MF1 and 0.020mmol of AIBN are added into a 25mL Schlenk bottle, 10mL of Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 48 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the solid is dried again in vacuum, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer compound obtained in example 1 was determined to be 35,700g/mol, and the degree of dispersion (PDI) was determined to be 1.78.
Example 2
Figure BDA0003246045820000342
Under argon atmosphere, 0.948mmol of MD2, 0.050mmol of MA2, 0.002 mmol of MF2 and 0.020mmol of AIBN are added into a 25mL Schlenk bottle, 10mL of Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 48 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the solid is dried again in vacuum, and the needed high molecular compound is obtained.
The polymer compound obtained in example 2 was examined to have a number average molecular weight of 23,500g/mol and a dispersity (PDI) of 2.01.
Example 3
Figure BDA0003246045820000343
Under argon atmosphere, 0.948mmol of MD1, 0.050mmol of MA3, 0.002 mmol of MF3 and 0.020mmol of AIBN are added into a 25mL Schlenk bottle, 10mL of Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 48 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the solid is dried again in vacuum, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer obtained in example 3 was found to be 27,600g/mol, and the degree of dispersion (PDI) was found to be 1.92.
Example 4
Figure BDA0003246045820000351
Under argon atmosphere, 0.948mmol of MD1, 0.050mmol of MA3, 0.002 mmol of MF4 and 0.020mmol of AIBN are added into a 25mL Schlenk bottle, 10mL of Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 48 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the solid is dried again in vacuum, and the needed high molecular compound is obtained.
The polymer compound obtained in example 4 was examined to have a number average molecular weight of 27,300g/mol and a dispersity (PDI) of 1.79.
Example 5
Figure BDA0003246045820000352
Under argon atmosphere, 0.948mmol of MD3, 0.050mmol of MA4, 0.002 mmol of MF5 and 0.020mmol of AIBN are added into a 25mL Schlenk bottle, 10mL of Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 48 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the solid is dried again in vacuum, and the needed high molecular compound is obtained.
The polymer compound obtained in detection example 5 had a number average molecular weight of 35,400g/mol and a dispersity (PDI) of 1.76.
Example 6
Figure BDA0003246045820000353
Under argon atmosphere, 0.946mmol MD4, 0.050mmol MA4, 0.004 mmol MF6 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer compound obtained in example 6 was found to be 26,500g/mol, and the degree of dispersion (PDI) was found to be 1.87.
Example 7
Figure BDA0003246045820000361
Under argon atmosphere, 0.946mmol MD5, 0.050mmol MA5, 0.004 mmol MF7 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The polymer compound obtained in example 7 was examined to have a number average molecular weight of 29,600g/mol and a dispersity (PDI) of 1.81.
Example 8
Figure BDA0003246045820000362
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA1, 0.004 mmol MF8 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer compound obtained in example 8 was determined to be 27,600g/mol, and the degree of dispersion (PDI) was determined to be 1.74.
Example 9
Figure BDA0003246045820000363
Under argon atmosphere, 0.946mmol MD1, 0.05mmol MA1, 0.004 mmol MF9 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The polymer compound obtained in example 9 was examined to have a number average molecular weight of 28,900g/mol and a dispersity (PDI) of 1.94.
Example 10
Figure BDA0003246045820000371
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA1, 0.004 mmol MF10 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The polymer compound obtained in example 10 was examined to have a number average molecular weight of 31,200g/mol and a dispersity (PDI) of 1.88.
Example 11
Figure BDA0003246045820000372
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA1, 0.004 mmol MF11 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The polymer compound obtained in example 11 was examined to have a number average molecular weight of 24,600g/mol and a dispersity (PDI) of 1.78.
Example 12
Figure BDA0003246045820000373
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA6, 0.004 mmol MF12 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer compound obtained in example 12 was determined to be 29,200g/mol, and the degree of dispersion (PDI) was determined to be 1.75.
Example 13
Figure BDA0003246045820000381
Under argon atmosphere, 0.946mmol MD1, 0.05mmol MA1, 0.004 mmol MF13 and 0.02mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The polymer compound obtained in example 13 was examined to have a number average molecular weight of 26,400g/mol and a dispersity (PDI) of 1.69.
Example 14
Figure BDA0003246045820000382
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA1, 0.004 mmol MF14 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer compound obtained in example 14 was determined to be 25,300g/mol, and the degree of dispersion (PDI) was determined to be 1.77.
Example 15
Figure BDA0003246045820000383
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA7, 0.004 mmol MF15 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer was determined to be 28,600g/mol and the degree of dispersion (PDI) was 1.83.
Example 16
Figure BDA0003246045820000391
Under argon atmosphere, 0.946mmol MD1, 0.050mmol MA8, 0.004 mmol MF16 and 0.020mmol AIBN are added into a 25mL Schlenk bottle, 10mL Tetrahydrofuran (THF) is added into the bottle, the temperature is raised to 50 ℃, the reaction is stirred under the protection of argon for 48 hours, then the temperature is cooled to room temperature, the reaction liquid is poured into acetone, the precipitated solid is filtered, the solid is dissolved by dichloromethane after vacuum drying, the solid is settled in methanol and the vacuum drying is carried out again, and the needed high molecular compound is obtained.
The number average molecular weight of the polymer compound obtained in example 16 was determined to be 26,100g/mol, and the degree of dispersion (PDI) was determined to be 1.78.
Device examples
Poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT/PSS) was spin-coated on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30min, followed by spin-coating a toluene (6mg/mL) solution of a high molecular compound at 1500rpm for 1min and annealing at 80 ℃ for 30min to form a 40nm light-emitting layer on PEDOT/PSS, followed by 4X 10-4Sequentially depositing TSPO1, TmPyPB and LiMF/Al cathode under Pa vacuum degreeAs a result, an organic electroluminescent device was obtained in which TSPO1 and TmPyPB were used as a hole blocking layer and an electron transport layer, respectively, and the structures thereof were as follows. The specific device structure is PEDOT, PSS (40nm)/EML (30nm)/TSPO1(8nm)/TmPyPB (42nm)/LiMF (1nm)/Al (100 nm). Device examples the resulting electroluminescent device performance parameters are listed in table 1.
Figure BDA0003246045820000392
Table 1 device examples the electroluminescent device performance parameters obtained
Figure BDA0003246045820000393
Note: the luminescence wavelength in the table is the wavelength corresponding to the maximum peak of the electroluminescence spectrum; the half-peak width is the peak width at half of the spectral peak height of the electroluminescence spectrum at room temperature, namely a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the straight line is the distance between two intersecting points on two sides of the peak; the starting voltage is 1cd m in luminance-2The driving voltage of the time device; the maximum external quantum efficiency was obtained from the current-voltage curve and the electroluminescence spectrum of the device according to the calculation method described in the literature (jpn.j.appl.phys.2001,40, L783).
The device data in table 1 show that the external quantum efficiency of the polymer compound provided by the invention reaches 14.7-19.5%, the external quantum efficiency exceeds the theoretical limit value (5%) of the traditional fluorescent polymer, the half-peak width of the electroluminescence spectrum is small, 30-44 nm, and the color purity is high. In particular, the external quantum efficiencies of the blue light polymer P14, the green light polymer P6, and the red light polymer P7 were 18.1%, 19.5%, and 17.5%, respectively, and the corresponding half-widths were 30, 41, and 48nm, respectively. Therefore, the electroluminescent device prepared by the macromolecular compound provided by the invention can realize high luminous efficiency and high color purity at the same time.

Claims (10)

1. A polymer compound containing a space charge transfer polymer sensitizer and a condensed ring unit of a resonance structure, wherein the polymer compound has a structure represented by formula (I) and/or formula (II):
Figure FDA0003246045810000011
wherein x and y are each independently any number from 0.0001 to 0.999, and x + y is less than 1; n is an integer of 2-9999;
Figure FDA0003246045810000012
is an electron donor selected from one or more of the groups of formulae (D1-1) to (D7-9) lacking one H:
Figure FDA0003246045810000013
Figure FDA0003246045810000021
Figure FDA0003246045810000031
Figure FDA0003246045810000032
is an electron acceptor selected from one or more of the groups formed by formula (A1-1) to formula (A13-2) lacking one H:
Figure FDA0003246045810000033
Figure FDA0003246045810000041
Figure FDA0003246045810000051
wherein R in the formulae (D1-1) to (D7-9) and the formulae (A1-1) to (A13-2)1～R8Each independently selected from H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups;
or R1～R8Are connected by chemical bonds to form a bridging structure;
Figure FDA0003246045810000052
is a condensed ring unit with a resonance structure, and is selected from one or more groups formed by the formulas (F-1) to (F-11) lacking one H;
Figure FDA0003246045810000061
wherein, X1～X3Each independently selected from B, N, P, P ═ O or P ═ S;
Y1～Y6each independently selected from B-R ', N-R', C-O, S-O, O-S-O, O, S, Se or Te; the B-R ' and R ' in N-R ' are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted alkyl; or the B-R ' and the R ' of the N-R ' are adjacent to each other through a connecting group or a single bond
Figure FDA0003246045810000062
One or both of which are linked;
Z1～Z3each independently selected from B, N, P, P ═ O or P ═ S;
Figure FDA0003246045810000063
each independently selected from an aryl ring of C6-C60 or a heteroaryl ring of C3-C60;
sp is selected from a linear alkylene group of C1-C20, a branched alkylene group of C1-C20, an ether oxygen group of C1-C20 or a cycloalkylene group of C3-C20;
or at least one hydrogen in the structures shown in formula (I) and/or formula (II) is replaced by halogen and/or heavy hydrogen.
2. The polymer compound according to claim 1, wherein x is any of 0.01 to 0.2; y is any value of 0.0001 to 0.02; n is an integer of 20 to 1000.
3. The polymer compound according to claim 1, wherein x is any of 0.01 to 0.1; y is any value of 0.0001 to 0.01.
4. A polymer compound according to claim 1,
Figure FDA0003246045810000071
in (1)
Figure FDA0003246045810000072
Figure FDA0003246045810000073
Each independently selected from one of the groups represented by the formulas (1) to (15):
Figure FDA0003246045810000074
wherein L in the formulae (1) to (15)1～L3Each independently selected from H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups;
or L1～L3Which are connected by chemical bonds to form a bridging structure.
5. The polymer compound according to claim 1, wherein the polymer compound is the one according to claim 1
Figure FDA0003246045810000075
One or more selected from the group consisting of formula (F1-1) to formula (F11-12) lacking a H:
Figure FDA0003246045810000081
Figure FDA0003246045810000091
Figure FDA0003246045810000101
Figure FDA0003246045810000111
Figure FDA0003246045810000121
r in the formulae (F1-1) to (F11-12)1～R12Each independently selected from H, halogen, -CN, -NO2Substituted or unsubstituted C1-C22 straight-chain alkyl, substituted or unsubstituted C1-C22 branched-chain alkyl, substituted or unsubstituted C1-C22 cycloalkyl, substituted or unsubstituted C1-C22 alkoxy chain, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, a combination of the above groups, or a mixture of the above groups;
or R1～R12Which are connected by chemical bonds to form a bridging structure.
6. The polymer compound according to any one of claims 1 to 5, wherein the substituents in the substituted C1-C22 linear alkyl group, the substituted C1-C22 branched alkyl group, the substituted C1-C22 cycloalkyl group, the substituted C1-C22 alkoxy chain, the substituted C6-C20 aryl group and the substituted C3-C20 heteroaryl group are such that one or more nonadjacent carbon atoms are replaced by O, S, Si, -CO-O-, and/or one or more hydrogen atoms are replaced by F.
7. The polymer compound according to claim 1, wherein the polymer compound is the one according to claim 1
Figure FDA0003246045810000131
One or more selected from the group consisting of formula (f1-1) to formula (f11-7) lacking a H:
Figure FDA0003246045810000132
Figure FDA0003246045810000141
Figure FDA0003246045810000151
Figure FDA0003246045810000161
Figure FDA0003246045810000171
8. the polymer compound according to claim 1, wherein the polymer compound has one or more of the structures represented by formulae (I-1) to (I-41) and formulae (II-1) to (II-50):
Figure FDA0003246045810000172
Figure FDA0003246045810000181
Figure FDA0003246045810000191
Figure FDA0003246045810000201
Figure FDA0003246045810000211
Figure FDA0003246045810000221
Figure FDA0003246045810000231
9. a method for producing a polymer compound containing a space charge transfer polymer sensitizer according to claim 1 and a condensed ring unit of resonance structure, comprising:
in a protective atmosphere, initiating a monomer shown in a formula (III), a monomer shown in a formula (IV) and a monomer shown in a formula (V) and/or a monomer shown in a formula (VI) in a first solvent by an initiator to react to obtain a macromolecular compound; the molar ratio of the monomer shown in the formula (III), the monomer shown in the formula (IV) to the monomer shown in the formula (V) and/or the monomer shown in the formula (VI) is (1-x-y): x: y;
Figure FDA0003246045810000232
10. an organic electroluminescent device comprising the polymer compound containing a space charge transfer polymer sensitizer according to any one of claims 1 to 8 and a condensed ring unit of a resonance structure or the polymer compound containing a space charge transfer polymer sensitizer and a condensed ring unit of a resonance structure prepared by the preparation method according to claim 9.
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