CN111363124B - TADF (TADF) polymer containing meta-position electron donor and electron acceptor alternately connected as well as preparation method and application thereof - Google Patents

TADF (TADF) polymer containing meta-position electron donor and electron acceptor alternately connected as well as preparation method and application thereof Download PDF

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CN111363124B
CN111363124B CN202010269396.5A CN202010269396A CN111363124B CN 111363124 B CN111363124 B CN 111363124B CN 202010269396 A CN202010269396 A CN 202010269396A CN 111363124 B CN111363124 B CN 111363124B
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丁军桥
饶建成
王利祥
王淑萌
赵磊
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, a preparation method thereof and application in the field of electroluminescent devices, wherein the polymer has a structure shown in a formula (I). The polymer provided by the invention is alternately connected by using the same electron donor unit and the same electron acceptor unit, and the delayed component of the photoinduced transient decay curve of the corresponding polymer is gradually increased from para position to meta position only by changing the connection mode between the electron donor and the electron acceptor, thereby showing that the TADF property is gradually enhanced. Polymers in which both the donor and the acceptor are connected in the meta position exhibit good electroluminescent properties: as a luminescent layer dye, the maximum external quantum efficiency of the device is 8.8%; as a light emitting layer sensitizer, a red phosphorescent dye was sensitized, and the maximum external quantum efficiency of the device was 8.2%.

Description

TADF (TADF) polymer containing meta-position electron donor and electron acceptor alternately connected as well as preparation method and application thereof
Technical Field
The invention belongs to the field of organic semiconductor photoelectric materials, and particularly relates to a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, and a preparation method and application thereof.
Background
In 2012, the subject group of Adachi professor at kyushu university of japan reported in Nature a series of carbazole and dicyanobenzene compounds based on distorted conformations, which have significant Thermally Activated Delayed Fluorescence (TADF) properties, wherein 4CzIPN exhibits high-efficiency electroluminescence with External Quantum Efficiency (EQE) of 19.3% (Nature,2012,492, 234-. Since this, there are many studies on the design, synthesis and performance of TADF molecules, and electroluminescent EQE over the full visible spectrum has been reported to approach or even exceed 30% (chem. soc. rev.,2017,46, 915-. Following traditional fluorescence and heavy metal phosphorescence, TADF is gradually becoming a third generation material applied in the field of organic light-emitting diodes (OLEDs). Until now, most of the TADF related studies have focused on small molecules, which rely on a fine and costly vacuum evaporation process. In contrast, TADF polymers suitable for simple and low cost solution processing suffer from significant hysteresis. Until 2015, research teams of cambridge display technology company used TADF fragments of a combination of triarylamines and triazines to embed non-conjugated polymer chains to first achieve polymers with TADF characteristics, corresponding to electroluminescence EQE of more than 10% (adv. mate., 2015,27, 7236-one 7240.).
TADF polymers can be divided into two broad categories according to the building motif: one is a polymer based on existing TADF fragments, which combines a polymer host (adv. mater.,2017,29,1604223.) that functions as a dispersion or a linker unit (angelw. chem. int.ed.,2020,59, 1320-; the other is based on electron donor and electron acceptor units, which produce the TADF effect by giving the acceptor a proper distribution in the polymer chain. The latter can be further divided into three subclasses: the first is the alternating linkage of the donor and acceptor in the backbone to form a polymer (adv. mater.,2016,28, 4019-; the second is donor-to-donor interconnection as the backbone and acceptor-to-acceptor discrete linkage in the side chains (Macromolecules,2016,49, 4373-4377.); the third is the random grafting of the donor and acceptor onto the polymer side chains (J.am. chem. Soc.,2017,139, 17739-17742.). Among them, alternate attachment to the receptor is the simplest and most intuitive construction method, but is rarely employed. The underlying reason for this is that excessive electron cloud overlap between frontline orbitals (FMOs) distributed to the receptors results in the lowest singlet state (S)1) And the lowest triplet state (T, the lowest triplet)1) Energy difference (Δ E)ST) Is too large to get from T1To S1The reverse intercross crossing (RISC) of (a) is difficult to occur under room temperature conditions, and thus tends not to have TADF effect.
Disclosure of Invention
In view of the above, the present invention fully utilizes the influence of meta-position connection on the front-line orbital overlap between electron donor and electron acceptor, thereby realizing the adjustment of the energy difference between the lowest singlet state and the lowest triplet state of the polymer and the TADF performance determined thereby, and finally solving the problem that the current polymers with alternately connected electron donor and electron acceptor have excessive front-line orbital overlap and are difficult to use as TADF materials. The invention aims to provide a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, and a preparation method and application thereof.
The invention provides a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, which has a structure shown in a formula (I):
Figure BDA0002442544570000021
wherein the content of the first and second substances,
Figure BDA0002442544570000022
is an electron donor unit;
Figure BDA0002442544570000023
is an electron acceptor unit;
n＝2～200；
the electron donor unit is selected from aryl-containing groups of C6-C60;
the electron acceptor unit is selected from aryl-containing groups of C6-C60;
the electron donor units and/or electron acceptor units are alternately connected by adopting meta-position sites.
Preferably, the
Figure BDA0002442544570000024
Any one selected from formulas (a-1) to (a-27):
Figure BDA0002442544570000025
Figure BDA0002442544570000031
Figure BDA0002442544570000041
p represents a para-attachment site, and m represents a meta-attachment site;
said T, M and J are independently selected from-NR4、-CR4R5-、-SiR4R5-, -O-or-S-; the R is1、R2、R3、R4And R5Independently selected from-H, -X, C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl;
x is independently selected from F, Cl, Br or I; the heteroatoms of the heteroalkyl and heteroaryl groups are independently selected from B, N, O, P, S or Si; the alkyl group, the heteroalkyl group, the aryl group and the heteroaryl group may be optionally substituted with a substituent.
Preferably, the
Figure BDA0002442544570000042
Any one selected from formulas (a-1-1) to (a-3-2):
Figure BDA0002442544570000051
p represents a para-attachment site, and m represents a meta-attachment site.
Preferably, the
Figure BDA0002442544570000052
Selected from any one of formulas (b-1) to (b-12):
Figure BDA0002442544570000053
Figure BDA0002442544570000061
p represents a para-attachment site, and m represents a meta-attachment site;
e and G are independently selected from-CO-, -SO2-、-BR9-or-POR9-; the R is6、R7、R8And R9Independently selected from-H, -X, C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl;
x is independently selected from F, Cl, Br or I; the heteroatoms of the heteroalkyl and heteroaryl groups are independently selected from B, N, O, P, S or Si; the alkyl group, the heteroalkyl group, the aryl group and the heteroaryl group may be optionally substituted with a substituent.
Preferably, the
Figure BDA0002442544570000062
Any one selected from the formulas (b-1-1) to (b-12-1):
Figure BDA0002442544570000063
p represents a para-attachment site, and m represents a meta-attachment site.
Preferably, the TADF polymer is selected in particular from any one of formulae (I-1) to (I-12):
Figure BDA0002442544570000071
the invention provides a preparation method of a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, which comprises the following steps:
under inert atmosphere, mixing a diboron ester monomer with a structure shown in a formula (II), a bisbromine monomer with a structure shown in a formula (III), a palladium catalyst, a phase transfer catalyst, alkali and a reaction solvent, heating to carry out Suzuki polymerization, respectively adding a bromine end capping agent and a boron ester end capping agent after the reaction is finished, and then adding a chelating agent to quench the palladium catalyst to obtain the TADF polymer with the structure shown in the formula (I):
Figure BDA0002442544570000081
preferably, the molar ratio of the diboron ester monomer with the structure of formula (II), the bisbromine monomer with the structure of formula (III), the palladium catalyst, the phase transfer catalyst and the alkali is 1:1 (0.001-0.01): 0.1-1: 2-20.
Preferably, the temperature of the polymerization reaction is 80-120 ℃; the time of the polymerization reaction is 1-24 h.
The invention provides an application of a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected in the technical scheme in the field of electroluminescent devices, which specifically comprises the following steps: as a light-emitting material; as host material or sensitizing material to desensitize fluorescent, phosphorescent and TADF luminescent objects.
The invention provides a polymer with a structure shown in a formula (I), wherein the same electron donor units and the same electron acceptor units are alternately connected, and the retardation component of a light-induced transient decay curve of the corresponding polymer is gradually increased from para position to meta position only by changing the connection mode between the electron donor units and the electron acceptor units, so that the TADF property is gradually enhanced. Finally, polymers in which both the donor and the acceptor are connected in the meta position exhibit good electroluminescent properties: as a luminescent layer dye, the maximum external quantum efficiency of the device is 8.8%; as a light emitting layer sensitizer, a red phosphorescent dye was sensitized, and the maximum external quantum efficiency of the device was 8.2%.
Drawings
FIG. 1 is an absorption emission spectrum of a polymer poly (TPAp-DCBp) prepared in comparative example 1 in which a para-para electron donor and an electron acceptor are alternately connected in a pure film state;
FIG. 2 is an absorption emission spectrum of TADF polymer poly (TPAp-DCBm) prepared in example 1, wherein the electron donor and the electron acceptor are alternately connected in a para-meta position, in a pure film state;
FIG. 3 is the absorption emission spectrum of TADF polymer poly (TPAm-DCBp) prepared in example 2 with alternating connection of the electron donor and the electron acceptor in the pure film state;
FIG. 4 is an absorption emission spectrum of TADF polymer poly (TPAm-DCBm) prepared in example 3 with alternating connection of electron donor and electron acceptor in a pure film state;
FIG. 5 is a graph showing the light induced transient decay curve of a polymer poly (TPAp-DCBp) prepared in comparative example 1 in which a para-para electron donor and an electron acceptor are alternately connected in a pure film state;
FIG. 6 is a graph showing the light induced transient decay curves of TADF polymer poly (TPAp-DCBm) prepared in example 1 in which the electron donor and the electron acceptor are alternately connected in the para-meta position in the pure film state;
FIG. 7 is a graph showing the light induced transient decay curves of TADF polymer poly (TPAm-DCBp) prepared in example 2 in which the electron donor and the electron acceptor are alternately connected in the meta-para position in the pure film state;
FIG. 8 is a graph showing the light induced transient decay curves of TADF polymer poly (TPAm-DCBm) prepared in example 3 in which the electron donor and the electron acceptor are alternately connected in the meta-meta position and the pure film state;
FIG. 9 is a comparison of light induced transient decay curves of a polymer poly (TPAp-DCBp) prepared in comparative example 1 and containing alternating connections of an electron donor and an electron acceptor and TADF polymers poly (TPAp-DCBm), poly (TPAm-DCBp) and poly (TPAm-DCBm) prepared in examples 1 to 3, wherein the polymers containing alternating connections of an electron donor and an electron acceptor are in a pure film state;
FIG. 10 is a comparison of the external quantum efficiencies of four electroluminescent devices A, B, C and D prepared in example 4;
FIG. 11 shows the emission spectrum and external quantum efficiency of an electroluminescent device E prepared in example 4.
Detailed Description
The invention provides a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, which has a structure shown in a formula (I):
Figure BDA0002442544570000091
wherein the content of the first and second substances,
Figure BDA0002442544570000092
is an electron donor unit;
Figure BDA0002442544570000093
is an electron acceptor unit;
n＝2～200；
the electron donor unit is selected from aryl-containing groups of C6-C60;
the electron acceptor unit is selected from aryl-containing groups of C6-C60;
the electron donor units and/or electron acceptor units are alternately connected by adopting meta-position sites.
The above-mentioned
Figure BDA0002442544570000094
Preferably selected from any one of formulae (a-1) to (a-27):
Figure BDA0002442544570000095
Figure BDA0002442544570000101
Figure BDA0002442544570000111
p represents a para-attachment site, and m represents a meta-attachment site;
said T, M and J are independently selected from-NR4、-CR4R5-、-SiR4R5-, -O-or-S-; the R is1、R2、R3、R4And R5Independently selected from-H, -X, C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl;
x is independently selected from F, Cl, Br or I; the heteroatoms of the heteroalkyl and heteroaryl groups are independently selected from B, N, O, P, S or Si; the alkyl group, the heteroalkyl group, the aryl group and the heteroaryl group may be optionally substituted with a substituent.
The above-mentioned
Figure BDA0002442544570000121
More preferably, it is selected from any one of the formulae (a-1-1) to (a-3-2):
Figure BDA0002442544570000122
p represents a para-attachment site, and m represents a meta-attachment site;
in a specific embodiment, the
Figure BDA0002442544570000123
Is a formula (a-1-1) or a formula (a-1-2).
The above-mentioned
Figure BDA0002442544570000124
Selected from any one of formulas (b-1) to (b-12):
Figure BDA0002442544570000125
Figure BDA0002442544570000131
p represents a para-attachment site, and m represents a meta-attachment site;
e and G are independently selected from-CO-, -SO2-、-BR9-or-POR9-; the R is6、R7、R8And R9Independently selected from-H, -X, C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl;
x is independently selected from F, Cl, Br or I; the heteroatoms of the heteroalkyl and heteroaryl groups are independently selected from B, N, O, P, S or Si; the alkyl group, the heteroalkyl group, the aryl group and the heteroaryl group may be optionally substituted with a substituent.
The above-mentioned
Figure BDA0002442544570000132
More preferably, it is selected from any one of the formulae (b-1-1) to (b-12-1):
Figure BDA0002442544570000133
p represents a para-attachment site, and m represents a meta-attachment site;
in a particular embodiment, the
Figure BDA0002442544570000134
Selected from formula (b-4-1) or formula (b-4-2).
In the present invention, the TADF polymer having an alternating connection of the electron donor and the electron acceptor in the meta position is specifically selected from any one of the formulas (I-1) to (I-12):
Figure BDA0002442544570000141
in a particular embodiment, the TADF polymer is selected from the group consisting of formulas (I-1) to (I-3).
The invention provides a preparation method of a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected, which comprises the following steps:
under inert atmosphere, mixing a diboron ester monomer with a structure shown in a formula (II), a bisbromine monomer with a structure shown in a formula (III), a palladium catalyst, a phase transfer catalyst, alkali and a reaction solvent, heating to carry out Suzuki polymerization, respectively adding a bromine end capping agent and a boron ester end capping agent after the reaction is finished, and then adding a chelating agent to quench the palladium catalyst to obtain the TADF polymer with the structure shown in the formula (I):
Figure BDA0002442544570000151
in the diboron ester monomer with the structure of the formula (II)
Figure BDA0002442544570000152
The technical proposal is as follows
Figure BDA0002442544570000153
The selection ranges are consistent, and detailed description is omitted here. In the double bromine monomer with the structure of the formula (III)
Figure BDA0002442544570000154
The technical proposal is as follows
Figure BDA0002442544570000155
The selected ranges are consistent and will not be described in detail herein.
In a specific embodiment of the present invention, the diboron ester monomer having the structure of formula (II) is specifically formula 101 or formula 102;
Figure BDA0002442544570000156
in a specific embodiment of the present invention, the diboron ester monomer having the structure of formula (iii) is specifically formula 201 or formula 202:
Figure BDA0002442544570000157
in the present invention, the palladium catalyst is preferably tetrakis (triphenylphosphine) palladium; the phase transfer catalyst is preferably methyl trioctyl ammonium chloride; the base is preferably potassium carbonate; the reaction solvent is preferably toluene and water (v/v ═ 0.5).
In the invention, the molar ratio of the diboron ester monomer with the structure of the formula (II), the bisbromine monomer with the structure of the formula (III), the palladium catalyst, the phase transfer catalyst and the alkali is preferably 1:1:0.01:0.1: 10.
In the invention, the temperature of the polymerization reaction is preferably 80-120 ℃, and more preferably 90-110 ℃; in a specific embodiment, the temperature of the polymerization reaction is 95 ℃. The time of the polymerization reaction is preferably 1-24 h.
In the invention, the bromine end-capping reagent is preferably bromobenzene, and the bromine end-capping reaction time is preferably 6-12 hours; the end capping agent of the boron ester is preferably phenylboronic acid, and the end capping reaction time of the boron ester is preferably 6-12 hours; the chelating agent is preferably sodium diethyldithiocarbamate trihydrate, and the time for the chelating agent to quench the palladium catalyst is preferably 6-12 hours.
The product obtained after quenching the palladium catalyst with a chelating agent is preferably subjected to a post-treatment to obtain a TADF polymer having the structure of formula (i). The post-treatment preferably comprises: diluting a reaction product by using a good solvent, washing by using a salt solution, drying by using a drying agent, concentrating, separating by using the good solvent as a mobile phase through a silica gel column, concentrating the obtained solution, settling in a poor solvent, performing vacuum filtration, purifying a solid phase by using an organic solvent through a Soxhlet extractor, and finally performing vacuum drying to obtain the TADF polymer with the structure of the formula (I). In the present invention, the good solvent used for the dilution and column separation is preferably selected from dichloromethane; the salt solution used for washing is preferably a saturated sodium chloride aqueous solution, the drying agent is preferably anhydrous sodium sulfate, the poor solvent used for settling is preferably methanol, the organic solvent used for Soxhlet extraction is preferably acetone, and the extraction and purification time is preferably 12-48 hours.
The invention provides an application of a TADF polymer containing a meta-position electron donor and an electron acceptor which are alternately connected in the technical scheme in the field of electroluminescent devices, which specifically comprises the following steps: as a light-emitting material; as host material or sensitizing material to desensitize fluorescent, phosphorescent and TADF luminescent objects.
In the present invention, the structure of the electroluminescent device preferably includes: anode/hole injection layer/light emitting layer/exciton blocking layer/electron transport layer/electron injection layer/cathode; the light-emitting layer comprises the TADF polymer which contains the meta-position electron donor and the electron acceptor which are alternately connected. The thickness of the light emitting layer is preferably 40 to 60nm, and more preferably 45 to 55 nm.
In a specific embodiment of the invention, the device structure is ITO/PEDOT: PSS (40 nm)/light emitting layer (50nm)/TSPO1(8nm)/TmPyPB (42nm)/LiF (1nm)/Al (100 nm).
To further illustrate the present invention, the TADF polymer containing an alternating linkage of a meta-position electron donor and an electron acceptor and its preparation and application are described in detail below with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Comparative example 1
A polymer with a structure of poly (TPAp-DCBp) and an electron donor and an electron acceptor which are connected alternately is synthesized by the following steps:
Figure BDA0002442544570000171
the synthesis conditions are as follows: i. sodium tert-butoxide, bis (dibenzylideneacetone) palladium, 1,1' -bis (diphenylphosphino) ferrocene, toluene, 120 ℃; pinacol bisborate, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, potassium acetate, dimethylformamide, 120 ℃; tetrakis (triphenylphosphine) palladium, methyltrioctylammonium chloride, aqueous potassium carbonate, toluene, 95 ℃.
(1) Synthesis of an intermediate having the chemical structure 1: p-bromoiodobenzene (11.88g,42mmol), p-octylaniline (4.11g,20mmol), sodium tert-butoxide (t-Buona,4.03g,42mmol), bis (dibenzylideneacetone) palladium (Pd)2(dba)30.92g,1mmol) and 1,1' -bis (diphenylphosphino) ferrocene (DPPF,2.22g,4mmol) were added to a round bottom flask with a stirring magneton. After evacuation and three cycles of nitrogen filling, 100ml of anhydrous and oxygen-free toluene (tolumen) was added as solvent and the temperature was raised to 120 ℃. After four hours, the reaction was complete and the system was allowed to cool to room temperature, diluted with 200ml of dichloromethane and washed three times with 300ml of saturated sodium chloride solution. Drying the separated organic phase by anhydrous sodium sulfate powder, decompressing and filtering, and concentrating the obtained solution to obtain a crude product. Using n-hexane as an eluent, the product was obtained as a colorless oily liquid after separation by silica gel chromatography, concentration of the solution and vacuum drying (7.0g, yield 68%).1H NMR(500MHz,CDCl3)δ7.34–7.29(m,4H),7.08(d,J＝8.4Hz,2H),6.99–6.95(m,2H),6.94–6.89(m,4H),2.59–2.53(m,2H),1.60(dt,J＝15.4,7.6Hz,2H),1.35–1.27(m,10H),0.89(t,J＝6.9Hz,3H).
(2) Monomer M1, synthesis: intermediate with chemical structure 1 (7.0g,13.6mmol), pinacol diboron (bis (pinacolato) -diboron, 10.3g,40.8mmol) and [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl20.59g,0.80mmol) and potassium acetate (KOAc,4.0g,40.8mmol) were added to a round bottom flask with a stirring magnet. After three cycles of vacuum-filling with nitrogen, 100ml of anhydrous and oxygen-free Dimethylformamide (DMF) was added as a reaction solvent, and the temperature was raised to 100 ℃. Twelve hours later, the reaction is finished, the reaction system is cooled to room temperature, the reaction solution is settled in 500ml of saturated sodium chloride aqueous solution, the reduced pressure suction filtration is carried out, the obtained filter residue is dissolved by 200ml of ethyl acetate, the filter residue is washed by the saturated sodium chloride aqueous solution with the same volume for three times, the separated organic phase is dried by anhydrous sodium sulfate powder and reduced pressure suction filtration, the obtained solution is concentrated to obtain a crude product, a mixed solvent of petroleum ether and ethyl acetate (v/v ═ 20:1) is used as an eluent, the crude product is separated by a silica gel chromatographic column, the solution is slowly cooled in hot methanol solution for recrystallization after being concentrated, and the separated solid is dried in vacuum to obtain a white solid (4.7g, the yield is 57%).1H NMR(500MHz,CDCl3)δ7.67(d,J＝8.4Hz,4H),7.05(td,J＝15.9,8.3Hz,8H),2.61–2.55(m,2H),1.66–1.58(m,2H),1.38–1.27(m,34H),0.90(t,J＝6.9Hz,3H).
(3) Synthesis of a Polymer with the chemical Structure poly (TPAp-DCBp): m1(0.6095g,1.0mmol), 2, 5-dibromoterephthalonitrile (0.2860g,1.0mmol) and methyltrioctylammonium chloride (Aliquat 336,. about.100 mg), tetrakis (triphenylphosphine) palladium (Pd (PPh) under an inert gas atmosphere3)410mg) was placed in a polymerization flask. Anhydrous and oxygen-free toluene (tolumen, 20ml) was introduced. After warming to 80 ℃, potassium carbonate aqueous solution (K) was added2CO3/H2O,2mol/L, 10ml), and the temperature is raised to 95 ℃. During the reaction, the viscosity of the system was observed, and when the egg white viscosity was reached, phenylboronic acid (50mg dissolved in 5ml toluene) was added to terminate the reaction for 8 hours. 0.5ml of bromobenzene was added for capping and the reaction was carried out for 8 hours. The catalyst was quenched by addition of an aqueous solution of sodium diethyldithiocarbamate trihydrate (1g/ml aqueous solution, 10 ml). The reaction was carried out for 8 hours, and the system was cooled to room temperature. The reaction solution was diluted with 100ml of dichloromethane and washed five times with an equal volume of saturated aqueous sodium chloride solution.The separated organic phase was dried over sodium sulfate powder, concentrated and passed through a silica gel column using dichloromethane as eluent to obtain a polymer solution. The resulting solution was concentrated to-5 ml, settled to 100ml methanol, suction filtered under reduced pressure to give a crude polymer, which was extracted in boiling acetone for 24 hours by a soxhlet extractor and finally dried under vacuum to give the final polymer product (320mg, 67% yield). The number average molecular weight Mn of the product was 13.1kDa by size exclusion chromatography, and the polydispersity PDI was 1.42.1H NMR(500MHz,CDCl3)δ7.95–7.87(m,2H),7.58–7.47(m,4H),7.35–7.23(m,4H),7.23–7.18(m,2H),7.19–7.13(m,2H),2.67–2.61(m,2H),1.71–1.61(m,2H),1.43–1.24(m,10H),0.90(t,J＝6.9Hz,3H).
FIG. 1 is an absorption emission spectrum of poly (TPAp-DCBp) polymer prepared in comparative example 1, wherein the poly (TPAp-DCBp) polymer has an absorption peak of 514nm, an emission peak of 533nm and a half-peak width of 71nm, and the poly (TPAp-DCBp) polymer has an electron donor and an electron acceptor alternately connected in a para-para position. FIG. 5 is a photo-transient retardation curve of poly (TPAp-DCBp) in pure film state, which can be seen to have almost no retardation component, indicating that it has no TADF property.
Example 1
A TADF polymer with a structure of poly (TPAp-DCBm) and an electron donor and an electron acceptor which are alternately connected in a para-meta position is synthesized by the following route:
Figure BDA0002442544570000191
the synthesis conditions are as follows: tetrakis (triphenylphosphine) palladium, methyl trioctyl ammonium chloride, potassium carbonate aqueous solution, toluene, 95 ℃.
Synthesis of a Polymer with the chemical Structure poly (TPAp-DCBm): m1(0.6095g,1.0mmol), 2, 6-dibromoterephthalonitrile (0.2860g,1.0mmol) and methyltrioctylammonium chloride (Aliquat 336,. about.100 mg), tetrakis (triphenylphosphine) palladium (Pd (PPh) under an inert gas atmosphere3)410mg) was placed in a polymerization flask. Anhydrous and oxygen-free toluene (tolumen, 20ml) was introduced. After warming to 80 ℃, potassium carbonate aqueous solution (K) was added2CO3/H2O,2mol/L, 10ml), and the temperature is raised to 95 ℃.During the reaction, the viscosity of the system was observed, and when the egg white viscosity was reached, phenylboronic acid (50mg dissolved in 5ml toluene) was added to terminate the reaction for 8 hours. 0.5ml of bromobenzene was added for capping and the reaction was carried out for 8 hours. The catalyst was quenched by addition of an aqueous solution of sodium diethyldithiocarbamate trihydrate (1g/ml aqueous solution, 10 ml). The reaction was carried out for 8 hours, and the system was cooled to room temperature. The reaction solution was diluted with 100ml of dichloromethane and washed five times with an equal volume of saturated aqueous sodium chloride solution. The separated organic phase was dried over sodium sulfate powder, concentrated and passed through a silica gel column using dichloromethane as eluent to obtain a polymer solution. The resulting solution was concentrated to-5 ml, settled to 100ml methanol, suction filtered under reduced pressure to give a crude polymer, which was extracted in boiling acetone for 24 hours by a soxhlet extractor and finally dried under vacuum to give the final polymer product (160mg, yield 34%). The number average molecular weight Mn of the polymer was 6.1kDa and the polydispersity number PDI was 1.33 as determined by size exclusion chromatography.1H NMR(500MHz,CDCl3)δ7.75–7.67(m,2H),7.56–7.41(m,4H),7.30–7.24(m,4H),7.22–7.12(m,4H),2.67–2.57(m,2H),1.66(dt,J＝15.1,7.6Hz,2H),1.46–1.20(m,10H),0.90(t,J＝6.7Hz,3H).
FIG. 2 is an absorption emission spectrum of TADF polymer poly (TPAp-DCBm) prepared in example 1, wherein the electron donor and the electron acceptor are alternately connected, in a pure film state, compared with comparative example 1, the absorption peak is blue-shifted to 496nm, the emission peak is hardly changed to 531nm, and the half-peak width is increased to 77 nm. FIG. 6 is a graph of the photo-induced transient retardation of poly (TPAp-DCBm) in the pure film state, and compared to comparative example 1, a significant retardation component can be seen, indicating significant TADF properties.
Example 2
A TADF polymer with a structure of poly (TPAm-DCBp) and an alternate connection of a meta-para electron donor and an electron acceptor is synthesized by the following steps:
Figure BDA0002442544570000201
the synthesis conditions are as follows: i. sodium tert-butoxide, bis (dibenzylideneacetone) palladium, 1,1' -bis (diphenylphosphino) ferrocene, toluene, 120 ℃; pinacol bisborate, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, potassium acetate, dimethylformamide, 120 ℃; tetrakis (triphenylphosphine) palladium, methyltrioctylammonium chloride, aqueous potassium carbonate, toluene, 95 ℃.
(1) Synthesis of an intermediate of chemical structure 2: m-bromoiodobenzene (11.88g,42mmol), p-octylaniline (4.11g,20mmol), sodium tert-butoxide (t-Buona,4.03g,42mmol), bis (dibenzylideneacetone) palladium (Pd)2(dba)30.92g,1mmol) and 1,1' -bis (diphenylphosphino) ferrocene (DPPF,2.22g,4mmol) were added to a round bottom flask with a stirring magneton. After three cycles of evacuation and nitrogen filling, 100ml of anhydrous and oxygen-free toluene (toluene) was added as solvent and the temperature was raised to 120 ℃. After four hours, the reaction was complete and the system was allowed to cool to room temperature, diluted with 200ml of dichloromethane and washed three times with 300ml of saturated sodium chloride solution. Drying the separated organic phase by anhydrous sodium sulfate powder, decompressing and filtering, and concentrating the obtained solution to obtain a crude product. Using n-hexane as an eluent, the product was obtained by silica gel column chromatography, concentration of the solution and vacuum drying (9.0g, yield 87%) as a colorless oily liquid.1H NMR(500MHz,CDCl3)δ7.17(t,J＝1.9Hz,2H),7.14–7.06(m,6H),7.01–6.94(m,4H),2.61–2.55(m,2H),1.62(dt,J＝15.5,7.7Hz,2H),1.39–1.23(m,10H),0.89(t,J＝6.9Hz,3H).
(2) Synthesis of monomer M2: 2(9.0g,17.5mmol), pinacol ester diboron (bis (pinacolato) -diboron, 13.2g,52.5mmol) and [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl20.76g,1.03mmol) and potassium acetate (KOAc,5.14g,52.5mmol) were added to a round bottom flask with a stirring magnet. After three cycles of vacuum-nitrogen filling, 100ml of anhydrous and oxygen-free Dimethylformamide (DMF) was added as a reaction solvent and the temperature was raised to 100 ℃. Twelve hours later, the reaction is finished, the reaction system is cooled to room temperature, the reaction solution is settled in 500ml of saturated sodium chloride aqueous solution, the pressure reduction and the suction filtration are carried out, the obtained filter residue is dissolved by 200ml of ethyl acetate, the filter residue is washed by the saturated sodium chloride aqueous solution with the same volume for three times, the separated organic phase is dried by anhydrous sodium sulfate powder, the pressure reduction and the suction filtration are carried out, the obtained solution is concentrated to obtain a crude product, and the crude product is obtained by using a mixed solvent (v & ltwill & gt/L & gt) of petroleum ether and ethyl acetatev ═ 20:1) as eluent, and was subjected to silica gel column chromatography, the solution was concentrated and then recrystallized in hot methanol solution with slow cooling, and the precipitated solid was dried under vacuum to give the product as a white solid (4.5g, 42% yield).1H NMR(500MHz,CDCl3)δ7.55(d,J＝1.9Hz,2H),7.44(d,J＝7.2Hz,2H),7.23(t,J＝7.7Hz,2H),7.15–7.10(m,2H),7.03(d,J＝8.4Hz,2H),6.94(d,J＝8.4Hz,2H),2.59–2.51(m,2H),1.64–1.57(m,2H),1.39–1.23(m,34H),0.89(t,J＝6.9Hz,3H).
(3) Synthesis of a Polymer with the chemical Structure poly (TPAm-DCBp): m2(0.6095g,1.0mmol), 2, 5-dibromoterephthalonitrile (0.2860g,1.0mmol) and methyltrioctylammonium chloride (Aliquat 336,. about.100 mg), tetrakis (triphenylphosphine) palladium (Pd (PPh) under an inert gas atmosphere3)410mg) was placed in a polymerization flask. Anhydrous and oxygen-free toluene (tolumen, 20ml) was introduced. After warming to 80 ℃, potassium carbonate aqueous solution (K) was added2CO3/H2O,2mol/L, 10ml), and the temperature is raised to 95 ℃. During the reaction, the viscosity of the system was observed, and when the egg white viscosity was reached, phenylboronic acid (50mg dissolved in 5ml toluene) was added to terminate the reaction for 8 hours. 0.5ml of bromobenzene was added for capping and the reaction was carried out for 8 hours. The catalyst was quenched by addition of an aqueous solution of sodium diethyldithiocarbamate trihydrate (1g/ml aqueous solution, 10 ml). The reaction was carried out for 8 hours, and the system was cooled to room temperature. The reaction solution was diluted with 100ml of dichloromethane and washed five times with an equal volume of saturated aqueous sodium chloride solution. The separated organic phase was dried over sodium sulfate powder, concentrated and passed through a silica gel column using dichloromethane as eluent to obtain a polymer solution. The resulting solution was concentrated to-5 ml, settled to 100ml methanol, suction filtered under reduced pressure to give a crude polymer, which was extracted in boiling acetone for 24 hours by a soxhlet extractor and finally dried under vacuum to give the final polymer product (170mg, 36% yield). The number average molecular weight Mn of the polymer was 4.1kDa and the polydispersity number PDI was 1.29 as determined by size exclusion chromatography.1H NMR(500MHz,CDCl3)δ7.88–7.74(m,2H),7.46–7.33(m,2H),7.30–7.20(m,4H),7.21–7.05(m,6H),2.63–2.55(m,2H),1.70–1.57(m,2H),1.37–1.25(m,10H),0.88(t,J＝6.8Hz,3H).
FIG. 3 is an absorption emission spectrum of TADF polymer poly (TPAm-DCBp) prepared in example 2 and having alternately connected meta-para electron donor and electron acceptor, compared with comparative example 1, wherein the absorption peak is blue-shifted to 455nm, the emission peak is hardly 524nm, and the half-peak width is increased to 79 nm; FIG. 7 is a graph of the photo-induced transient retardation of poly (TPAm-DCBp) in the pure film state, and compared to comparative example 1, it is possible to see a significant retardation component, indicating a significant TADF property.
Example 3
A TADF polymer with a structure of poly (TPAm-DCBm) and an electron donor and an electron acceptor which are connected alternately at meta-meta positions is synthesized by the following steps:
Figure BDA0002442544570000221
the synthesis conditions are as follows: tetrakis (triphenylphosphine) palladium, methyl trioctyl ammonium chloride, potassium carbonate aqueous solution, toluene, 95 ℃.
Synthesis of a Polymer with the chemical Structure poly (TPAm-DCBm): m2(0.6095g,1.0mmol), 2, 6-dibromoterephthalonitrile (0.2860g,1.0mmol) and methyltrioctylammonium chloride (Aliquat 336,. about.100 mg), tetrakis (triphenylphosphine) palladium (Pd (PPh) under an inert gas atmosphere3)410mg) was placed in a polymerization flask. Anhydrous and oxygen-free toluene (tolumen, 20ml) was introduced. After warming to 80 ℃, potassium carbonate aqueous solution (K) was added2CO3/H2O,2mol/L, 10ml), and the temperature is raised to 95 ℃. During the reaction, the viscosity of the system was observed, and when the egg white viscosity was reached, phenylboronic acid (50mg dissolved in 5ml toluene) was added to terminate the reaction for 8 hours. 0.5ml of bromobenzene was added for capping and the reaction was carried out for 8 hours. The catalyst was quenched by addition of an aqueous solution of sodium diethyldithiocarbamate trihydrate (1g/ml aqueous solution, 10 ml). The reaction was carried out for 8 hours, and the system was cooled to room temperature. The reaction solution was diluted with 100ml of dichloromethane and washed five times with an equal volume of saturated aqueous sodium chloride solution. The separated organic phase was dried over sodium sulfate powder, concentrated and passed through a silica gel column using dichloromethane as eluent to obtain a polymer solution. Concentrating the obtained solution to 5ml, settling in 100ml methanol, vacuum filtering to obtain crude polymer product, and extracting in boiling acetone with Soxhlet extractorExtraction was carried out for 24 hours and finally vacuum-dried to give the final polymer product (150mg, 31% yield). The number average molecular weight Mn of the polymer was 7.5kDa by size exclusion chromatography, and the polydispersity PDI was 1.92.1H NMR(500MHz,CDCl3)δ7.73–7.56(m,2H),7.41–7.30(m,2H),7.25–7.14(m,4H),7.15–7.01(m,6H),2.62–2.52(m,2H),1.61(d,J＝7.2Hz,2H),1.38–1.22(m,10H),0.87(t,J＝6.9Hz,3H).
FIG. 4 is an absorption emission spectrum of TADF polymer poly (TPAm-DCBm) prepared in example 3, wherein the electron donor and the electron acceptor are alternately connected, in a pure film state, and compared with examples 1 and 2, the absorption peak is further blue-shifted to 448nm, the emission peak is hardly changed to 529nm, and the half-peak width is further increased to 88 nm; FIG. 8 is a photo-transient retardation curve of poly (TPAm-DCBm) in pure film state, which can be seen to have more retardation component than those of examples 1 and 2, indicating further enhanced TADF properties.
FIG. 9 is a comparison of light induced transient decay curves of a polymer poly (TPAp-DCBp) prepared in comparative example 1 and containing an alternating linkage of an electron donor and an electron acceptor and TADF polymers poly (TPAp-DCBm), poly (TPAm-DCBp) and poly (TPAm-DCBm) prepared in examples 1 to 3, wherein the polymer poly (TPAp-DCBp) and the polymer poly (TPAm-DCBm) contain an alternating linkage of an electron donor and an electron acceptor in a pure film state.
Example 4
Preparation of electroluminescent device:
the structure of the device is ITO/PEDOT, PSS (40 nm)/luminous layer (50nm)/TSPO1(8nm)/TmPyPB (42nm)/LiF (1nm)/Al (100 nm). Wherein Indium Tin Oxide (ITO) loaded on a glass substrate is used as an anode, after the ultraviolet-ozone treatment is carried out for 40 minutes, a layer of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT/PSS) is coated on the ITO by spin coating to be used as a hole injection layer, and the ITO is annealed for 1 hour at the temperature of 120 ℃; followed by spin coating to dissolve 5 wt.% polymer synthesized by the above-described comparative example 1, example 2, example 3, and 5 wt.% polymer of example 3 and 1 wt.% (TPAPQ), respectively, of the present invention2Ir (acac), a red phosphorescent dye, from Synthetic Metals,2005,155,539-548, in the order of device numbers corresponding to the above five light-emitting layers, was added to a solution of mCP (1, 3-dicarbazolylbenzene) chlorobenzene (10mg/ml) as a light-emitting layerA, B, C, D and E), annealing at 100 ℃ for 30 minutes; finally transferring to vacuum evaporation station at a temperature below 4 × 10-4In Pa vacuum, TSPO1 (diphenyl-4-triphenylsilylphenyl-phosphine oxide) was deposited as exciton blocking layer, TmPyPB (1,3, 5-tris [ (3-pyridyl) -phen-3-yl]Benzene) as an electron transport layer, LiF (lithium fluoride) as an electron injection layer, and aluminum (Al) as a cathode. The test was carried out using five electroluminescent devices of example 4, the results of which are shown in table 1:
table 1 test results of electroluminescent devices prepared in example 4
Figure BDA0002442544570000241
As can be seen from table 1, the electroluminescent devices A, B, C and D obtained using the polymers prepared in comparative example 1, example 2 and example 3 as the light-emitting layer dye have similar on-state voltages (around 4.0V) and emission spectra (x-polar difference of 0.07 and y-polar difference of 0.06 in color coordinates). But from a to B, C to D, the maximum external quantum efficiency of the corresponding device is improved from 4.2% to 5.2%, 5.9% and even further to 8.8%, as shown in fig. 10. It is shown that for alternating polymers obtained with the same electron donor and the same electron acceptor, the meta-linkages have less influence on the emission spectra they produce, but have a large influence on their TADF properties, thus determining their performance as luminescent layer dyes in electroluminescent devices. The resulting electroluminescent device E, using the TADF polymer prepared in example 3 as a light-emitting layer sensitizer in combination with a red phosphorescent dye, also exhibits a similar ignition voltage (4.0V). As can be seen from fig. 11, unlike the green emission of device D, device E exhibits red emission (color coordinates of 0.65,0.35) of the phosphorescent dye and a maximum external quantum efficiency of 8.2%, indicating that the TADF polymer having the electron donor and the electron acceptor alternately connected in the meta position provided by the present invention can also be applied to an electroluminescent device as a light-emitting layer host or a sensitizer.
As can be seen from the above examples, the present invention provides a polymer having the structure of formula (I) which is alternately connected using the same electron donor unit and the same electron acceptor unit, and the retardation component of the light induced transient decay curve of the corresponding polymer gradually increases from the para position to the meta position only by changing the connection mode between the electron donor and the electron acceptor, indicating that the TADF properties are gradually enhanced. Finally, polymers in which both the donor and the acceptor are connected in the meta position exhibit good electroluminescent properties: as a luminescent layer dye, the maximum external quantum efficiency of the device is 8.8%; as a light emitting layer sensitizer, a red phosphorescent dye was sensitized, and the maximum external quantum efficiency of the device was 8.2%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A TADF polymer containing an alternating linkage of a meta-position electron donor and an electron acceptor has the structure of formula (I):
Figure FDA0003005523130000011
wherein the content of the first and second substances,
Figure FDA0003005523130000012
is an electron donor unit;
Figure FDA0003005523130000013
is an electron acceptor unit;
n＝2～200；
the electron donor units and/or the electron acceptor units are alternately connected by adopting meta-position sites;
the above-mentioned
Figure FDA0003005523130000014
Any one selected from formulas (a-1-1) to (a-3-2):
Figure FDA0003005523130000015
the above-mentioned
Figure FDA0003005523130000016
Any one selected from the formulas (b-1-1) to (b-12-1):
Figure FDA0003005523130000021
p represents a para-attachment site, and m represents a meta-attachment site.
2. The TADF polymer according to claim 1, characterized in that it is selected in particular from any one of formulae (i-1) to (i-12):
Figure FDA0003005523130000022
Figure FDA0003005523130000031
3. a method for preparing TADF polymer containing alternately connected meta-position electron donor and electron acceptor according to any of claims 1-2, comprising the steps of:
under inert atmosphere, mixing a diboron ester monomer with a structure shown in a formula (II), a bisbromine monomer with a structure shown in a formula (III), a palladium catalyst, a phase transfer catalyst, alkali and a reaction solvent, heating to carry out Suzuki polymerization, respectively adding a bromine end capping agent and a boron ester end capping agent after the reaction is finished, and then adding a chelating agent to quench the palladium catalyst to obtain the TADF polymer with the structure shown in the formula (I):
Figure FDA0003005523130000041
the molar ratio of the diboron ester monomer with the structure of formula (II), the bisbromine monomer with the structure of formula (III), the palladium catalyst, the phase transfer catalyst and the alkali is 1:1 (0.001-0.01): 0.1-1: 2-20;
the temperature of the polymerization reaction is 80-120 ℃; the time of the polymerization reaction is 1-24 h.
4. The TADF polymer containing the alternatively-connected meta-position electron donor and the alternatively-connected electron acceptor, which is prepared by the preparation method of claim 3, is applied to the field of electroluminescent devices.
5. The use according to claim 4, wherein the TADF polymer comprising an alternating connection of an electron donor and an electron acceptor in meta-position is used as a light-emitting material.
6. The use according to claim 4, wherein the TADF polymer containing the meta-position electron donor and the electron acceptor alternately connected is used as a host material or a sensitizing material for desensitizing fluorescent, phosphorescent and TADF luminescent objects.
CN202010269396.5A 2020-04-08 2020-04-08 TADF (TADF) polymer containing meta-position electron donor and electron acceptor alternately connected as well as preparation method and application thereof Active CN111363124B (en)

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