CN109516985B - 1, 3-di (2-pyridyl) benzene acceptor unit and indacenodipyridinedione organic semiconductor material and application - Google Patents

1, 3-di (2-pyridyl) benzene acceptor unit and indacenodipyridinedione organic semiconductor material and application Download PDF

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CN109516985B
CN109516985B CN201811301645.3A CN201811301645A CN109516985B CN 109516985 B CN109516985 B CN 109516985B CN 201811301645 A CN201811301645 A CN 201811301645A CN 109516985 B CN109516985 B CN 109516985B
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王亚飞
谭帅
吴秀刚
朱卫国
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Abstract

The invention discloses a 1, 3-di (2-pyridyl) benzene acceptor unit and indacenodipyridinedione organic semiconductor material and application thereof. 1, 3-di (2-pyridyl) benzene is used as a basic framework, an electron-withdrawing group is introduced into the 6' position of a pyridine ring through Friedel-crafts reaction, an intramolecular cyclization reaction is utilized to construct a novel electron acceptor framework of the indacenodipyridinedione, and an indacenodipyridinedione framework unit is further used as an electron acceptor to construct a donor-acceptor-donor type organic semiconductor material through a coupling reaction.

Description

1, 3-di (2-pyridyl) benzene acceptor unit and indacenodipyridinedione organic semiconductor material and application
Technical Field
The invention relates to a novel organic semiconductor material, in particular to a 1, 3-di (2-pyridyl) benzene acceptor unit, an indacenodipyridone organic semiconductor material constructed by the 1, 3-di (2-pyridyl) benzene acceptor unit and an organic donor unit, and application of the indacenodipyridone organic semiconductor material in a light-emitting device, belonging to the technical field of organic electronic materials.
Background
1, 3-di (2-pyridyl) benzene is known as a chelating ligand because of the characteristics of better conjugated structure, unique metal chelating effect, easy modification of molecules and the like, and is widely applied to inorganic/organic metal complexes. The 1, 3-di (2-pyridyl) benzene unit has an N, C, N three-coordination framework, wherein N is a neutral donor unit, and C represents an anionic aromatic ring C atom. In the past decades, a large number of organometallic complexes based on 1, 3-bis (2-pyridyl) benzene chelate ligands, such as the metals platinum, iridium, palladium, ruthenium, etc., have been developed as light emitting materials, dye sensitized cells, catalysts, etc. It is worth noting that structural modification of the N, C, N chelating ligand has a greater impact on the performance of its metal complex. The current structural modification means for 1, 3-bis (2-pyridyl) benzene skeleton can be roughly divided into the following two types: 1. an electron donor or electron acceptor unit (such as a compound 1 in the attached figure 1) is introduced at the 4,5 and 6 positions of a benzene ring or 3',4' and 5' of a pyridine ring, but the method can only adjust the highest occupied orbital (HOMO) or the lowest unoccupied orbital (LUMO) of the material, and cannot effectively adjust and control the space structure of the material, so that the intermolecular action of the material is stronger; 2. the introduction of an aromatic ring structure (such as compound 2 in figure 1) on the pyridine ring is only a simple introduction of a fused ring structure, and does not effectively increase the conjugation degree of the 1, 3-bis (2-pyridyl) benzene.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a novel indacenodipyridinedione acceptor unit which is constructed by introducing an electron-withdrawing group into the 6' position of a pyridine ring of a 1, 3-bis (2-pyridyl) benzene framework or utilizing an intramolecular cyclization reaction, and the acceptor unit has better planarity, higher conjugation degree and stronger electron acceptor performance than the existing 1, 3-bis (2-pyridyl) benzene framework acceptor unit.
Another object of the present invention is to provide a series of indacenodipyridinedione donor-acceptor-donor type organic semiconductor materials having excellent luminescence properties, which are constructed with 1, 3-bis (2-pyridyl) benzene acceptor units.
A third object of the present invention is to provide the use of such donor-acceptor-donor type materials based on 1, 3-bis (2-pyridyl) benzene derivatives as light emitting materials for organic electroluminescent diodes, exhibiting excellent electroluminescent properties.
In order to achieve the above technical objects, the present invention provides a 1, 3-bis (2-pyridyl) benzene electron acceptor unit having a structure of formula 1, formula 2 or formula 3:
Figure GDA0002430204240000021
wherein,
r is a halogen substituent;
R1is an oxygen atom, a sulfur atom or a seleno groupA seed;
R2is a hydrogen atom or a halogen substituent.
Preferred 1, 3-bis (2-pyridyl) benzene electron acceptor units have R as the chloro substituent and R is1Is an oxygen atom, R2Is a hydrogen atom.
The present invention also provides a donor-acceptor-donor type organic semiconductor material of indacenodipyridinedione based on a 1, 3-bis (2-pyridyl) benzene electron acceptor unit, having a structure of formula 4, formula 5, formula 6, formula 7, or formula 8:
Figure GDA0002430204240000031
wherein,
R1is oxygen atom, sulfur atom or selenium atom;
R3are donor units.
Preferred donor-acceptor-donor organic semiconductor materials based on indacenodipyridindione of the 1, 3-bis (2-pyridyl) benzene electron acceptor units have R3 being one of the following structures:
Figure GDA0002430204240000032
the invention also provides application of the donor-acceptor-donor type organic semiconductor material of the indacenodipyridinedione based on the 1, 3-di (2-pyridyl) benzene electron acceptor unit, which is used as a luminescent layer material of an organic electroluminescent diode.
The invention takes 1, 3-di (2-pyridyl) benzene skeleton as the base, and modifies an electron-withdrawing group on the 6' position of a pyridine ring; and an intramolecular cyclization reaction is utilized to construct the indacenodipyridinedione derivative, and the indacenodipyridinedione derivative can be coupled with the existing common donor unit to obtain a series of donor-acceptor-donor organic semiconductor materials of the indacenodipyridinedione.
The invention introduces an electron-withdrawing group at the 6' position of a pyridine ring through Friedel-crafts reaction, the method can effectively adjust the space structure of molecules and further adjust the intermolecular action, and simultaneously, in order to further increase the conjugation degree of 1, 3-di (2-pyridyl) benzene and enhance the electron-withdrawing performance, the invention constructs the rigid skeleton of the indacene bipyridyl diketone through intramolecular cyclization reaction. Compared with the existing 1, 3-di (2-pyridyl) benzene skeleton, the indacenodipyridinedione rigid skeleton has obvious advantages, and is mainly reflected in better conjugation degree and electron-withdrawing capability. Compared with the prior art, the indacenodipyridone rigid framework has good photoelectric property and is an organic semiconductor material with commercial prospect.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention introduces an electron-withdrawing group on the 6-position of a pyridine ring in a 1, 3-di (2-pyridyl) benzene skeleton for the first time; meanwhile, an intramolecular cyclization reaction is utilized to construct a molecular framework of the indacenodipyridinedione for the first time.
Compared with the reported 1, 3-di (2-pyridyl) benzene molecular skeleton, the indacenodipyridone molecular skeleton has better planarity and conjugation degree and stronger electron acceptor performance, is favorable for constructing a donor-acceptor-donor type organic semiconductor material, and expands the types of acceptor units of the organic semiconductor material.
The invention further introduces different donor units into the indacenodipyridinedione skeleton to construct a series of organic semiconductor materials with novel structures.
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FIG. 1 is a method for modifying the structure of a 1, 3-bis (2-pyridyl) benzene derivative according to the prior art and the technical scheme of the present invention.
Fig. 2 shows a single crystal derivative structure of compound 9 obtained in example 1 of the present invention.
FIG. 3 shows a single crystal derivative structure of Compound 18 obtained in example 2 of the present invention.
FIG. 4 is a diagram showing UV-VIS absorption spectra of compound 9 and compound 10 in dichloromethane solution, which were obtained in example 1 of the present invention.
FIG. 5 is a diagram showing an ultraviolet-visible absorption spectrum of Compound 18 obtained in example 2 of the present invention in a dichloromethane solution.
FIG. 6 shows photoluminescence spectra of compound 9 and compound 10 prepared in example 1 of the present invention in a dichloromethane solution.
FIG. 7 is a photoluminescence spectrum of compound 18 prepared in example 2 of the present invention in a dichloromethane solution.
Detailed Description
The following specific examples are intended to further illustrate the invention, but these specific embodiments do not limit the scope of the invention in any way.
Example 1
Figure GDA0002430204240000051
Synthesis of Compounds 5-11: the reaction conditions are a) MeOH, room temperature, 2h, b)1, 3-benzenediboronic acid, Pd (dppf) Cl2，K2CO3，THF/H2O，85℃，24h，c)NaOH aq.，ethanol，80℃，12h，d)AlCl3，benzene，135℃，24h.
Synthesis of Compound 6
In a 250mL single-necked flask, 2-bromonicotinic acid (5.0g, 24.8mmol), dichloromethane (100mL) and 3 drops of DMF were added, oxalyl chloride (10mL) was added dropwise at 0 deg.C, and the mixture was stirred at room temperature for 2 h. The solvent was removed by rotary evaporation under reduced pressure, anhydrous methanol was added dropwise at 0 ℃ and stirred at room temperature for 2 hours, then the methanol was removed under reduced pressure, the crude product was dissolved in dichloromethane, washed with water, the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure and dried to give a yellow liquid (3.8g, 71%).1H NMR(400MHz,CDCl3)8.51(dd,J＝4.8,1.6Hz,1H),8.17(dd,J＝8.0,1.6Hz,1H),7.34-7.31(m,1H),3.95(s,3H)。
Synthesis of Compound 7
In a 100mL three-necked flask, 1, 3-benzenediboronic acid (0.66g, 4mmol), compound 6(1.8g,8.4mmol), potassium carbonate (1.1g,7.97mmol), 1,1' -bis diphenylphosphinoferrocene palladium dichloride (0.146g,0.2mmol) and tetrahydrofuran/water (20mL/4mL) were added in this order, and the mixture was stirred under nitrogenAfter the reaction solution was cooled to room temperature for 24 hours, the solvent was removed under reduced pressure, the residue was transferred to a separatory funnel with dichloromethane, washed with water (3 × 100mL), the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, and the crude product was separated by column chromatography using petroleum ether/ethyl acetate (V/V ═ 5:1) as an eluent to give a colorless thick substance (1.0g, 74%).1H NMR(400MHz,CDCl3)8.78(dd,J＝4.8,1.6Hz,2H),8.11(dd,J＝8.0,2.0Hz,2H),7.79(t,J＝1.2Hz,1H),7.64-7.57(m,2H),7,52-7.48(m,1H),7.36-7.33(m,2H),3.71(s,6H)。
Synthesis of Compound 8
In a 100mL single-neck flask, Compound 7(2.6g,7.47mmol), sodium hydroxide (1.55g,38.9mmol), ethanol (60mL) and distilled water (12mL) were added and the mixture was refluxed at 80 ℃ overnight. Ethanol was removed under reduced pressure, dilute hydrochloric acid was added dropwise to the residue to PH 2, large amount of ethanol was added, the filtrate was collected, the solvent was removed under reduced pressure, and dried to give a white solid (2.2g, 90%).1H NMR(400MHz,DMSO)8.77(dd,J＝4.8,1.6Hz,2H),8.12(dd,J＝7.6,1.6Hz,2H),7.85(t,J＝1.6Hz,1H),7.64-7.61(m,2H),7.54-7.49(m,3H)。
Synthesis of Compound 9 and Compound 10
In a 100mL single-neck flask was added compound 8(1.0g,3.13mmol), AlCl3(3.74g,28.1mmol) and benzene, mixture N2Stirring is carried out for 24 hours under reflux. After the reaction was cooled to room temperature, 10mL of saturated sodium bicarbonate was added to quench, the reaction residue was evaporated under reduced pressure to remove the solvent, and the crude product was subjected to column chromatography using petroleum ether/ethyl acetate (V/V ═ 3:2) as an eluent to give compound 9(350mg, 22%) and compound 10(170mg, 10%) as white solids. Compound 9:1H NMR(400MHz,CDCl3)8.81(dd, J ═ 4.8,1.6Hz,2H),7.91(t, J ═ 2.0Hz,1H),7.80(dd, J ═ 7.6,1.6Hz,2H),7.56-7.53(m,4H),7.37(ddd, J ═ 12.4,7.6,4.8Hz,4H),7.26-7.23(m,4H),7.09(t, J ═ 7.6Hz, 1H). Compound 10:1H NMR(400MHz,CDCl3)8.83(dd,J＝18.4,4.0Hz,2H),7.96(dd,7.6 0.8Hz,1H),7.81-7.76(m,2H),7.56-7.54(m,2H),7.41-7.36(m,4H),7.30-7.12(m,6H),7.08-7.04(m,1H).
example 2
Figure GDA0002430204240000071
Synthesis of Compounds 12-16: reaction conditions are as follows: a) pd (PPh)3)42-pyridineboronic acid, b) PCC, BuOH, H2O；c)n-BuLi,THF。
Synthesis of Compound 13
2-Pyridineboronic acid (0.05mol), 1, 5-dibromo-2, 4-dimethylbenzene (5.3g,0.02mol), and Pd (PPh) were sequentially added to a 100mL three-necked flask3)4(0.28g,0.4mmol) and toluene, the mixture was reacted at 116 ℃ under nitrogen for 24 h. After the reaction was cooled to room temperature, it was washed with water (50mL) and sodium bicarbonate solution (10%, 150mL) in that order. The organic phase was dried over magnesium sulfate and the solvent was evaporated under reduced pressure and the crude product was isolated by column chromatography using n-hexane/dichloromethane (V/V ═ 8:1) as eluent to give an off-white solid (3.6g, 69%).1H NMR(400MHz,CDCl3)8.70(d,J＝4.9,2H),7.73(td,J＝7.74,1.8Hz,2H),7.49(s,1H),7.45(d,J＝8,2H),7.25-7.22(m,3H),2.42(s,6H).
Synthesis of Compound 14
In a 250mL three-necked flask, compound 13(1.6g,6.15mmol), sodium hydroxide (0.49g,12.3mmol) and t-butanol/water (1:1) (100mL) were added in this order, and after the mixture was heated to 100 ℃, PCC (9.7g) was added in portions and stirred for 4 hours. After the reaction, the reaction mixture was filtered while it was hot, the filtrate was adjusted to PH 5 with 1N hydrochloric acid, filtered under suction, and the filter cake was washed with water and dried to obtain a white solid (1.4g, 72%).1H NMR(300MHz,d-DMSO)13.00(bs,2H),8.63(d,J＝6Hz,2H),8.01(s,2H),7.90(dd,J＝9Hz,3Hz,1H),7.78(s,1H),7.74(d,J＝9Hz,1H),7.43-7.39(dd,J＝6Hz,3Hz,2H).
Synthesis of Compound 15
Compound 14(0.16g,0.50mmol) and tetrahydrofuran (6mL) were added to a 25mL three-necked flask, n-butyllithium (2M,1.3mL,2.6mmol) was added at 0 ℃, the mixture was reacted at room temperature for 2 hours, and then 2mL of water was added to quench the reaction, the reaction solution was extracted with dichloromethane (3 × 20mL), the organic phase was dried over magnesium sulfate, the solvent was distilled under reduced pressure, and the residue was subjected to column chromatography using dichloromethane/ethyl acetate (V/V ═ 1:1) as an eluent to give a brown solid (63mg, 44%).1H NMR(400MHz,CDCl3)8.75(d,J＝4.3,2H),8.44(s,1H),8.07(s,1H),7.98(d,J＝7.4,2H),7.34-7.40(m,2H)。
Example 3
Figure GDA0002430204240000081
Synthesis of Compounds 18, 19. Reaction conditions are as follows: a) pd (PPh)3)4,THF、K2CO3,80℃,8h；b)Pd(PPh3)4Toluene, ethanol, K2CO3,80℃,16h。
Synthesis of Compound 18
A50 mL three-necked flask was charged with Compound 17(0.5g,1.14mmol), diphenylamine (0.5g,3mmol), Pd (PPh)3)4(0.05eq), 2M K2CO3The reaction solution was extracted with dichloromethane (3 × 20mL), the organic phase was dried over magnesium sulfate, the solvent was distilled under reduced pressure, and the residue was subjected to column chromatography using petroleum ether/ethyl acetate (V/V ═ 1:1) as an eluent to give a white solid (0.5g, 72%).1H NMR(400MHz,CDCl3)9.10(s,1H),8.07(s,1H),7.96(s,1H),7.52(d,J＝7.3,2H),8.44(s,1H),7.24-7.28(m,8H),7.08-7.00(m,12H)。
Synthesis of Compound 19
A50 mL three-necked flask was charged with compound 19(0.5g,1.14mmol), diphenylamine (0.5g,3mmol), Pd (PPh)3)4(0.05eq), 2M K2CO3The reaction solution was extracted with dichloromethane (3 × 20mL), the organic phase was dried over magnesium sulfate, the solvent was distilled under reduced pressure, and the residue was subjected to column chromatography using dichloromethane/ethyl acetate (V/V ═ 1:1) as an eluent to give a white solid (0.58g, 83%).1H NMR(400MHz,CDCl3)9.23(s,2H),7.96(s,2H),7.52(s,2H),7.24-7.28(m,8H),7.08-7.00(m,12H)。
Example 4
Uv-vis absorption spectrum test of compound 9 in example 1, compound 10 and compound 18 in example 2.
Dissolving compound 9, compound 10 and compound 18 in dichloromethane solution respectively to prepare 10-5And M, testing the ultraviolet visible absorption spectrum of the solution. As can be seen from the figure, the ultraviolet-visible absorption spectra of the compound 9 and the compound 10 in the dichloromethane solution are approximately the same, the maximum absorption peak is 262nm, and the maximum absorption peak is mainly derived from pi-pi electron transition; compound 18 exhibited a distinct absorption spectrum in dichloromethane solution compared to compound 9 and compound 10. It has absorption peaks at 264nm, 280nm and 340nm, respectively. Wherein the absorption at 264nm is from pi-pi electron transition, and the absorption at 280nm and 340nm is attributed to n-pi*And (4) electron transition.
Example 5
Steady state fluorescence spectroscopy test for compound 9 in example 1, compound 10 and compound 18 in example 2.
Dissolving compound 9, compound 10 and compound 18 in dichloromethane solution respectively to prepare 10-5M solution, and testing the photoluminescence spectrum of the solution. Fig. 6 and 7 are photoluminescence spectra of compound 9, compound 10 and compound 18 in solution.
As can be seen, under the excitation of light, the compound 9 and the compound 10 show similar emission spectra in a dichloromethane solution, and the maximum emission peak is 365 nm; the emission spectrum of compound 18 in dichloromethane solution exhibited a large red shift with a maximum emission peak of 518nm, indicating that compound 18 has a greater degree of conjugation than compound 9 and compound 10.
While the present invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In light of the present inventive concept, those skilled in the art will recognize that certain changes may be made in the embodiments of the invention to which the invention pertains without departing from the spirit and scope of the claims.
Example 6
Electroluminescent device performance testing of compound 18 in example 2.
Dissolving Compound 18 in IIPreparing 10mg/mL solution in chlorobenzene solution, and preparing a solution-processed organic electroluminescent device by using a compound 18 as a luminescent layer dopant, PVK as a hole transport layer, mCP as a main material and Liq as a cathode material. The device results show that: the maximum external quantum efficiency of the electroluminescent device based on the compound 18 reaches 19.2 percent, and the maximum luminous brightness reaches 12000cd/m2And the efficiency roll-off is very small, so that the method has a very good commercialization prospect.

Claims (2)

1. A donor-acceptor-donor type organic semiconductor material of indacenodipyridindione based on 1, 3-bis (2-pyridyl) benzene electron acceptor units, characterized in that: has the structure of formula 6 or formula 7:
Figure FDA0002570565500000011
wherein,
R1is oxygen atom, sulfur atom or selenium atom;
R3is one of the following structures:
Figure FDA0002570565500000012
2. use of a donor-acceptor-donor type organic semiconducting material of indacenodipyridinedione based on 1, 3-bis (2-pyridyl) benzene electron acceptor units according to claim 1, characterized in that: the organic electroluminescent material is applied as a luminescent layer material of an organic electroluminescent diode.
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