CN109535166B - Luminescent organic semiconductor framework material and application thereof - Google Patents
Luminescent organic semiconductor framework material and application thereof Download PDFInfo
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Abstract
The invention discloses a luminescent organic semiconductor framework material and application thereof, wherein hetero atoms such as N, O, S and the like are arranged at the same end of an aromatic condensed ring to induce molecules to generate static dipole moment, intermolecular forces such as intermolecular hydrogen bond, dipole-dipole interaction and the like are used for regulating and controlling an accumulation microstructure in a molecular aggregation state, and the luminescent property of the material, the luminescent color of the material and the carrier transmission property of the material have excellent aggregation state luminescent property.
Description
Technical Field
The invention belongs to the technical field of light-emitting organic semiconductor materials, and particularly relates to a light-emitting organic semiconductor framework material and application thereof.
Background
Organic electronics taking organic conjugated molecules as a core is an important international leading-edge research field at present, and the hasten organic photoelectron industry becomes an important supporting point for promoting the development of international economy and is one of strategic emerging industries which are mainly supported by our country. Organic light-emitting transistors (OLEDs) combine the light-emitting function of OLEDs and the switching function of OTFTs, and therefore, they have important application prospects in the fields of display technologies, micro-nano scale integrated light sources, optical communications, Organic electrically pumped lasers and the like instead of active matrix driving OLEDs (amoleds) in the future, and become a new favorite in the field of Organic electronic components. The development of multifunctional organic semiconductor materials with good charge transport properties and excellent light-emitting efficiency in an aggregate state is the basis for promoting the industrialization of the electronic components.
From the viewpoint of carrier transport, the organic active layer is made of a single-component material, which facilitates close and ordered packing of molecules. Thus, the basic requirement of organic semiconductor materials for oleds is to have multiple functions such as high solid-state fluorescence quantum efficiency and double-carrier transport property in addition to high carrier transport property in an aggregation state (for convenience, such multifunctional organic semiconductor materials are referred to as "light-emitting organic semiconductors"). Such multifunctional materials are also the core foundation for the realization of organic electrically pumped lasers, but obtaining such multifunctional materials poses significant challenges. The organic semiconductor material realizes excellent carrier transmission characteristics, organic molecules are required to have strong intermolecular interaction and close and ordered accumulation in a solid state, the organic luminescent material realizes excellent luminescent performance, the organic molecules are required to be far away from each other as possible and cannot have strong interaction with each other, and the known luminescence quenching induced by aggregation state exists when the molecules are close to each other. As such, most organic semiconductors having high carrier mobility in the field of OTFTs have very weak light emitting properties in the solid state. In contrast, materials with excellent emission properties in the field of OLEDs exhibit low carrier mobility due to lack of tightly ordered packing in the aggregated state, accompanied by severe aggregation-induced luminescence quenching. The research on light-emitting organic semiconductor materials faces a pair of contradictions, namely, the fluorescence quantum efficiency is sacrificed when the carrier mobility is improved, and conversely, the carrier mobility is sacrificed when the fluorescence quantum efficiency is improved.
Disclosure of Invention
The present invention aims to solve the above-mentioned problems in the prior art, and provide a light-emitting organic semiconductor framework material and its application, wherein the aggregation state has high light-emitting efficiency, good charge transport performance, and excellent thermal stability.
The invention adopts the following technical scheme:
a luminous organic semiconductor framework material is characterized in that multiple N, O and S heteroatoms are simultaneously introduced into a condensed ring system of a focusing induction luminous material to perform hybridization substitution on one end of a linear aromatic condensed ring, molecules are induced to generate static dipole moment, C-H … pi action, hydrogen bond action and local dipole-dipole interaction between adjacent molecules are selectively enhanced to push pi planes of the adjacent molecules to be staggered, pi-pi action between the adjacent molecules is weakened, molecules in a microscopic aggregation state are closely stacked to form the luminous organic semiconductor framework material, a core construction framework is furan benzo-quinoxaline or thiophene quinoxaline, and the constructed molecules contain furan [2,3-b ] quinoxaline or thiophene [2,3-b ] quinoxaline core frameworks.
Furthermore, the invention is characterized in that: the structural general formula (I) of the light-emitting organic semiconductor framework material is as follows:
wherein n is 1,2 or 3; x, Y and Z represent heteroatoms; r1Is H, -F, -CN, alkyl substituted with 0 to 30 carbon atoms, alkoxy substituted with 0 to 30 carbon atoms, mercapto substituted with 0 to 30 carbon atoms or amine substituted with 0 to 30 carbon atoms, and combinations thereof; ar is an aromatic ring.
Wherein, when X ═ Y ═ N and Z is O, the following structure is implemented:
furthermore, the invention is characterized in that: the structural general formula (II) of the light-emitting organic semiconductor framework material is as follows:
wherein n is 1,2 or 3; x, Y and Z represent heteroatoms; r1Is H, -F, -CN, alkyl substituted with 0 to 30 carbon atoms, alkoxy substituted with 0 to 30 carbon atoms, mercapto substituted with 0 to 30 carbon atoms or amine substituted with 0 to 30 carbon atoms, and combinations thereof; ar is an aromatic ring; r2Is H, -F, -CN, alkyl substituted with 0 to 10 carbon atoms, having 0 to 10 carbon atomsA substituted alkoxy group, a mercapto group substituted with 0 to 10 carbon atoms or an amino group substituted with 0 to 10 carbon atoms, triisopropylsilacetylene, and combinations thereof.
Wherein when N is 1, X ═ Y ═ N, and Z is O or S, the following structure is implemented:
furthermore, the invention is characterized in that: the structural general formula (III) of the light-emitting organic semiconductor framework material is as follows:
wherein n is 1,2 or 3; x, Y and Z represent heteroatoms; r1Is H, -F, -CN, alkyl substituted with 0 to 30 carbon atoms, alkoxy substituted with 0 to 30 carbon atoms, mercapto substituted with 0 to 30 carbon atoms or amine substituted with 0 to 30 carbon atoms, and combinations thereof; ar is an aromatic ring.
Wherein when N is 1, X ═ Y ═ N, and Z is O or S, the following structure is implemented:
wherein the aromatic ring comprises a benzene ring, furan, thiophene, pyrrole, triazine, pyridine, or styryl, furan/thiophene/pyrrolyl, triazine/pyridylyl, or phenylacetylene, furan/thiophene/pyrrolyl ethynyl or triazine/pyridylyl ethynyl; x and Y are both N and C atoms, and Z is independently selected from N, O and S atoms.
Another technical solution of the present invention is an organic light emitting field effect transistor, which includes the light emitting organic semiconductor skeleton material.
The invention also provides an electrically pumped organic laser device, which comprises the light-emitting organic semiconductor framework material.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the light-emitting organic semiconductor structure provided by the invention, hetero atoms such as N, O, S and the like are arranged at the same end of the aromatic condensed ring to induce molecules to generate static dipole moment, and intermolecular forces such as intermolecular hydrogen bonds, dipole-dipole interaction and the like are used for regulating and controlling a molecular aggregation state accumulation microstructure, the light-emitting performance of a material and the light-emitting color and carrier transmission performance of the material.
Furthermore, heteroatoms in the structure II are arranged at two ends of the linear condensed ring molecules and are in a symmetrical structure, the structure is regular, the ordered accumulation of the molecules is facilitated, and the molecules can be properly substituted and modified in a direction perpendicular to the long axis of the condensed ring, so that the accumulation structure of the molecules is further regulated and controlled.
Furthermore, the structure III is a dimer structure, two condensed ring skeletons are connected through a chemical single bond, the intermolecular distance is small, the intermolecular charge transmission is facilitated, in addition, the dimer structure can extend the conjugation length of a pi system, and the two-dimensional and three-dimensional stacking structure of molecules is regulated and controlled.
Furthermore, the aromatic rings with different structures can endow the material with new intermolecular interaction such as hydrogen bonds and the like in molecules, different electronic effects such as electron-withdrawing characteristic of the nitrogen-containing six-membered aromatic ring and electron-supplying characteristic of the thiophene ring can help to regulate and control the micro-stacking structure of the molecules by more means through the new intermolecular interaction and electronic effect, and further regulate and control the optical and electrical properties of the molecules.
Furthermore, X and Y are N and C atoms at the same time, and the O atom independently selected by Z can utilize the high fluorescence efficiency of furan rings and smaller molecular frameworks, so that the closer packing of molecules is facilitated, the charge transmission performance is improved, and the good luminescence performance is ensured; the S atom independently selected by Z can improve the charge transfer performance of the material by utilizing the excellent charge transfer performance of the thiophene ring; the independent selection of N atom in Z can regulate and control the HOMO and LUMO energy levels of the material, change the charge transport characteristics of the semiconductor and realize multiple purposes of the material.
In conclusion, the invention establishes a new organic light-emitting semiconductor material system which has stable structure, high light-emitting efficiency and excellent charge transmission performance, realizes the win-win of the material aggregation state light-emitting efficiency and the charge transmission performance by comprehensively introducing molecular dipole-dipole interaction, hydrogen bond and pi-pi and other interactions into the molecular system to regulate and control the aggregation state accumulation structure, and simultaneously provides powerful material support for further improving the performance of the light-emitting organic field effect transistor device and new material selection for exploring an organic electric pumping laser device.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a nuclear magnetic spectrum of I-7;
FIG. 2 is a nuclear magnetic spectrum of I-13;
FIG. 3 is a nuclear magnetic spectrum of III-1;
FIG. 4 is a graph of I-7 in water: photoluminescence emission spectra in tetrahydrofuran mixed solution;
FIG. 5 is a graph of the transfer and output of thin films (a, b) and single crystal (c, d) field effect transistors of the I-7 active layer;
FIG. 6 is a device structure diagram of an organic field effect transistor of I-7 active layer, the device is prepared on OTS/SiO2a/Si substrate.
Detailed Description
The invention provides a luminescent organic semiconductor framework material, which can effectively solve the difficulty of balancing luminescence and charge transmission in the design of a luminescent organic semiconductor material, and specifically comprises the following two points:
firstly, the research on the correlation nature of fluorescence quantum efficiency and carrier mobility of the aggregation material is expected to be carried out only when the research goes deep into the intermolecular interaction layer behind the microscopic accumulation structure, so that the dependence relationship between the fluorescence quantum efficiency and the carrier mobility is expected to be clarified;
and heteroatom such as N, O and the like is introduced into a proper position in a condensed ring system at the same time, so that C-H … pi action, hydrogen bond action, local dipole-dipole interaction and the like among adjacent molecules are strengthened to promote the micro aggregation molecules to be tightly stacked, and the carrier transmission performance is ensured. The strengthened actions (C-H … pi action, hydrogen bond action and local dipole-dipole) push the pi planes of adjacent molecules to be staggered, weaken the pi-pi action between the adjacent molecules, further block the formation of dimers and excimers which cause no radiation loss of excited state energy, and improve the radiation luminous efficiency of excitons.
The aromatic fused heterocyclic molecular structure with stable static dipole moment is provided, the pi-pi action between adjacent molecules is weakened through the design selectivity of the molecular structure, such as the strengthening of C-H … pi action, hydrogen bond action, hetero-condensed ring dipole-dipole interaction and the like, the micro molecular stacking structure beneficial to the improvement of aggregation state luminescence is regulated and controlled, the win-win of solid state luminescence efficiency and carrier mobility is realized, the core building framework is furan benzo quinoxaline or thiophene quinoxaline, and the built molecule contains furan [2,3-b ] quinoxaline or thiophene [2,3-b ] quinoxaline core framework.
The luminescent organic semiconductor framework material adopts a plurality of nitrogen, oxygen and sulfur heteroatom hybrid linear aromatic condensed rings to induce molecules to generate fixed static dipole moment, so that a micro-stacking structure which is favorable for high-efficiency luminescence is formed when the molecules are aggregated, and the molecular material has good carrier transmission performance and excellent aggregation state luminescence performance. The luminescent organic semiconductor material provided by the invention can be used for realizing a luminescent field effect transistor, improving various performance indexes of the luminescent transistor and trying to be applied to an electrically pumped organic laser device.
The invention relates to a luminescent organic semiconductor framework material, which structurally comprises three types of I, II and III, and the specific structural general formula is as follows:
wherein n is 1,2 or 3;
x, Y and Z represent heteroatoms, X and Y are N and C atoms, and Z is N, O or S atom;
r1 is H, -F, -CN, alkyl substituted with 0 to 30 carbon atoms, alkoxy substituted with 0 to 30 carbon atoms, mercapto substituted with 0 to 30 carbon atoms or amine substituted with 0 to 30 carbon atoms, and combinations thereof;
ar is an aromatic ring and comprises a benzene ring, furan, thiophene, pyrrole, triazine, pyridine and other heterocyclic rings, or is styryl, furan/thiophene/pyrrylethenyl, triazine/pyridinylethenyl, or is phenylacetylene, furan/thiophene/pyrrylethynyl, triazine/pyridinylethynyl;
r2 is H, -F, -CN, or an alkyl group substituted with 0 to 10 carbon atoms, an alkoxy group substituted with 0 to 10 carbon atoms, a mercapto group substituted with 0 to 10 carbon atoms or an amino group substituted with 0 to 10 carbon atoms, triisopropylsilacetylene, and combinations thereof.
The molecular structures of the present invention have different embodiments, and when N is 1,2 or 3, X ═ Y ═ N, and Z is O in the (I) group, the embodiments of I-1 to 27 are as follows:
when N in class (II) is 1, X ═ Y ═ N, and Z is O or S, the following structures are implemented in class II-1 to class II-13:
when N is 1, X is Y is N, and Z is O or S in group (III), the following structures are implemented in III-1 to 14:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.
In order to illustrate the organic electroluminescent material of the present invention in detail and understand the synthesis method thereof, the compounds I-7, I-13 and III-1 are used as examples to illustrate the synthesis method of the present invention.
(1) The synthesis scheme for I-7 is as follows:
the NMR spectrum of I-7 is shown in FIG. 1.
The chemical synthesis of intermediates 3a, 3b is as follows:
12g of acetophenone is dissolved in 150ml of THF, 105mmol of lithium diisopropylamide is slowly dropped at 0 ℃, stirred for 30 minutes at 0 ℃ after the dropping is finished, then 15ml of trimethylchlorosilane is slowly dropped, and the reaction is carried out at room temperature overnight. After the completion of the thin layer chromatography-based reaction, THF was distilled off, then anhydrous hexane was added, filtration was carried out, and the filtrate was used in the next reaction directly after further removal of the solvent.
The intermediate prepared above was dissolved in 40ml of anhydrous ether, and 8.8ml of oxalyl chloride was slowly added dropwise at room temperature, followed by stirring overnight. And after the detection reaction of the thin-layer plate is finished, directly filtering to obtain a solid crude product. The crude product was dissolved in dichloromethane and recrystallized to give 6.2g of 3 a.
1H-NMR(300MHzCDCl3):(ppm)7.92～7.95(m,2H,),7.69～7.72(m,1H),7.57～7.72(m,2H),6.42(s,1H)。
Intermediate 3b used a similar experimental procedure, but the yield was relatively lower.
The chemical synthesis of intermediates 4a, 4b is as follows:
0.47g of 2, 3-naphthalenediamine, 0.59g of intermediate 3a and 30ml of acetic acid were charged into a three-necked flask, refluxed for 4 to 5 hours, and directly filtered after completion of the reaction by thin layer chromatography to obtain 0.3g of crude yellow solid, which was washed with ethyl acetate to obtain 0.74g of pure 4a (yield: 76%).
1H-NMR(400MHz DMSO):(ppm)13.596(s,1H,),12.211(s,1H,),8.004-8.044(t,3H),7.832～7.855(t,2H),7.607～7.643(t,1H),7.543～7.584(t,3H),7.411～7.431(t,2H),6.920(s,1H)；MS(EI):m/z＝314(M+)。
4b：1H-NMR(400MHz DMSO):(ppm)13.569(s,1H,),12.183(s,1H,),7.937-7.972(t,3H),7.823～7.846(t,2H),7.531(s,1H),7.403～7.427(t,2H),7.359～7.379(d,J＝8Hz,2H),6.897(s,1H)2.638～2.676(t,2H),1.587～1.621(t,2H),1.250～1.298(m,10H),0.841～0.875(t,3H)；MS(EI):m/z＝426(M+)。
The chemical synthesis of I-7 is as follows:
0.74g of intermediate 4a and 15g of polyphosphoric acid were mixed, purged with nitrogen, and heated to 140 ℃ for 5 hours. Then, the mixture was cooled to room temperature, 100ml of water was added, the mixture was neutralized with sodium hydrogencarbonate, and the mixture was filtered to obtain a filter cake, which was then separated by column chromatography to obtain 0.51g of I-7 as a final product.
1H-NMR(400MHz DMSO):(ppm)8.861(s,1H,),8.766(s,1H),8.256-8.297(t,2H),8.197-8.221(d,2H),7.957(s,1H),7.641-7.678(m,5H)；13C:165.43,154.67,146.40,139.42,136.09,133.19,132.91,131.68,129.24,128.35,128.33,128.01,126.87,126.49,126.42,126.27,100.80,40.48,40.27,40.06,39.64,29.70；HRMS(ES):m/z calc.ForC20H12N2O 296.0950,found297.10245[M+H]
I-11：1H-NMR(300MHz CDCl3):(ppm)9.02(s,1H,),8.85(s,1H),8.55-8.56(d,J＝4.5Hz,1H),8.31-8.35(m,2H),8.17-8.19(d,J＝4.8Hz,1H),.7.82-7.85(m,1H),7.70-7.72(m,3H)1.587～1.621(t,2H),1.250～1.298(m,10H),0.841～0.875(t,3H)；13C:165.84,154.75,147.52,146.61,139.46,136.10,133.09,132.89,129.35,128.32,128.01,126.75,126.46,126.37,126.20,125.79,99.99,36.09,31.88,31.20,29.45,29.30,29.24,22.67,14.11；HRMS(ES):m/z calc.for C28H28N2O,408.2202,found 409.22813(M++H)
(2) The synthesis scheme for I-13 is as follows:
the NMR spectrum of I-13 is shown in FIG. 2.
In a three-necked flask were charged 1.32g of 4-phenyl-1, 2-phenylenediamine, 1.25g of intermediate 3a, and 50ml of acetic acid, and the mixture was refluxed for 4 to 5 hours, and directly filtered after completion of the reaction by thin layer chromatography to obtain 1.65g (yield: 67.4%) of crude 6a as a yellow solid.
Subsequently, 1.49g of intermediate 6a and 30g of polyphosphoric acid were mixed, purged with nitrogen, and heated to 140 ℃ for 5 hours. Then, it was cooled to room temperature, 100ml of water was added, neutralized with sodium hydrogencarbonate to neutrality, filtered to obtain a filter cake, and the filter cake was separated by column chromatography to obtain 0.97g (yield 65%) of the final product I-13 as a mixture of two isomers.
(3) The synthesis scheme of III-1 is as follows:
the NMR spectrum of III-1 is shown in FIG. 3.
To a three-necked flask were added 0.75g of [1,1' -diphenyl l ] -3, 4-diamine, 1.3g of intermediate 3a, 50ml of acetic acid, and the mixture was refluxed for 4 to 5 hours, followed by direct filtration after completion of the reaction by thin layer chromatography to obtain crude 7a1.75g (yield 95%) as a dark red solid.
Subsequently, 1.5g of intermediate 7a and 30g of polyphosphoric acid were mixed, purged with nitrogen, and heated to 140 ℃ for 5 hours. Then cooled to room temperature, 100ml of water was added, neutralized to neutrality with sodium bicarbonate, and filtered to obtain 1.25g (yield 90%) of a filter cake as a mixture of two isomers.
Photoelectric property of material
Referring to fig. 4 and 5, the compounds I-7 and I-13 have good luminescence properties in an aggregate state, the compound I-7 has an absolute fluorescence quantum efficiency of 9.19% in a solution of dichloromethane, the fluorescence quantum efficiency is enhanced to 22.14% in a solid powder state, the absolute fluorescence quantum efficiency is 19.74% in a 50% water-tetrahydrofuran solution, and the hole mobility of the organic single crystal and the thin film transistor device using the compound I-7 as an active layer can reach 2.58 × 10-2cm2·V-1·s-1And 5.7 × 10-3cm2·V-1·s-1。
Compound I-13 emits deep blue light with an absolute fluorescence quantum efficiency of 45.06% in methylene chloride solution, although 28.91% absolute fluorescence quantum efficiency is also present in the powder state. Since there are many defects at the powder grain boundary that cause a decrease in luminous efficiency, better solid-state fluorescence quantum efficiency is expected for growing into a single crystal. I-13 also showed an increase in fluorescence in the aggregate state, with a gradual increase in fluorescence intensity when water was added to a solution of tetrahydrofuran, and a maximum fluorescence quantum efficiency of 70.47% when increased to 50% water.
The III-1 compound emits blue fluorescence, and the fluorescence quantum efficiency of the compound in dichloromethane solution is as high as 80.61%.
The three compounds all show excellent luminescence performance, particularly show fluorescence enhancement phenomenon in an aggregation state, and further expand the molecular system of the aggregation state fluorescence enhancement material. In addition, the developed molecules show better charge transmission performance through preliminary tests of organic field effect transistors, which shows that the material system is a multifunctional molecular framework with great application prospect.
Referring to fig. 6, fig. 6 shows an organic field effect transistor device structure, in which silicon is used as a substrate and a gate electrode, silicon dioxide is used as a dielectric layer, the silicon dioxide dielectric layer is interface-modified with octadecyltrichlorosilane, an organic thin film disclosed in the embodiment example of evaporating about 50nm on the dielectric layer is used as an organic semiconductor active layer, and gold is evaporated on the organic semiconductor layer to form a source electrode and a drain electrode
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (4)
1. An organic light-emitting field effect transistor comprising a light-emitting organic semiconductor framework material, the light-emitting organic semiconductor framework material having the following structure:
the implementation structure is as follows:
2. an organic light-emitting field-effect transistor comprising a light-emitting organic semiconductor framework material having the following general structural formula (I):
wherein n is 1,2 or 3; x, Y and Z represent heteroatoms; r1Is H, -F, -CN; ar is a benzene ring; x and Y are N atoms at the same time, and Z is independently selected from O atoms.
3. An organic light-emitting field-effect transistor comprising a light-emitting organic semiconductor framework material having the following general structural formula (III):
wherein n is 1,2 or 3; x, Y and Z represent heteroatoms; r1Is H, -F, -CN; ar is a benzene ring; x and Y are N atoms at the same time, and Z is independently selected from O atoms.
4. An electrically pumped organic laser device, characterized in that said device comprises a light emitting organic semiconductor backbone material according to claim 1 or 2 or 3.
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