Organic compound with azafluorene as core and preparation method and application thereof
阅读说明：本技术 一种以氮杂芴为核心的有机化合物及其制备方法与应用 (Organic compound with azafluorene as core and preparation method and application thereof ) 是由 李崇 王芳 徐浩杰 于 2018-08-17 设计创作，主要内容包括：本发明公开了一种以氮杂芴为核心的有机化合物及其制备方法和应用。本发明提供的化合物中π共轭效应使得其有很强的空穴传输能力,高的空穴传输速率能够降低器件的起始电压,提高有机电致发光器件的效率；且其中不对称的三芳胺结构能够降低分子的结晶性,降低分子的平面性,增强分子的刚性,从而提高分子的热稳定性；作为OLED发光器件的发光功能层材料使用时,氮杂芴搭配本发明范围内的支链可有效提高激子利用率和辐射效率。(The invention discloses an organic compound taking azafluorene as a core, and a preparation method and application thereof. The pi conjugation effect in the compound provided by the invention enables the compound to have strong hole transmission capability, the high hole transmission rate can reduce the initial voltage of the device, and the efficiency of the organic electroluminescent device is improved; the asymmetric triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules and enhance the rigidity of the molecules, thereby improving the thermal stability of the molecules; when the azafluorene branched organic light emitting diode is used as a light emitting functional layer material of an OLED light emitting device, the azafluorene can be matched with the branched chain within the range of the invention to effectively improve the exciton utilization rate and the radiation efficiency.)
1. An organic compound with azafluorene as a core is characterized in that the structure of the organic compound is shown as a general formula (1):
in the general formula (1), - - - - - - - - - - -represents that two groups are connected or not connected; x, Y each occurrence is represented, identically or differently, as one of a nitrogen atom, a carbon atom, or C-H, and at least one of X or Y is represented as a nitrogen atom; when- - - - - - -indicates that the two groups are not connected, X is not a nitrogen atom;
a, b, c and d are respectively and independently represented as a number 1 or 2, and a + b + c + d is more than or equal to 2;
the R is1、R2、R3、R4Each independently represents a hydrogen atom, a cyano group, a halogen atom, C1-20Alkyl of (C)1-20Alkenyl of (a), substituted or unsubstituted C6-30An aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, or a structure represented by the general formula (2); and R is1、R2、R3、R4One and only one is represented by a structure shown as a general formula (2); two or more adjacent R1、R2、R3、R4Can also form a monocyclic, aliphatic or aromatic polycyclic ring with each other;
in the general formula (2), L represents a single bond, substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
said L1、L2Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group and a substituted or unsubstituted benzofuranyl group;
the R is5、R6Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a structure represented by general formula (3) or general formula (4); the R is5When represented by the structure of the general formula (4), L1Cannot represent a single bond; the R is6When represented by the structure of the general formula (4), L2Cannot represent a single bond;
in the general formulae (3) and (4), X1、X2、X3Independently represent-O-, -S-, -C (R)7)(R8) -or-N (R)9)-；X2、X3May also represent a single bond; z is1Each occurrence being represented, identically or differently, by a nitrogen atom or C-R10；
The R is7～R9Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl radicals, containing one or more hetero atomsOne of a substituted or unsubstituted 5 to 30 membered heteroaryl; r7And R8Can also be connected with each other to form a ring;
the R is10Each independently represents a hydrogen atom, a halogen, a cyano group, C1-20Alkyl of (C)1-20Alkenyl of (a), substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R13May also form a monocyclic, aliphatic or aromatic polycyclic ring with each other; (ii) a
The substituent of the substitutable group is selected from halogen atom, cyano, C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The organic compound of claim 1, wherein R is1、R2、R3、R4Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, a furyl group, or a structure represented by general formula (2); and R is1、R2、R3、R4One and only one is represented by a structure shown as a general formula (2);
the L represents one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted benzofuranyl and a substituted or unsubstituted carbazolyl;
the R is7～R9Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuranyl, carbazolyl, benzothienyl, or furanyl;
the R is10Represented by hydrogen atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl groupPropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl or pyridyl;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuryl, carbazolyl, benzothienyl or furyl.
3. The organic compound according to claim 1, wherein the compound has a structure represented by any one of the following general formulae:
4. an organic compound according to claim 1, wherein the compound has the specific structure:
5. A method for producing an organic compound according to any one of claims 1 to 4, wherein the method involves two cases:
(1) when L in the general formula (2) represents a single bond;
in the above formula, Ra、Rb、Rc、RdEach independently represents one of Cl, Br, I or H, and Ra、Rb、Rc、RdNot hydrogen at the same time; the intermediate amine compound is selected from R1-H、R2-H、R3-H or R4-H；
The preparation method comprises the following steps: weighing reactant A and intermediate B, and dissolving with toluene(ii) a Then adding Pd2(dba)3、P(t-Bu)3Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate B is 1:1.2-3.0, and Pd2(dba)3The molar ratio of the reactant A to the reactant A is 0.006-0.02:1, P (t-Bu)3The molar ratio of the sodium tert-butoxide to the reactant A is 0.006-0.02:1, and the molar ratio of the sodium tert-butoxide to the reactant A is 1.0-3.0: 1;
(2) when L in the general formula (2) is not a single bond;
in the above formula, Ra、Rb、Rc、RdEach independently represents one of Cl, Br, I or H, and Ra、Rb、Rc、RdNot hydrogen at the same time; the intermediate boron compound is selected from
The preparation method comprises the following steps: weighing a reactant A and an intermediate C, and dissolving the reactant A and the intermediate C in a mixed solvent of toluene and ethanol with a volume ratio of 2: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate C is 1: 1.0-2.0; na in aqueous solution2CO3The molar ratio of the reactant A to the reactant A is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the reactant A to the reactant A is 0.006-0.02: 1.
6. An organic electroluminescent device comprising at least one functional layer containing the azafluorene-based organic compound according to any one of claims 1 to 4.
7. An organic electroluminescent device comprising a hole transport layer or an electron blocking layer, wherein the hole transport layer or the electron blocking layer contains the azafluorene-based organic compound according to any one of claims 1 to 4.
8. An organic electroluminescent device comprising a light-emitting layer, wherein the material of the light-emitting layer contains the azafluorene-based organic compound according to any one of claims 1 to 4.
9. A lighting or display element, characterized in that the element comprises an organic electroluminescent device according to any one of claims 6 to 8.
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound taking azafluorene as a core, and a preparation method and application thereof.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides an organic compound with azafluorene as a core, and a preparation method and an application thereof. The organic compound provided by the invention is not easy to crystallize, has good film-forming property and thermal stability, higher glass transition temperature and appropriate HOMO and LUMO energy levels, and the device adopting the organic compound provided by the invention can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through structure optimization, thereby better adapting to and meeting the application requirements of panel manufacturing enterprises.
The technical scheme of the invention is as follows:
an organic compound taking azafluorene as a core has a structure shown as a general formula (1):
in the general formula (1) above,
a, b, c and d are respectively and independently represented as a
the R is1、R2、R3、R4Each independently represents a hydrogen atom, a cyano group, a halogen atom, C1-20Alkyl of (C)1-20Alkenyl of (a), substituted or unsubstituted C6-30An aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, or a structure represented by the general formula (2); and R is1、R2、R3、R4One and only one is represented by a structure shown as a general formula (2); two or more adjacent R1、R2、R3、R4Can also form a monocyclic, aliphatic or aromatic polycyclic ring with each other;
in the general formula (2), L represents a single bond, substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
said L1、L2Each independently represents a single bond, substituted or unsubstitutedOne of substituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted carbazolyl and substituted or unsubstituted benzofuranyl;
the R is5、R6Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a structure represented by general formula (3) or general formula (4); the R is5When represented by the structure of the general formula (4), L1Cannot represent a single bond; the R is6When represented by the structure of the general formula (4), L2Cannot represent a single bond;
in the general formulae (3) and (4), X1、X2、X3Independently represent-O-, -S-, -C (R)7)(R8) -or-N (R)9)-；X2、X3May also represent a single bond; z is1Each occurrence being represented, identically or differently, by a nitrogen atom or C-R10；
The R is7～R9Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r7And R8Can also be connected with each other to form a ring;
the R is10Each independently represents a hydrogen atom, a halogen, a cyano group, C1-20Alkyl of (C)1-20Alkenyl of (a), substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R13May form a monocyclic, aliphatic or aromatic polycyclic ring with each other; (ii) a
The substituent of the substitutable group is selected from halogen atom, cyano, C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
Further preferably, R is1、R2、R3、R4Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, a furyl group, or a structure represented by general formula (2); and R is1、R2、R3、R4One and only one is represented by a structure shown as a general formula (2);
the L represents one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted carbazolyl and a substituted or unsubstituted benzofuranyl;
the R is7～R9Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuranyl, carbazolyl, benzothienyl, or furanyl;
the R is10Independently represent a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group or a pyridyl group;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuryl, carbazolyl, benzothienyl or furyl.
Further preferably, the organic compound having azafluorene as a core is represented by any one of the following general formulae:
more preferably, the organic compound with azafluorene as the core has a specific structure:
A preparation method of an organic compound taking azafluorene as a core relates to the following two cases:
(1) when L in the general formula (2) represents a single bond;
in the above formula, Ra、Rb、Rc、RdEach independently represents one of Cl, Br, I or H, and Ra、Rb、Rc、RdNot hydrogen at the same time; the intermediate amine compound is selected from R1-H、R2-H、R3-H or R4-H；
The preparation method comprises the following steps: weighing a reactant A and an intermediate B, and dissolving the reactant A and the intermediate B by using toluene; then adding Pd2(dba)3、P(t-Bu)3Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate B is 1:1.2-3.0, and Pd2(dba)3The molar ratio of the reactant A to the reactant A is 0.006-0.02:1, P (t-Bu)3The molar ratio of the sodium tert-butoxide to the reactant A is 0.006-0.02:1, and the molar ratio of the sodium tert-butoxide to the reactant A is 1.0-3.0: 1;
the preparation method of the intermediate B comprises the following steps:
the specific preparation method of the reaction comprises the following steps: weighing
the reaction mainly utilizes the substitution reaction between the amino compound and the halogen atom, the dosage of each substance is the dosage of one-time substitution reaction, when multiple substitution reactions exist, the structure of the amino compound is changed according to one-time substitution reaction, and the one-time substitution reaction is repeated for multiple times;
(2) when L in the general formula (2) is not a single bond;
in the above formula, Ra、Rb、Rc、RdEach independently represents one of Cl, Br, I or H, and Ra、Rb、Rc、RdNot hydrogen at the same time; the intermediate boron compound is selected from
The preparation method comprises the following steps: weighing a reactant A and an intermediate C, and dissolving the reactant A and the intermediate C in a mixed solvent of toluene and ethanol with a volume ratio of 2: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate C is 1: 1.0-2.0; na in aqueous solution2CO3The molar ratio of the reactant A to the reactant A is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the reactant A to the reactant A is 0.006-0.02: 1.
The preparation method of the intermediate C comprises the following steps:
the preparation method comprises the following steps: weighing the intermediate B and the
weighing intermediate X, bis (pinacolato) diboron and Pd (dppf) Cl in the atmosphere of nitrogen2Dissolving potassium acetate in toluene, reacting at the temperature of 100-120 ℃ for 12-24 hours, sampling a sample point plate, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate to obtain a crude product, and passing through a neutral silica gel column to obtain an intermediate C; the molar ratio of the intermediate X to the bis (pinacolato) diboron is 2:1-1.5, and the intermediate X is in contact with Pd (dppf) Cl2The molar ratio of the intermediate X to the potassium acetate is 1: 2-2.5;
the reaction formula mainly utilizes the coupling reaction between the boron compound and the halogen atom, the dosage of each substance is the dosage of one-time coupling reaction, and when multiple coupling reactions exist, the structure of the boron compound is changed according to one-time coupling reaction, and the one-time coupling reaction is repeated for multiple times.
An organic electroluminescent device comprising at least one functional layer containing an organic compound having azafluorene as a core.
An organic electroluminescent device comprises a hole transport layer or an electron blocking layer, and is characterized in that the material of the hole transport layer or the electron blocking layer contains an organic compound taking azafluorene as a core.
An organic electroluminescent device comprises a light-emitting layer, wherein the material of the light-emitting layer contains an organic compound taking azafluorene as a core.
A lighting or display element comprising said organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the pi conjugation effect in the compound provided by the invention enables the compound to have strong hole transmission capability, the high hole transmission rate can reduce the initial voltage of the device, and the efficiency of the organic electroluminescent device is improved; the asymmetric triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules and enhance the rigidity of the molecules, thereby improving the thermal stability of the molecules; meanwhile, the structure of the compound provided by the invention enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the azafluorene branched organic electroluminescent material is used as a luminescent functional layer material of an OLED luminescent device, the azafluorene branched organic electroluminescent material can effectively improve the exciton utilization rate and the high fluorescent radiation efficiency by matching with the branched chain in the range of the invention, reduce the efficiency roll-off under the high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device.
Although the material No. 7 in the patent CN105218302B is in a structure that the spirofluorene is connected with the triarylamine, the evaporation temperature of the material is too high (298 ℃) and exceeds the bond endurance temperature (287 ℃) of the material, so that the bond is easy to break when the material is heated for a long time, the service life of the material after being made into a device is influenced, and the material is not suitable for mass production.
After the parent nucleus of the compound is substituted by the branched chain, the distance between molecules is increased, the interaction force between molecules is weakened, and therefore the compound has lower evaporation temperature, and the industrial processing window of the material is widened.
When the compound is applied to an OLED device, high film stability can be kept through device structure optimization, and the photoelectric performance of the OLED device and the service life of the OLED device can be effectively improved. The compound has good application effect and industrialization prospect in OLED luminescent devices.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
in the figure: 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is an electron transport/hole blocking layer, 8 is an electron injection layer, and 9 is a cathode reflection electrode layer.
FIG. 2 is a graph of efficiency measured at different temperatures for a device made according to the present invention and a comparative device.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
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