CN110642732B - Organic compound containing spirofluorene anthrone structure and application thereof - Google Patents
Organic compound containing spirofluorene anthrone structure and application thereof Download PDFInfo
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Abstract
The invention discloses an organic compound containing a spirofluorene anthrone structure and application thereof, wherein pi conjugated effect in the compound enables the compound to have strong hole transmission capability, and the high hole transmission rate can reduce the initial voltage of a device and improve the efficiency of an organic electroluminescent device; the asymmetric triarylamine structure can reduce the crystallinity and the planarity of molecules and prevent the molecules from moving on a plane, so that the thermal stability of the molecules is improved; 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 light-emitting layer.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound containing spirofluorene anthrone in a structure and application thereof in an organic electroluminescent device.
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 the two end electrodes of the OLED light-emitting device and the electric field acts on positive and negative charges in the organic layer functional material film layer, the positive and negative charges are further compounded in the light-emitting layer to generate OLED electroluminescence.
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 requirements of the current OLED display illumination industry, the development of the current OLED materials is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop higher-performance organic functional materials as material enterprises.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides an organic compound containing a spirofluorene anthrone structure and applications thereof. The compound contains the spirofluorene anthrone structure, has higher glass transition temperature and molecular thermal stability, proper HOMO energy level and T1 energy level and high hole mobility, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.
The technical scheme of the invention is as follows:
an organic compound containing a spirofluorene anthrone structure, wherein the structure of the organic compound is shown as a general formula (1):
in the general formula (1), R is 1 、R 2 、R 3 、R 4 Each independently represents a hydrogen atom, a halogen, a cyano group, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted C 6-60 An aryl group, a substituted or unsubstituted 5-to 60-membered heteroaryl group containing one or more heteroatoms, or a structure of formula (2); r 1 、R 2 、R 3 、R 4 Are respectively connected with the framework structure in the general formula (1) through a single bond or a benzo ring structure; and R is 1 、R 2 、R 3 、R 4 At least one of the structures represented by the general formula (2);
in the general formula (2), L represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene;
said L is 1 、L 2 Represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene;
R 5 、R 6 is represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a structure represented by a general formula (3) or a general formula (4);
said X 1 、X 2 Each independently represents a single bond, -O-, -S-, -C (R) 8 )(R 9 ) -or-N (R) 10 )-；
Said L 1 、L 2 Represented by substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene; l is a radical of an alcohol 1 Also represents a single bond, and when X 1 And X 2 Respectively represent a single bond and-N (R) 10 ) When is, L 1 Represents only a single bond;
R 8 ～R 10 are each independently represented by C 1 -C 20 Alkyl, substituted or unsubstituted C 6-30 One of an aryl, substituted or unsubstituted 5-to 50-membered heteroaryl; said R is 8 And R 9 May also be linked to form a 5-to 30-membered aliphatic or aromatic ring;
the substituent is halogen, cyano, C 1 -C 20 One of alkyl groups of (a).
In a preferred embodiment, the R group 1 、R 2 、R 3 、R 4 Independently represent a structure represented by general formula (5) or general formula (6):
in the general formula (5), a is represented by
Said X 3 、X 4 、X 5 Independently represent-O-, -S-, -C (R) 11 )(R 12 ) -or-N (R) 13 )-；
The R is 11 ～R 13 Are each independently represented by C 1-20 Alkyl, substituted or unsubstituted C 6-30 One of an aryl, substituted or unsubstituted 5-to 50-membered heteroaryl; the R is 11 And R 12 May also be linked to form a 5-to 30-membered aliphatic or aromatic ring;
the general formula (5) and the general formula (6) are respectively connected with the skeleton structure in the general formula (1) through a form of forming a benzo ring;
the substituent is halogen, cyano, C 1 -C 20 Alkyl group of (1).
Preferably, the structure of the organic compound is any one of general formulas (I) to (VII):
further preferably, R is 1 、R 2 、R 3 、R 4 Are respectively independentIs represented by one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridyl group or a furyl group.
Further preferably, R is 8 ～R 13 Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; r 8 And R 9 、R 11 And R 12 And may be linked to form a 5-to 30-membered aliphatic or aromatic ring.
The preferred specific structure of the organic compound is:
An organic electroluminescent device containing the organic compound comprises a light-emitting layer, and the material of the light-emitting layer contains the organic compound containing the spirofluorene anthrone structure.
An organic electroluminescent device containing the organic compound comprises a hole transport layer/electron blocking layer, and the material of the hole transport layer/electron blocking layer contains the organic compound containing the spirofluorene anthrone structure.
An illumination or display element comprising the above organic electroluminescent device.
Preferably, when the structure of the compound of the invention is shown in the general formula (I), L, R 5 And R 6 Has the meanings as listed in table 1 below:
TABLE 1
Compounds 41-56, which in turn have the same structure as compounds 25-40, except that R is 6 Is shown as
Compounds 57-72, which in turn have the same structure as compounds 25-40, except that R is 6 Is shown as
Compounds 73-88, which in turn have the same structure as compounds 25-40, except that R is 6 Is shown as
Compounds 89-104, which in turn have the same structure as compounds 25-40, except that R is 6 Is shown as
The compound 105-120, which in turn has the same structure as the compounds 25-42, except that R is 6 Is shown as
Compounds 121-240 which in turn have the same structures as compounds 1-120, except that L is represented by
The compound 241-360, which in turn has the same structure as the compounds 1-120, except that L is represented by
Compound 361-465 having the same structure as compounds 1-105 in this order except that L represents
When the structure of the compound is shown as the general formula (II), R 1 When the structure is represented by the general formula (2), the structure of the formula (II) is preferably represented by the formula (H), the formula (B), the formula (C) or the formula (D):
preferably, the compound 466-585, which in turn has the same structure as the compounds 1 to 120, except that the parent nucleus in the formula (I) is replaced by the parent nucleus in the formula (H);
compound 586-705, in turn, having the same structure as compounds 1-120, except that the parent nucleus in formula (I) is replaced with the parent nucleus in formula (B);
compound 706-825, in turn, having the same structure as compounds 1-120, except that the parent nucleus in formula (I) is replaced with the parent nucleus in formula (C);
compound 826-;
preferably, when the structure of formula (1) is as shown in formula (II), R 1 、L、R 5 And R 6 Having the meanings set forth in table 2 below, the compounds of the present invention are preferably, but not limited to, the following structures;
TABLE 2
Note: "+" in the table indicates the attachment site;
preferred embodiment, compound 986-1001, which in turn has the same structure as compound 970-985, except that R 6 Is shown as
The compound 1002-1017, which in turn has the same structure as the compound 970-985, except that R 6 Is shown as
Compound 1018-1033 having the same structure as that of compound 970-985 in this order except that R is 6 Is shown as
When the structure of the compound is shown as the general formula (III), R 1 、R 2 、L、R 5 And R 6 Having the meanings set forth in table 3 below, the compounds of the present invention are preferably, but not limited to, the following structures;
TABLE 3
Note: "+" in the table indicates the attachment site;
compound 1074-1089 having in turn the same structure as compound 1058-1073, except that R 6 Is shown as
Compound 1090-1105 in turn having the same structure as compound 1058-1073, except that R 6 Is shown as
The compound 1106-1121 (f) comprises (a) a compound 1121,which in turn has the same structure as compound 1058-1073, except that R is 6 Is shown as
Preferably, when the structure of the compound is shown as the general formula (IV), the compound of the present invention is preferably, but not limited to, the following structure; in the formula (IV), L, R 5 And R 6 Has the following meanings as listed in table 4 below:
TABLE 4
Compound 1162-1177, which in turn has the same structure as compound 1146-1161, except that R 6 Is shown as
Compound 1178-1193, which in turn has the same structure as compound 1146-1161, except that R 6 Is shown as
Compound 1194-1209, which in turn has the same structure as compound 1146-1161, except that R 6 Is shown as
Chemical combination ofObject 1210-1225, which in turn has the same structure as compound 1146-1161, except that R 6 Is shown as
Compound 1226-1241, which in turn has the same structure as compound 1146-1161, except that R 6 Is shown as
Compound 1242-1361 which in turn has the same structure as compound 1122-1361 except that L is represented by
Compound 1362-1481 which in turn has the same structure as compound 1122-1241, with the difference that L is represented by
Compound 1482-1601 which in turn has the same structure as compound 1122-1241, except that L is represented by
Preferably, when the structure of the compound is shown as the general formula (V), the compound of the present invention is preferably, but not limited to, the following structure; in the formula (V), L, R 1 、R 5 And R 6 Has the following meanings as listed in the following table 5:
TABLE 5
Note: "+" in the table indicates the attachment site;
compound 1642-1657 having the same structure as compound 1626-1641 in that order except that R 6 Is shown as
Compound 1658-1673 having the same structure as compound 1626-1641 in that R is different 6 Is shown as
Compound 1674- 6 Is shown as
The invention also provides a preparation method of the organic compound containing the spirofluorene anthrone structure, which comprises the following two conditions:
(1) when L represents a single bond, the steps are as follows: under the protection of inert gas, dissolving the raw material I and the intermediate A in toluene, and adding Pd 2 (dba) 3 Reacting the mixed solution at 95-110 ℃ for 10-24 h, naturally cooling to room temperature, filtering, rotatably evaporating filtrate, and passing the residue through a neutral silica gel column to obtain a target product;
the reaction equation is as follows:
(2) when L does not represent a single bond, the procedure is as follows: under the protection of inert gas, dissolving the raw material I and the intermediate B by using a THF solvent, and adding K 2 CO 3 Aqueous solution and Pd (PPh) 3 ) 4 Reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 h, naturally cooling to room temperature, filtering, carrying out rotary evaporation on the filtrate, and passing the residue through a silica gel column to obtain a target product;
the reaction equation is as follows:
further, the molar ratio of the raw material I to the intermediate A is 1: 1.0-1.5; the Pd 2 (dba) 3 The molar ratio of the raw material I to the raw material I is 0.005-0.01: 1; the molar ratio of the tri-tert-butylphosphine to the raw material I is 0.005-0.02: 1; the molar ratio of the sodium tert-butoxide to the raw material I is 1.5-3.0: 1; the molar ratio of the raw material I to the intermediate B is 1: 1-2; the volume ratio of the toluene to the ethanol is 2-2.5: 1; na (Na) 2 CO 3 The molar ratio of the raw material I to the raw material I is 1.0-3.0: 1; pd (PPh) 3 ) 4 The molar ratio of the raw material I to the raw material I is 0.006-0.02: 1.
Further, the preparation of the intermediate A comprises the following steps:
weighing raw material O and raw material P, dissolving with toluene, and adding Pd 2 (dba) 3 、P(Ph) 3 And sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate A;
the reaction equation is as follows:
further, the molar ratio of the raw material O to the raw material P is 1 (1.0-1.5); pd 2 (dba) 3 The molar ratio of the sodium tert-butoxide to the raw material O is (0.006-0.02): 1, and the molar ratio of the sodium tert-butoxide to the raw material O is (2.0-3.0): 1; p (Ph) 3 The molar ratio of the raw material O to the raw material O is (2.0-3.0): 1;
further, the preparation of the intermediate B comprises the following steps:
(1) weighing the intermediate A and the raw material N, and dissolving the intermediate A and the raw material N in toluene; then adding Pd 2 (dba) 3 、P(Ph) 3 Sodium tert-butoxide; under inert atmosphere, the above-mentionedReacting the mixed solution of the reactants for 10-24 hours at 95-110 ℃, cooling and filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate Z;
(2) weighing intermediate Z, bis (pinacolato) diboron and Pd (dppf) Cl in the atmosphere of nitrogen 2 Dissolving potassium acetate in toluene, reacting for 12-24 hours at 100-120 ℃, sampling a sample, completely reacting, naturally cooling, filtering, rotatably steaming filtrate to obtain a crude product, and passing through a neutral silica gel column to obtain an intermediate B;
the reaction equation is as follows:
further, in the step (1), the molar ratio of the intermediate A to the raw material N is 1:1.0-1.5, and Pd 2 (dba) 3 The molar ratio of the intermediate A to the intermediate A is 0.006-0.02: 1, P (Ph) 3 The molar ratio of the sodium tert-butoxide to the intermediate A is 0.006-0.02: 1, and the molar ratio of the sodium tert-butoxide to the intermediate A is 1.0-3.0: 1;
in the step (2), the molar ratio of the intermediate Z to the bis (pinacolato) diboron is 2: 1-1.5, and the intermediate Z and Pd (dppf) Cl 2 The molar ratio of the intermediate Z to the potassium acetate is 1: 0.01-0.05, and the molar ratio of the intermediate Z to the potassium acetate is 1: 2-2.5.
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 prevent the molecules from accumulating and crystallizing, 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 spirofluorene anthrone serving as a light-emitting functional layer material of an OLED light-emitting device is used, the spirofluorene anthrone can be matched with the branched chain in the range of the spirofluorene anthrone so as to effectively improve the exciton utilization rate and the high fluorescence radiation efficiency, reduce the efficiency roll-off under high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device.
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 diagram of the application of the compounds of the present invention to an OLED device;
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 or electron blocking layer; 5 is a luminescent layer; 6 is an electron transport or hole blocking layer; 7 is an electron injection layer; and 8, a cathode reflective electrode layer.
FIG. 2 is a graph of current efficiency measured at different temperatures for OLED devices prepared with the compounds of the present invention.
Fig. 3 is a graph showing a reverse voltage leakage current test performed on the device 19 manufactured in the comparative example 1 and the device 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
EXAMPLE 1 preparation of the intermediate
(1) Preparation of intermediate A1
Adding 0.01mol of raw material O1, 0.012mol of raw material P1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10 -5 molPd 2 (dba) 3 ，5×10 -5 mol P(Ph) 3 Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, sampling a sample point plate, and displaying that no bromide is left and the reaction is complete; naturally cooling the mixture to the room temperature,filtering, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate A1; HPLC purity 99.67%, yield 77.8%; elemental analysis Structure (molecular formula C) 24 H 19 N): theoretical value: c, 89.68; h, 5.96; n, 4.36; test values are: c, 89.67; h, 5.96; n, 4.37. ESI-MS (M/z) (M) + ): the theoretical value is 321.42, and the actual value is 321.45.
(2) Preparation of intermediate B1
Adding 0.01mol of intermediate A1, 0.012mol of raw material N1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10 -5 molPd 2 (dba) 3 ，5×10 -5 mol P(Ph) 3 Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate Z1;
0.02mol of intermediate Z1, 0.012mol of bis (pinacolato) diboron and 0.0002mol of Pd (dppf) Cl were weighed out under a nitrogen atmosphere 2 Dissolving 0.05mol of potassium acetate in toluene, reacting at 100-120 ℃ for 12-24 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably steaming filtrate to obtain a crude product, and passing through a neutral silica gel column to obtain an intermediate B1; HPLC purity 99.25%, yield 74.0%; elemental analysis Structure (molecular formula C) 36 H 34 BNO 2 ): theoretical values are as follows: c, 82.60; h, 6.55; b, 2.07; n, 2.68; o, 6.11; test values are: c,82.6: 1; h, 6.54; b, 2.07; n, 2.70; and O, 6.11. ESI-MS (M/z) (M) + ): the theoretical value is 523.48, and the actual value is 523.53.
The preparation method of the other intermediate A is similar to that of the intermediate A1, the preparation method of the other intermediate B is similar to that of the intermediate B1, and the specific structural formulas of the intermediate A and the intermediate B used in the invention are respectively shown in the following tables 6 and 7.
TABLE 6
TABLE 7
EXAMPLE 2 preparation of Compound 7
Adding 0.01mol of raw material 1, 0.012mol of intermediate A1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10 -5 molPd 2 (dba) 3 ，5×10 -5 mol P(t-Bu) 3 Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, sampling a sample point plate, and displaying that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, rotatably evaporating the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product with the HPLC purity of 99.88 percent and the yield of 77.3 percent. Elemental analysis Structure (molecular formula C) 50 H 33 NO): theoretical value C, 90.47; h, 5.01; n, 2.11; o, 2.41; test value C, 90.46; h, 5.01; n, 2.11; o, 2.42. HPLC-MS: the molecular weight of the material is 663.82, and the measured molecular weight is 663.85.
EXAMPLE 3 preparation of Compound 26
Compound 26 was prepared as in example 2, except starting material 2 was used instead of starting material 1 and intermediate a2 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 53 H 37 NO): theoretical value C, 90.44; h, 5.30; n, 1.99; o, 2.27; test values are: c, 90.43; h, 5.30; n, 1.99; o, 2.28. ESI-MS (M/z) (M) + ): theoretical value is 703.88, found 703.90.
EXAMPLE 4 preparation of Compound 40
EXAMPLE 5 preparation of Compound 50
EXAMPLE 6 preparation of Compound 77
Compound 77 can be prepared as in example 2, except thatFeed 4 replaced feed 1 and intermediate a1 was replaced with intermediate a 5. Elemental analysis Structure (molecular formula C) 56 H 36 N 2 O): theoretical value: c, 89.33; h, 4.82; n, 3.72; o, 2.12; test values: c, 89.33; h, 4.83; n, 3.72; o, 2.11. ESI-MS (M/z) (M) + ): the theoretical value is 752.92, and the actual value is 752.90.
EXAMPLE 7 preparation of Compound 128
Adding 0.01mol of intermediate 3 and 0.015mol of intermediate B1 into a 250ml three-necked bottle, and dissolving by using a mixed solvent of toluene and ethanol with a volume ratio of 2: 1; under inert atmosphere, 0.02mol of Na is added 2 CO 3 Aqueous solution (2M), 0.0001mol Pd (PPh) 3 ) 4 (ii) a And (3) reacting the mixed solution of the reactants for 24 hours at the reaction temperature of 100 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain the target product with the HPLC purity of 99.79% and the yield of 73.5%. Elemental analysis Structure (molecular formula C) 56 H 37 NO): theoretical value: c, 90.90; h, 5.04; n, 1.89; o, 2.16; test values: c, 90.91; h, 5.04; n, 1.89; o, 2.15. HPLC-MS: the molecular weight of the material was 739.92, and 739.90 was found.
Preparation of Compound 487 of example 8
Compound 487 was prepared as in example 2, except that starting material 5 was used instead of starting material 1 and intermediate a6 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 56 H 35 NO 2 ): theoretical values are as follows: c, 89.22; h, 4.68; n, 1.86; o, 4.24; test values are: c, 89.22; h, 4.67; n, 1.85; and O, 4.24. ESI-MS (M/z) (M) + ): theoretical value is 753.90, found 753.87.
EXAMPLE 9 preparation of Compound 861
Compound 861 was prepared as in example 2, except that feed 6 was used in place of feed 1 and intermediate a7 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C) 62 H 45 NO): theoretical value C, 90.81; h, 5.53; n, 1.71; o, 1.95; test values are: c, 90.82; h, 5.53; n, 1.70; o, 1.95. ESI-MS (M/z) (M) + ): the theoretical value is 820.05, and the actual value is 820.01.
EXAMPLE 10 preparation of Compound 949
Compound 949 was prepared as in example 2, except starting material 7 was used in place of starting material 1 and intermediate A8 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C) 54 H 41 NO): theoretical value: c, 90.09; h, 5.74; n, 1.95; o, 2.22; test values are: c, 90.09; h, 5.75; n, 1.95; o, 2.21. ESI-MS (M/z) (M) + ): theoretical value is 719.93, found 719.90.
EXAMPLE 11 preparation of Compound 979
Compound 979 was prepared as in example 2, except starting material 8 was used instead of starting material 1 and intermediate a7 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 57 H 45 NO): theoretical value: c, 90.08; h, 5.97; n, 1.84; o, 2.11; test values are: c, 90.07; h, 5.97; n, 1.84; o, 2.12. ESI-MS (M/z) (M) + ): theoretical value is 759.99, found 760.11.
EXAMPLE 12 preparation of Compound 993
Compound 993 was prepared as in example 2, except starting material 9 was used instead of starting material 1 and intermediate a9 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 54 H 39 NO 2 ): theoretical value C, 88.38; h, 5.36; n, 1.91; o, 4.36; test values are: c, 88.38; h, 5.36; n, 1.92; and O, 4.35. ESI-MS (M/z) (M) + ): theoretical value 733.91, found 733.90.
EXAMPLE 13 preparation of Compound 1032
Compound 1032 was prepared as in example 2, except starting material 10 was used instead of starting material 1 and intermediate a10 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 63 H 48 N 2 O): theoretical values are as follows: c, 89.12; h, 5.70; n, 3.30; o, 1.88; test values are: c, 89.12; h, 5.70; n, 3.30; o, 1.88. ESI-MS (M/z) (M) + ): theoretical 849.09, found 849.09.
EXAMPLE 14 preparation of Compound 1050
Compound 1050 was prepared as in example 2, except starting material 11 was used instead of starting material 1 and intermediate a11 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 58 H 49 NO): theoretical value C, 89.77; h, 6.36; n, 1.80; o, 2.06; test values are: c, 89.78; h, 6.36; n, 1.80; o, 2.05. ESI-MS (M/z) (M) + ): theoretical value is 776.04, found 776.0.
EXAMPLE 15 preparation of compound 1099
Preparation of compound 1099 is as in example2 except that starting material 12 was substituted for starting material 1 and intermediate a12 was substituted for intermediate a 1. Elemental analysis Structure (molecular formula C) 58 H 47 NOS): theoretical values are as follows: c, 86.42; h, 5.88; n, 1.74; o, 1.98; s, 3.98; test values: c, 86.43; h, 5.88; n, 1.75; o, 1.98; and S, 3.97. HPLC-MS: the molecular weight of the material is 806.08, and the measured molecular weight is 806.05.
Preparation of compound 1122 example 16
Compound 1122 was prepared as in example 2, except starting material 13 was used instead of starting material 1 and intermediate A8 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 50 H 33 NO): theoretical values are as follows: c, 90.47; h, 5.01; n, 2.11; o, 2.41; test values: c, 90.47; h, 5.00; n, 2.11; o, 2.42. ESI-MS (M/z) (M) + ): theoretical value 663.82, found 663.85.
EXAMPLE 17 preparation of 1159
Compound 1159 was prepared as in example 2, except starting material 14 was used instead of starting material 1 and intermediate A3 was used instead of intermediate a 1. Elemental analysis Structure (molecular formula C) 56 H 41 NO): theoretical value: c, 90.41; h, 5.56; n, 1.88; o, 2.15; test values: c, 90.41; h, 5.57; n, 1.88; o, 2.14. ESI-MS (M/z) (M) + ): theoretical value 743.95, found 743.91.
EXAMPLE 18 preparation of Compound 1412
Compound 1412 is prepared as in example 7, except starting material 15 is substituted for starting material 3 and intermediate B2 is substituted for intermediate B1. Elemental analysis Structure (molecular formula C) 56 H 35 NO 2 ): theoretical value C, 89.22; h, 4.68; n, 1.86; o, 4.24; test values are: c, 89.23; h, 4.68; n, 1.85; and O, 4.24. ESI-MS (M/z) (M) + ): theoretical value 753.90, found 753.88.
EXAMPLE 19 preparation of Compound 1641
Compound 1641 is prepared as in example 2, except starting material 16 is substituted for starting material 1 and intermediate A3 is substituted for intermediate a 1. Elemental analysis Structure (molecular formula C) 60 H 49 NO): theoretical value C, 90.08; h, 6.17; n, 1.75; o, 2.00; test values are: c, 90.08; h, 6.17; n, 1.74; and O, 2.01. ESI-MS (M/z) (M) + ): theoretical value 800.06, found 800.07.
The compound of the invention can be used in a luminescent device, can be used as a hole transport layer/electron barrier layer material, and can also be used as a host-guest material of a luminescent layer. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, and HOMO energy level, respectively, and the test results are shown in table 8:
TABLE 8
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10 -5 The toluene solution of (2); the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; highest occupied molecular orbital HOMOThe energy level was tested by the ionization energy test system (IPS3) in an atmospheric environment.
The data in the table show that the compound has high glass transition temperature, can improve the phase stability of the material film, and further prolongs the service life of the device; the material has high triplet state energy level, and can block energy loss of a light-emitting layer, so that the light-emitting efficiency of the device is improved. Meanwhile, the material has a proper HOMO energy level, so that the problem of injection of current carriers can be solved, and the voltage of a device can be reduced; therefore, the organic material containing the spirofluorene anthrone can effectively improve the luminous efficiency and the service life of the device after being applied to different functional layers of an OLED device.
The effect of the use of the compounds of the present invention in OLED devices will now be described in detail by device example 1. Compared with the comparative example, the device embodiment has the advantages that the manufacturing process of the device is completely the same, the same substrate material and the same electrode material are adopted, the film thickness of the electrode material is also kept consistent, and the difference is that the device embodiments 1-3 change the light-emitting layer material in the device; device examples 4-18 change hole transport layer/electron blocking layer materials of devices, and performance test results of devices obtained in each example are shown in table 9.
Device example 1 preparation of device 1
As shown in fig. 1, an electroluminescent device is prepared by the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 for 15 minutes by using deionized water, acetone and ethanol, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes;
b) evaporating HAT-CN as a hole injection layer 3 on the cleaned ITO anode layer 2 in a vacuum evaporation mode, wherein the evaporation thickness is 10 nm;
c) evaporating NPB (nitrogen-phosphorus) on the hole injection layer 3 in a vacuum evaporation mode to form a hole transport layer/electron blocking layer 4, wherein the evaporation thickness is 80 nm;
d) depositing a light-emitting layer 5 on the hole transporting/electron blocking layer 4, wherein the light-emitting layer 5 uses the compound 128 of the present invention as a host material, Ir (ppy) 3 As doping materials, Compound 1 and Ir (ppy) 3 The mass ratio of the luminescent layer 5 is 90:10, and the evaporation thickness of the luminescent layer 5 is 40 nm;
e) evaporating TPBI as a hole blocking/electron transport layer 6 on the light-emitting layer 5 in a vacuum evaporation mode, wherein the evaporation thickness is 40 nm;
f) evaporating LiF as an electron injection layer 7 on the hole blocking/electron transport layer 6 in a vacuum evaporation mode, wherein the evaporation thickness is 1 nm;
g) on the electron injection layer 7, a cathode Al was vacuum-deposited as a cathode reflective electrode layer 8, and the thickness was 100nm, thereby obtaining a device 1.
The structural formula of the material used in the device embodiment is as follows:
device example 2 preparation of device 2
This embodiment differs from device embodiment 1 in that: the host material of the light emitting layer of the electroluminescent device is changed into the compound 1032 prepared by the invention, and the doping material is Ir (ppy) 3 Compound 1032 and Ir (ppy) 3 In a mass ratio of 90: 10.
Device example 3 preparation of device 3
The main materials of the light-emitting layer of the electroluminescent device are changed into a compound 1412 and a compound GH prepared by the invention, and the doping materials are Ir (ppy) 3 Compounds 1412, GH and Ir (ppy) 3 The mass ratio of the three components is 60:30: 10.
Device example 4 preparation of device 4
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 7 of the invention, and the main material of the luminescent layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 The mass ratio of (2) is 88: 12.
Device example 5 preparation of device 5
The material of hole transport layer/electron barrier layer of electroluminescent device is the compound 26 of the invention, and the main material of the luminescent layer of electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 6 preparation of device 6
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 40 of the invention, and the main material of the light emitting layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 7 preparation of device 7
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 50 of the invention, and the main material of the light emitting layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 8 preparation of device 8
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 77 of the invention, and the main material of the light emitting layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 9 preparation of device 9
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 487 of the present invention, and the host material of the light emitting layer of the electroluminescent device is CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 10 preparation of device 10
The material of hole transport layer/electron barrier layer of electroluminescent device is inventive compound 861, and the host material of light emitting layer of electroluminescent device is CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 11 preparation of device 11
The material of hole transport layer/electron barrier layer of electroluminescent device is the compound 949 of the invention, and the main material of the luminescent layer of electroluminescent device is CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 12 preparation of device 12
The material of hole transport layer/electron barrier layer of electroluminescent device is inventive compound 979, and the main material of light emitting layer of electroluminescent device is CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 13 preparation of device 13
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 993 of the invention, and the main material of the luminescent layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 The mass ratio of (2) is 88: 12.
Device example 14 preparation of device 14
The material of hole transport layer/electron barrier layer of electroluminescent device is the compound 1050 of the present invention, and the main material of the light emitting layer of electroluminescent device is CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 15 preparation of device 15
The material of hole transport layer/electron barrier layer of electroluminescent device is the compound 1099 of the invention, and the main material of the luminescent layer of electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 16 preparation of device 16
The material of the hole transport layer/electron blocking layer of the electroluminescent device is the compound 1122 of the invention, and the main material of the light emitting layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 Is 88: 12.
Device example 17 preparation of device 17
The material of the hole transport layer/electron barrier layer of the electroluminescent device is the compound 1159 of the invention, and the main material of the luminescent layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 The mass ratio of (2) is 85: 15.
Device example 18 preparation of device 18
The material of the hole transport layer/electron barrier layer of the electroluminescent device is the compound 1641, and the main material of the light-emitting layer of the electroluminescent device is changed into CBP, CBP and Ir (ppy) 3 In a mass ratio of 85: 15.
Device comparative example 1 preparation of device 19
The present comparative example differs from device example 1 in that: the main material of the light-emitting layer of the OLED device is CBP, and the material of the hole transport layer/electron blocking layer is NPB.
After the electroluminescent device was prepared, the current efficiency and lifetime of the device were measured, and the results are shown in table 9.
TABLE 9
Note: the life test system is an OLED device life tester which is researched by the owner of the invention together with Shanghai university.
From the results in table 9, it can be seen that the spirofluorene anthrone-containing compound prepared by the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative device examples, the efficiency and lifetime of the compound are greatly improved compared with the known OLED materials, and especially the lifetime decay of the device is greatly improved.
The efficiency of the OLED device prepared by the compound is stable when the OLED device works at low temperature, the devices 2, 7 and 18 and the device 19 are subjected to efficiency test at the temperature of-10-80 ℃, and the obtained results are shown in a table 10 and a figure 2.
As can be seen from the data in table 10 and fig. 2, the devices 2, 7, and 18 are device structures in which the compound of the present invention and the known compound are combined, and compared to the device 19 prepared in comparative device 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase.
In order to further test the beneficial effects of the compound of the present invention, the device 2 of the present invention and the device 19 fabricated in the device comparative example 1 were tested for leakage current under reverse voltage, and the test data is shown in fig. 3, which shows that, as shown in fig. 3, the device 2 using the compound of the present invention has a smaller leakage current and a more stable current curve than the device 19 fabricated in the device comparative example 1, so that the material of the present invention has a longer service life after being applied to the device fabrication.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. An organic compound containing a spirofluorene anthrone structure is characterized in that the specific structure of the organic compound is as follows:
2. An organic electroluminescent element comprising the organic compound according to claim 1, comprising a light-emitting layer, wherein the light-emitting layer material contains the organic compound containing a spirofluorene anthrone structure.
3. An organic electroluminescent element comprising the organic compound according to claim 1, comprising a hole transport layer/electron blocking layer, wherein the hole transport layer/electron blocking layer material contains the organic compound containing a spirofluorene anthrone structure.
4. A lighting or display element comprising the organic electroluminescent device according to any one of claims 2 to 3.
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| PB01 | Publication | ||
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Address after: 214112 Wuxi New District, Jiangsu, Xinzhou Road, No. 210 Applicant after: Jiangsu March Technology Co.,Ltd. Address before: 214112 Wuxi New District, Jiangsu, Xinzhou Road, No. 210 Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd. |
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