CN109824577B - Spirofluorene derivative organic compound and application thereof in OLED device - Google Patents
Spirofluorene derivative organic compound and application thereof in OLED device Download PDFInfo
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Abstract
The invention relates to a spirofluorene derivative organic compound and application thereof in OLED devices, wherein the compound has a structure that spirofluorene is connected with an indole fused ring structure in a ring manner through a carbon-carbon double bond, the carbon-carbon double bond ring formation connection not only improves the chemical stability of materials, but also avoids the exposure of active positions of branched chain groups, and the whole molecule is a larger rigid structure and has a high triplet state energy level (T1); the steric hindrance is large, the rotation is not easy, and the three-dimensional structure is more stable, so that the compound has higher glass transition temperature and molecular thermal stability; in addition, the HOMO and LUMO distribution positions of the compound are separated from each other, so that the compound has proper HOMO and LUMO energy levels; therefore, after the compound is applied to an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a spirofluorene derivative organic compound and application thereof in OLED devices.
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 like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved. Current research into improving the performance of OLED light emitting devices 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 photoelectric functional material of the OLED are required 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 categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
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, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission 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 transmission material, a light emitting material, an electron transmission 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 material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher 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 lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a spirofluorene derivative organic compound and its application in an OLED device. The compound contains a spirofluorene structure, has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows:
a spirofluorene derivative organic compound has a structure shown in a general formula (1):
in the general formula (1) above,
through CL1-CL2Key, CL2-CL3Key, CL3-CL4A bond is linked to spirofluorene;
in the general formula (1), Ar represents substituted or unsubstituted C6-60One of an aryl group, a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur;
in the general formula (1), R represents a structure shown in a general formula (3);
in the general formula (2), X1Represented by oxygen atom, sulfur atom, C1-10Straight chain or C1-10One of a branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl substituted imino group or an aryl substituted imino group;
general formula (2) by CL’1-CL’2Key, CL’2-CL’3Bond or CL’3-CL’4The bond is linked to a structure represented by the general formula (1).
The structure of the compound is shown in a general formula (3), a general formula (4), a general formula (5), a general formula (6) or a general formula (7):
ar represents one of phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl or triazinyl; ar is also represented by a structure represented by general formula (8):
in the general formula (8), X represents an oxygen atom, a sulfur atom, C1-10One of linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl substituted imino or aryl substituted imino.
In the general formula (1)
Expressed as:
A method for producing the organic compound, the method involving a reaction equation:
the preparation method comprises the following steps:
(1) weighing the raw material I and the intermediate II, and dissolving the raw material I and the intermediate II in a toluene/ethanol mixed solvent with a volume ratio of 1.5-3.0: 1; then adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Under the protection of nitrogen, stirring the mixed solution at 90-110 ℃ for reaction for 10-24 hours, then cooling to room temperature, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate III; the molar ratio of the raw material I to the intermediate II is 1: 1.5-3.0; pd (PPh)3)4The molar ratio of the raw material I to the raw material I is 0.006-0.02: 1, and Na2CO3The molar ratio of the raw material I to the raw material I is 2.0-3.0: 1;
(2) under the protection of nitrogen, dissolving the intermediate III prepared in the step (1) in o-dichlorobenzene, adding triphenylphosphine, reacting for 12-16 hours at 170-190 ℃ under stirring, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming the filtrate, and passing through a neutral silica gel column to obtain an intermediate IV; the molar ratio of the intermediate III to triphenylphosphine is 1: 1-2;
(3) under the protection of nitrogen, sequentially weighing the intermediate IV, the raw material V, sodium tert-butoxide and Pd2(dba)3Stirring and mixing tri-tert-butylphosphine with toluene, heating to 100-120 ℃, performing reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate IV remains and the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain a target product; the molar ratio of the intermediate IV to the raw material V is 1: 1-2; the Pd2(dba)3The molar ratio of the tri-tert-butylphosphine to the intermediate IV is 0.006-0.02: 1, and the molar ratio of the tri-tert-butylphosphine to the intermediate IV is 0.006-0.02: 1; the molar ratio of the sodium tert-butoxide to the intermediate IV is 2.0-3.0: 1.
The application of the spirofluorene derivative organic compound is used for preparing an organic electroluminescent device.
An organic electroluminescent device containing the spirofluorene derivative organic compound comprises at least one functional layer containing the spirofluorene derivative organic compound.
An organic electroluminescent device containing the spirofluorene derivative organic compound comprises an electron blocking layer, wherein the electron blocking layer is made of the spirofluorene derivative organic compound.
An organic electroluminescent device containing the spirofluorene derivative organic compound comprises a light-emitting layer, wherein the light-emitting layer contains the spirofluorene derivative organic compound.
A lighting or display element containing the organic electroluminescent device, the lighting or display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound takes spirofluorene as a framework, and is connected with an indole fused ring structure in a ring form through a carbon-carbon double bond, and the carbon-carbon double bond is connected in the ring form, so that the stability of the material is improved, and the exposure of the active position of a branched chain group is avoided; besides the greater rigidity of the spirofluorene, the indole fused ring structure is also a large pi-bond conjugated rigid structure, the steric hindrance is large, and the compound material is not easy to rotate, so that the three-dimensional structure of the compound material is more stable. The spin density distribution of the triplet state energy level T1 of the compound is basically on a branch chain, and the branch chain has a high T1 energy level, so that the compound also has a high T1 energy level; when the compound is used as an electron blocking layer material of an OLED, the high T1 energy level can effectively block energy from being transferred from a light emitting layer to a hole transport layer, energy loss is reduced, and the energy of a main material of the light emitting layer is fully transferred to a doping material, so that the light emitting efficiency of the material applied to a device is improved.
The organic compound has a structure which enables the distribution of electrons and holes in the light-emitting layer to be more balanced, and under the proper 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 derivative is used as a light-emitting functional layer material of an OLED light-emitting device, the spirofluorene derivative can be matched with the branched chain in the range of the spirofluorene derivative 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 organic compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, and the photoelectric property 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 light-emitting devices.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
the organic electroluminescent device comprises a transparent substrate layer 1, a transparent substrate layer 2, an ITO anode layer 3, a hole injection layer 4, a hole transport layer 5, an electron blocking layer 6, a light emitting layer 7, a hole blocking/electron transport layer 8, an electron injection layer 9 and a cathode reflection electrode layer.
Fig. 2 is a graph of efficiency of devices measured at different temperatures.
Detailed Description
Example 1: synthesis of intermediate II
(1) Weighing the raw material A, dissolving the raw material A in acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing liquid bromine, dissolving the liquid bromine in glacial acetic acid, slowly dropwise adding the liquid bromine into an acetic acid solution of the raw material A, stirring for 5 hours at room temperature, sampling a sample point plate, and completely reacting when no raw material A remains; after the reaction is finished, adding alkali liquor into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase for filtration, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate II; the molar ratio of the intermediate II to the liquid bromine is 1: 1-1.5;
synthesis example of intermediate II-1:
(4) adding 0.3mol of raw material A1 into a 100mL three-necked bottle, dissolving with 30mL of acetic acid, and cooling to 0 ℃ by using an ice salt bath; adding 18.4ml (3.6mol) of liquid bromine dissolved in 20ml of glacial acetic acid into the reaction system dropwise at 0 ℃, heating to room temperature, and stirring for 5 hours; a sample point panel showed no raw material a1 remaining and the reaction was complete; after the reaction is finished, adding a sodium carbonate solution into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase, drying and filtering, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate II-1, wherein the HPLC purity is 99.6%, and the yield is 70.4%.
Elemental analysis Structure (molecular formula C)12H6BrNO3): theoretical value C, 49.35; h, 2.07; br, 27.36; n, 4.80; o, 16.43; test values are: c, 49.34; h, 2.06; br, 27.35; n, 4.81; o, 16.44. ESI-MS (M/z) (M)+): theoretical value is 292.09, found 292.23.
Synthesis of intermediate II: intermediate II is formed by bromination of starting material A, and the specific structure is shown in Table 1.
TABLE 1
Example 2: synthesis of Compound 2:
(1) in a 250ml three-necked flask, 0.05mol of the raw material I-1, 0.075mol of the intermediate II-1 was added under nitrogen protection, dissolved in a mixed solvent (90ml of toluene, 45ml of ethanol), and then 0.15mol of Na was added2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate III-1 with the purity of 99.1 percent and the yield of 77.3 percent. Elemental analysis Structure (molecular formula C)37H21NO3): theoretical value C, 84.24; h, 4.01; n, 2.65; o, 9.10; test values are: c, 84.23; h, 4.02; n, 2.63; and O, 9.12. ESI-MS (M/z) (M)+): theoretical value is 527.15, found 527.36.
(2) Adding 0.03mol of intermediate III-1 and 0.036mol of triphenylphosphine into a 100ml three-neck flask under the protection of nitrogen, dissolving the mixture by using 50ml of o-dichlorobenzene, heating the mixture to 170 ℃, reacting for 15 hours, sampling a sample, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate IV-1 with the purity of 99.3 percent and the yield of 76.6 percent. Elemental analysis Structure (molecular formula C)37H21NO): theoretical value C, 89.67; h, 4.27; n, 2.83; o, 3.23; test values are: c, 89.66; h, 4.26; n, 2.84; and O, 3.24. ESI-MS (M/z) (M)+): theoretical value is 495.16, found 495.43.
(3) Adding 0.01mol of intermediate IV-1, 0.012mol of bromobenzene and 0.03mol of intermediate IV-1 into a 250ml three-mouth bottle under the protection of nitrogenmol sodium tert-butoxide, 5X 10-5mol Pd2(dba)3，5×10-5Dissolving the tri-tert-butylphosphine in 150ml of toluene, heating and refluxing for 24 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product, wherein the HPLC purity is 99.4%, and the yield is 78.1%; elemental analysis Structure (molecular formula C)43H25NO): theoretical value C, 90.34; h, 4.41; n, 2.45; o, 2.80; test values are: c, 90.33; h, 4.42; n, 2.44; o, 2.81. ESI-MS (M/z) (M)+): theoretical value is 571.19, found 571.45.
Example 3: synthesis of compound 13:
(1) in a 250ml three-necked flask, under the protection of nitrogen, 0.05mol of the raw material I-1, 0.075mol of the intermediate II-2 was added, dissolved in a mixed solvent (90ml of toluene, 45ml of ethanol), and then 0.15mol of Na was added2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate III-2 with the purity of 98.9 percent and the yield of 76.8 percent. Elemental analysis Structure (molecular formula C)40H27NO2): theoretical value C, 86.78; h, 4.92; n, 2.53; o, 5.78; test values are: c, 86.76; h, 4.93; n, 2.55; and O, 5.76. ESI-MS (M/z) (M)+): theoretical value is 553.20, found 553.47.
(2) Adding 0.03mol of intermediate III-2 and 0.036mol of triphenylphosphine into a 100ml three-neck flask under the protection of nitrogen, dissolving the mixture by using 50ml of o-dichlorobenzene, heating the mixture to 170 ℃, reacting for 15 hours, sampling a sample, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate IV-2 with the purity of 99.3 percent and the yield of 76.6 percent. Elemental analysis Structure (molecular formula C)40H27N): theoretical value C, 92.10; h, 5.22; n, 2.69; test values are: c, 92.12; h, 5.21; n, 2.67. ESI-MS (M/z) (M +): theoretical value of 521.21, foundThe value is 521.44.
(3) Adding 0.01mol of intermediate IV-2, 0.012mol of bromobenzene, 0.03mol of sodium tert-butoxide and 5X 10-5mol of Pd in a 250ml three-neck flask under the protection of nitrogen2(dba)3Dissolving 5 x 10-5mol of tri-tert-butylphosphine in 150ml of toluene, heating and refluxing for 24 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product, wherein the HPLC purity is 99.4%, and the yield is 78.1%; elemental analysis Structure (molecular formula C)46H31N): theoretical value C, 92.43; h, 5.23; n, 2.34; test values are: c, 92.44; h, 5.24; and N, 2.32. ESI-MS (M/z) (M)+): theoretical value is 597.25, found 597.54.
Example 4: synthesis of compound 24:
the preparation method of the intermediate III-3 is the same as that of the intermediate III-1, except that the intermediate II-3 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-3 is the same as that of the intermediate IV-1, except that the intermediate III-3 is used for replacing the intermediate III-1;
compound 24 was prepared as compound 2, except that intermediate IV-3 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2): theoretical value C, 90.99; h, 4.68; n, 4.33; test values are: c, 90.97; h, 4.68; and N, 4.35. ESI-MS (M/z) (M)+): theoretical value is 646.24, found 646.51.
Example 5: synthesis of compound 49:
the preparation method of the intermediate III-4 is the same as that of the intermediate III-1, except that the intermediate II-4 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-4 is the same as that of the intermediate IV-1, except that the intermediate III-4 is used for replacing the intermediate III-1;
compound 49 was prepared using compound 2, except intermediate IV-4 was used instead of intermediate IV-1 and 3-bromo-N-phenylcarbazole instead of bromobenzene. Elemental analysis Structure (molecular formula C)55H32N2O): theoretical value C, 89.65; h, 4.38; n, 3.80; o, 2.17; test values are: c, 89.63; h, 4.37; n, 3.82; o, 2.18. ESI-MS (M/z) (M)+): theoretical value is 736.25, found 736.53.
Example 6: synthesis of compound 64:
the preparation method of the intermediate III-5 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-5 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-5 is the same as that of the intermediate IV-1, except that the intermediate III-5 is used for replacing the intermediate III-1;
compound 64 was prepared as compound 2, except that intermediate IV-5 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)43H25NO): theoretical value C, 90.34; h, 4.41; n, 2.45; o, 2.80; test values are: c, 90.32; h, 4.42; n, 2.43; o, 2.83. ESI-MS (M/z) (M)+): theoretical value is 571.19, found 571.47.
Example 7: synthesis of compound 73:
the preparation method of the intermediate III-6 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-6 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-6 is the same as the intermediate IV-1, except that the intermediate III-6 is used for replacing the intermediate III-1;
compound 73 was prepared using compound 2, except that intermediate IV-6 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31N): theoretical value C, 92.43; h, 5.23; n, 2.34; test values are: c, 92.42; h, 5.25; n, 2.33. ESI-MS (M/z) (M)+): theoretical value is 597.25, found 597.48.
Example 8: synthesis of compound 78:
the preparation method of the intermediate III-7 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-7 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-7 is the same as that of the intermediate IV-1, except that the intermediate III-7 is used for replacing the intermediate III-1;
compound 78 was prepared as compound 2, except that intermediate IV-7 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2): theoretical value C, 90.99; h, 4.68; n, 4.33; test values are: c, 90.98; h, 4.67; and N, 4.35. ESI-MS (M/z) (M)+): theoretical value is 646.24, found 646.56.
Example 9: synthesis of compound 82:
the preparation method of the intermediate III-8 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-3 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-8 is the same as that of the intermediate IV-1, except that the intermediate III-8 is used for replacing the intermediate III-1;
compound 82 was prepared as compound 2, except that intermediate IV-8 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2): theoretical value C, 90.99; h, 4.68; n, 4.33; test values are: c, 90.97; h, 4.67; n, 4.36. ESI-MS (M/z) (M)+): theoretical value is 646.24, found 646.48.
Example 10: synthesis of compound 97:
the preparation method of the intermediate III-6 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-3 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-6 is the same as the intermediate IV-1, except that the intermediate III-6 is used for replacing the intermediate III-1;
compound 97 was prepared using compound 2 except intermediate IV-6 was used instead of intermediate IV-1 and 2-bromobiphenyl was used instead of bromobenzene. Elemental analysis Structure (molecular formula C)52H35N): theoretical value C, 92.69; h, 5.24; n, 2.08; test values are: c, 92.67; h, 5.26; and N, 2.07. ESI-MS (M/z) (M)+): theoretical value is 673.28, found 673.45.
Example 11: synthesis of compound 100:
the preparation method of the intermediate III-9 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-8 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-9 is the same as the intermediate IV-1, except that the intermediate III-9 is used for replacing the intermediate III-1;
compound 100 was prepared as compound 2, except intermediate IV-9 was used in place of intermediate IV-1 and 2-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)52H35N): theoretical value C, 92.69; h, 5.24; n, 2.08; test values are: c, 92.66; h, 5.27; and N, 2.07. ESI-MS (M/z) (M)+): theoretical value is 673.28, found 673.47.
Example 12: synthesis of compound 107:
the preparation method of the intermediate III-10 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-9 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-10 is the same as that of the intermediate IV-1, except that the intermediate III-10 is used for replacing the intermediate III-1;
compound 100 was prepared as compound 2, except intermediate IV-10 was used in place of intermediate IV-1 and 3-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)49H29NO): theoretical value C, 90.86; h, 4.51; n, 2.16; o, 2.47; test values are: c, 90.85; h, 4.53; n, 2.15; o, 2.48. ESI-MS (M/z) (M)+): theoretical value is 647.22, found 647.42.
Example 13: synthesis of compound 118:
the preparation method of the intermediate III-11 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-10 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-11 is the same as the intermediate IV-1, except that the intermediate III-11 is used for replacing the intermediate III-1;
compound 118 was prepared as compound 2, except intermediate IV-11 was used instead of intermediate IV-1 and 3-bromobiphenyl was used instead of bromobenzene. Elemental analysis Structure (molecular formula C)49H29NS): theoretical value C, 88.66; h, 4.40; n, 2.11; s, 4.83; test values are: c, 88.65; h, 4.41; n, 2.12; and S, 4.82. ESI-MS (M/z) (M)+): theoretical value is 663.20, found 663.44.
Example 14: synthesis of compound 136:
the preparation method of the intermediate III-5 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-5 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-5 is the same as that of the intermediate IV-1, except that the intermediate III-5 is used for replacing the intermediate III-1;
compound 136 was prepared as compound 2, except intermediate IV-5 was used in place of intermediate IV-1 and 4-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)49H29NO): theoretical value C, 90.86; h, 4.51; n, 2.16; o, 2.47; test values are: c, 90.87; h, 4.52; n, 2.17; o, 2.44. ESI-MS (M/z) (M)+): theoretical value is 647.22, found 647.46.
Example 15: synthesis of compound 151:
the preparation method of the intermediate III-12 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-11 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-12 is the same as the intermediate IV-1, except that the intermediate III-12 is used for replacing the intermediate III-1;
compound 151 was prepared using compound 2 except intermediate IV-12 was used instead of intermediate IV-1 and 4-bromobiphenyl was used instead of bromobenzene. Elemental analysis Structure (molecular formula C)55H34N2): theoretical value C, 91.38; h, 4.74; n, 3.88; test values are: c, 91.37; h, 4.76; and N, 3.87. ESI-MS (M/z) (M)+): theoretical value is 722.27, found 722.55.
Example 16: synthesis of compound 169:
the preparation method of the intermediate III-6 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-6 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-6 is the same as the intermediate IV-1, except that the intermediate III-6 is used for replacing the intermediate III-1;
compound 169 was prepared as compound 2, except that intermediate IV-6 was used instead of intermediate IV-1 and 4-bromodibenzofuran was used instead of bromobenzene. Elemental analysis Structure (molecular formula C)52H33NO): theoretical value C, 90.80; h, 4.84; n, 2.04; o, 2.33; test values are: c, 90.82; h, 4.82; n, 2.02; o, 2.34. ESI-MS (M/z) (M)+): theoretical value is 687.26, found 687.53.
Example 17: synthesis of compound 185:
the preparation method of the intermediate III-13 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-9 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-13 is the same as the intermediate IV-1, except that the intermediate III-13 is used for replacing the intermediate III-1;
compound 185 was prepared as compound 2 except intermediate IV-13 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)43H25NO): theoretical value C, 90.34; h, 4.41; n, 2.45; o, 2.80; test values are: c, 90.31; h, 4.40; n, 2.46; o, 2.83. ESI-MS (M/z) (M)+): theoretical value is 571.19, found 571.42.
Example 18: synthesis of compound 197:
the preparation method of the intermediate III-14 is the same as that of the intermediate III-1, except that the raw material I-3 is used for replacing the raw material I-1 and the intermediate II-2 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-14 is the same as that of the intermediate IV-1, except that the intermediate III-14 is used for replacing the intermediate III-1;
compound 197 is prepared as compound 2, except that intermediate IV-14 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31N): theoretical value C, 92.43; h, 5.23; n, 2.34; test values are: c, 92.45; h, 5.21; and N, 2.34. ESI-MS (M/z) (M)+): theoretical value is 597.25, found 597.45.
Example 19: synthesis of compound 204:
the preparation method of the intermediate III-15 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-7 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-15 is the same as that of the intermediate IV-1, except that the intermediate III-15 is used for replacing the intermediate III-1;
compound 204 was prepared as compound 2, except that intermediate IV-15 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2): theoretical value C, 90.99; h, 4.68; n, 4.33; test values are: c, 90.98; h, 4.70; n, 4.32. ESI-MS (M/z) (M)+): theoretical value is 646.24, found 646.53.
Example 20: synthesis of compound 205:
the preparation method of the intermediate III-16 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-11 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-16 is the same as that of the intermediate IV-1, except that the intermediate III-16 is used for replacing the intermediate III-1;
compound 205 was prepared as compound 2, except that intermediate IV-16 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2): theoretical value C, 90.99; h, 4.68; n, 4.33; test values are: c, 91.01; h, 4.66; n, 4.33. ESI-MS (M/z) (M)+): theoretical value is 646.24, found 646.57.
Example 21: synthesis of compound 223:
the preparation method of the intermediate III-17 is the same as that of the intermediate III-1, except that the raw material I-3 is used for replacing the raw material I-1 and the intermediate II-6 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-17 is the same as that of the intermediate IV-1, except that the intermediate III-17 is used for replacing the intermediate III-1;
compound 223 was prepared as described for compound 2, except that intermediate IV-17 was used in place of intermediate IV-1 and 2-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)52H35N): theoretical value C, 92.69; h, 5.24; n, 2.08; test values are: c, 92.68; h, 5.21; n, 2.11. ESI-MS (M/z) (M)+): theoretical value is 673.28, found 673.54.
Example 22: synthesis of compound 246:
the preparation method of the intermediate III-18 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-12 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-18 is the same as that of the intermediate IV-1, except that the intermediate III-18 is used for replacing the intermediate III-1;
compound 246 was prepared as described for compound 2, except that intermediate IV-18 was used in place of intermediate IV-1 and 3-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)52H35N): theoretical value C, 92.69; h, 5.24; n, 2.08; test values are: c, 92.71; h, 5.23; and N, 2.06. ESI-MS (M/z) (M)+): theoretical value is 673.28, found 673.58.
Example 23: synthesis of compound 259:
the preparation method of the intermediate III-19 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-4 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-19 is the same as the intermediate IV-1, except that the intermediate III-19 is used for replacing the intermediate III-1;
compound 259 was prepared as compound 2, except that intermediate IV-19 was used instead of intermediate IV-1 and 4-bromobiphenyl was used instead of bromobenzene. Elemental analysis Structure (molecular formula C)49H29NO): theoretical value C, 90.86; h, 4.51; n, 2.16; o, 2.47; test values are: c, 90.85; h, 4.53; n, 2.17; o, 2.45. ESI-MS (M/z) (M)+): theoretical value is 647.22, found 647.51.
Example 24: synthesis of compound 272:
the preparation method of the intermediate III-20 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-13 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-20 is the same as that of the intermediate IV-1, except that the intermediate III-20 is used for replacing the intermediate III-1;
compound 272 was prepared as described for compound 2, except intermediate IV-20 was used in place of intermediate IV-1 and 4-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)52H35N): theoretical value C, 92.69; h, 5.24; n, 2.08; test values are: c, 92.70; h, 5.21; and N, 2.09. ESI-MS (M/z) (M)+): theoretical value is 673.28, found 673.62.
Example 25: synthesis of compound 286:
the preparation method of the intermediate III-21 is the same as that of the intermediate III-1, except that the raw material I-3 is used for replacing the raw material I-1 and the intermediate II-5 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-21 is the same as that of the intermediate IV-1, except that the intermediate III-21 is used for replacing the intermediate III-1;
compound 286 is prepared as compound 2, except that intermediate IV-21 is used instead of intermediate IV-1 and 4-bromodibenzofuran is used instead of bromobenzene. Elemental analysis Structure (molecular formula C)49H27NO2): theoretical value C, 88.94; h, 4.11; n, 2.12; o, 4.84; test values are: c, 88.92; h, 4.12; n, 2.11; and O, 4.85. ESI-MS (M/z) (M)+): theoretical value is 661.20, found 661.50.
Example 26: synthesis of compound 298:
the preparation method of the intermediate III-22 is the same as that of the intermediate III-1, except that the raw material I-3 is used for replacing the raw material I-1 and the intermediate II-14 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-22 is the same as the intermediate IV-1, except that the intermediate III-22 is used for replacing the intermediate III-1;
compound 298 was prepared as compound 2, except that intermediate IV-22 was used instead of intermediate IV-1 and 4-bromodibenzofuran was used instead of bromobenzene. Elemental analysis Structure (molecular formula C)55H32N2O): theoretical value C, 89.65; h, 4.38; n, 3.80; o, 2.17; test values are: c, 89.66; h, 4.35; n, 3.83; o, 2.16. ESI-MS (M/z) (M)+): theoretical value is 736.25, found 736.58.
Example 27: synthesis of compound 309:
the intermediate III-23 is prepared by the same method as the intermediate III-1 except that the intermediate II-1 is replaced by the intermediate II-5; the preparation method of the intermediate IV-23 is the same as that of the intermediate IV-1, except that the intermediate III-23 is used for replacing the intermediate III-1;
compound 309 is prepared as compound 2, except that intermediate IV-23 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)43H25NO): theoretical value C, 90.34; h, 4.41; n, 2.45; o, 2.80; test values are: c, 90.36; h, 4.40; n, 2.42; o, 2.82. ESI-MS (M/z) (M)+): theoretical value is 571.19, found 571.51.
Example 28: synthesis of compound 324:
the intermediate III-24 is prepared by the same method as the intermediate III-1 except that the intermediate II-11 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-24 is the same as that of the intermediate IV-1, except that the intermediate III-24 is used for replacing the intermediate III-1;
compound 324 can be prepared using compound 2 except that intermediate IV-24 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2): theoretical value C, 90.99; h, 4.68; n, 4.33; test values are: c, 90.98; h,4.65N, 4.38. ESI-MS (M/z) (M)+): theoretical value is 646.24, found 646.55.
Example 29: synthesis of compound 343:
the intermediate III-25 is prepared by the same method as the intermediate III-1 except that the intermediate II-6 replaces the intermediate II-1; the preparation method of the intermediate IV-25 is the same as that of the intermediate IV-1, except that the intermediate III-25 is used for replacing the intermediate III-1;
preparation of Compound 324The preparation method is the same as that of the compound 2, except that the intermediate IV-25 is used for replacing the intermediate IV-1 and the bromobenzene is replaced by the 2-bromobiphenyl. Elemental analysis Structure (molecular formula C)52H35N): theoretical value C, 92.69; h, 5.24; n, 2.08; test values are: c, 92.70; h, 5.22; and N, 2.08. ESI-MS (M/z) (M)+): theoretical value is 673.28, found 673.65.
Example 30: synthesis of compound 357:
the preparation method of the intermediate III-3 is the same as that of the intermediate III-1, except that the intermediate II-3 replaces the intermediate II-1; the preparation method of the intermediate IV-26 is the same as the intermediate IV-1, except that the intermediate III-3 is used for replacing the intermediate III-1;
compound 357 is prepared as compound 2 except intermediate IV-26 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)55H34N2): theoretical value C, 91.38; h, 4.74; n, 3.88; test values are: c, 91.35; h, 4.75; and N, 3.90. ESI-MS (M/z) (M)+): theoretical value is 722.27, found 722.66.
Example 31: synthesis of compound 379:
the preparation method of the intermediate III-26 is the same as that of the intermediate III-1, except that the raw material I-4 is used for replacing the raw material I-1 and the intermediate II-6 is used for replacing the intermediate II-1; the intermediate IV-27 is prepared by the same method as the intermediate IV-1, except that the intermediate III-26 is used for replacing the intermediate III-1;
compound 379 was prepared as compound 2, except intermediate IV-27 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31N): theoretical value C, 92.43; h, 5.23; n, 2.34; test values are: c, 92.42; h, 5.22; and N, 2.36. ESI-MS (M/z) (M)+): theory of the inventionThe value was 597.25, found 597.48.
The organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer material or a light-emitting layer host material. The compounds of the present invention were tested for thermal properties, HOMO energy levels, and cyclic voltammetric stability, as shown in Table 2.
TABLE 2
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of (4); 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; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3) in an atmospheric environment. The cyclic voltammetry stability is characterized by observing the redox characteristics of the material by cyclic voltammetry; and (3) testing conditions are as follows: the test sample was dissolved in a mixed solvent of dichloromethane and acetonitrile at a volume ratio of 2:1 at a concentration of 1mg/mL, and the electrolyte was 0.1M of an organic solution of tetrabutylammonium tetrafluoroborate or hexafluorophosphate. The reference electrode is an Ag/Ag + electrode, the counter electrode is a titanium plate, the working electrode is an ITO electrode, and the cycle time is 20 times.
The data in the table show that the organic compound has different HOMO energy levels and can be applied to different functional layers, and the spirofluorene derivative organic compound has higher triplet state energy level, higher thermal stability and chemical stability, so that the efficiency and the service life of the manufactured OLED device containing the organic compound are improved.
The application effect of the synthesized OLED material in the device is explained in detail through device examples 1-30 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 30 and the device comparative example 1 have the same manufacturing process, adopt the same substrate material and electrode material, and keep the film thickness of the electrode material consistent, except that the device embodiments 2 to 17 use the material of the invention as an electron blocking layer; device embodiments 18-30 have variations in host materials for light emitting layers in the devices. The results of the performance tests of the devices obtained in the examples are shown in table 3.
Device example 1: as shown in fig. 1, an electroluminescent device is prepared by the steps of:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a hole transport material NPB (N-propyl bromide) on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 60nm, and the hole transport layer is a hole transport layer 4; d) evaporating an electron blocking layer material, namely the compound 24 of the invention, on the hole transport layer 4 in a vacuum evaporation mode, wherein the thickness of the layer is 20nm, and the layer is an electron blocking layer 5; e) depositing a light-emitting layer 6 on the electron blocking layer 5, using CBP as a host material, Ir (ppy)3As doping material, Ir (ppy)3The mass ratio of CBP to CBP is 10:90, and the thickness is 30 nm; f) an electron transport material TPBI is evaporated on the light-emitting layer 6 in a vacuum evaporation mode, the thickness of the TPBI is 40nm, and the organic material of the TPBI layer is used as a hole blocking/electron transport layer 7; g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8; h) vacuum evaporating cathode Al (100nm) on the electron injection layer 8, which is a cathode reflection electrode layer 9; electroluminescent devices were fabricated as described above, and the current efficiency and lifetime of the devices were measured, and the results are shown in table 3. The molecular structural formula of the related material is shown as follows:
device example 2: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is compound 64 of the present invention. Device example 3: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 73 of the present invention. Device example 4: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 78 of the present invention. Device example 5: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is compound 82 of the present invention. Device example 6: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 97 of the present invention. Device example 7: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 100 of the present invention. Device example 8: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 136 of the present invention. Device example 9: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 151 of the present invention. Device example 10: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 204 of the present invention. Device example 11: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 205 of the present invention. Device example 12: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 223 of the present invention. Device example 13: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 309 of the present invention. Device example 14: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is the compound 324 of the invention. Device structureExample 15: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 343 of the present invention. Device example 16: this embodiment differs from device embodiment 1 in that: the material of the electron blocking layer of the electroluminescent device is the compound 357 of the present invention. Device example 17: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is the compound 379 of the invention. Device example 18: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 13 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 13 in a mass ratio of 10: 90. Device example 19: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 118 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 118 in a mass ratio of 10: 90. Device example 20: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 169 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 169 in a mass ratio of 10: 90. Device example 21: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 197 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 197 in a mass ratio of 10: 90. Device example 22: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 246 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 246 in a mass ratio of 10: 90. Device example 23: this embodiment differs from device embodiment 1 in that: the electron barrier material of the electroluminescent device is NPB, and the main body material of the luminescent layer of the electroluminescent deviceThe material is changed into the compound 259 of the invention, and the doping material is Ir (ppy)3， Ir(ppy)3And compound 259 in a mass ratio of 10: 90. Device example 24: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 286, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 286 in a mass ratio of 10: 90. Device example 25: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 2 and the compound GHN, and the doping material is Ir (ppy)3 Compound 2, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 26: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 49 and the compound GHN, and the doping material is Ir (ppy)3Compound 49, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 27: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 107 and the compound GHN of the invention, and the doping material is Ir (ppy)3Compound 107, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 28: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 185 and the compound GHN, and the doping material is Ir (ppy)3Compound 185, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 29: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 272 and the compound GHN, and the doping material is Ir (ppy)3Compound 272, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 30:this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 298 and the compound GHN of the invention, and the doping material is Ir (ppy)3Compounds 298, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device comparative example 1: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is known compound CBP, and the doping material is Ir (ppy)3，Ir(ppy)3And CBP at a mass ratio of 10:90, the detection data of the resulting electroluminescent device are shown in Table 3.
TABLE 3
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 3, it can be seen that the spirofluorene derivative organic compound of the present invention can be applied to the fabrication of an OLED light emitting device, and compared with comparative device example 1, the voltage of the device is significantly reduced, and the efficiency and the lifetime of the device are both improved greatly compared with those of the known OLED material, especially the lifetime decay of the device is greatly improved.
Further, the OLED devices prepared from the material of the invention can maintain long service life at high temperature, and the device examples 1-30 and the device comparative example 1 are subjected to a high-temperature driving life test at 85 ℃, and the obtained results are shown in Table 4.
TABLE 4
As can be seen from the data in Table 4, the OLED device provided by the invention has a very good driving life at high temperature compared with the device comparative example 1 in the device structure of the device examples 1-30 in which the material of the invention is matched with the known material.
In order to compare the efficiency attenuation conditions of different devices under high current density, the efficiency attenuation coefficient is defined
Carrying out representation;
it indicates a drive current of 100mA/cm2Maximum efficiency mu of time device100Maximum efficiency of the devicemaxDifference between the maximum efficiency mu and themaxThe ratio of the amount of the first and the second,
the larger the value, the more serious the efficiency roll-off of the device is, and conversely, the problem that the device rapidly decays under high current density is controlled.
The organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer material or a light-emitting layer host material. The efficiency attenuation coefficients of the device examples 1 to 30 and the device comparative example 1 were measured
The measurement results are shown in Table 5.
TABLE 5
As can be seen from the data in table 5, compared with comparative device 1, the OLED device provided by the present invention has a relatively gentle roll-off trend of efficiency at high current density, and provides a good prospect for industrialization.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 4, 20 and 28 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 6 and the figure 2.
TABLE 6
As can be seen from the data in table 6 and fig. 2, device examples 4, 20, and 28 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
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 (6)
1. The spirofluorene derivative organic compound is characterized in that the specific structural formula of the organic compound is as follows:
2. use of the spirofluorene derivative-based organic compound according to claim 1 for the preparation of organic electroluminescent devices.
3. An organic electroluminescent element comprising the spirofluorene derivative-based organic compound according to claim 1, wherein the organic electroluminescent element comprises at least one functional layer comprising the spirofluorene derivative-based organic compound.
4. An organic electroluminescent device comprising the spirofluorene derivative-based organic compound according to claim 1, comprising an electron blocking layer, wherein the electron blocking layer is made of the spirofluorene derivative-based organic compound.
5. An organic electroluminescent device comprising the spirofluorene derivative-based organic compound according to claim 1, comprising a light-emitting layer, wherein the light-emitting layer contains the spirofluorene derivative-based organic compound.
6. A lighting or display element comprising the organic electroluminescent device according to any one of claims 3 to 5.
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