CN112500396B - Dibenzopyran spiro organic luminescent compound and preparation method and application thereof - Google Patents

Dibenzopyran spiro organic luminescent compound and preparation method and application thereof Download PDF

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CN112500396B
CN112500396B CN202011379762.9A CN202011379762A CN112500396B CN 112500396 B CN112500396 B CN 112500396B CN 202011379762 A CN202011379762 A CN 202011379762A CN 112500396 B CN112500396 B CN 112500396B
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dibenzopyran
spiro
organic light
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汪康
王进政
李贺
曹淼
杨冰
白金凤
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention provides a dibenzopyran spiro organic luminescent compound and a preparation method and application thereof, wherein the organic luminescent compound has a structure shown in a formula I. The oxygen atoms introduced into the parent nucleus of the compound increase the steric hindrance of the whole compound, and the asymmetric specific spatial structure is beneficial to reducing the intermolecular cohesion, reducing the crystallization possibility and improving the glass transition temperature; the pyridine, diazine or triazine side chain group containing N atoms is an electron-obtaining group, has good electron transport characteristics, improves the mobility of an electron transport material, and further ensures that the prepared organic electroluminescent device has higher luminous efficiency.

Description

Dibenzopyran spiro organic luminescent compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a dibenzopyran spiro-based organic light-emitting compound and a preparation method and application thereof.
Background
After the 21 st century, people need a new generation of flat panel displays with better performance and meeting future life needs to meet the coming of the "4C" (i.e., communication, automotive electronics, computers, consumer electronics) and "4G" (i.e., fourth generation mobile communication) era. Organic Light Emitting Diodes (OLEDs), as a new generation of display technology, have advantages over liquid crystal flat panel displays: self-luminescence, wide visual angle (more than 175 ℃), flexible display, short reaction time, ultra-thin design (the thickness can be less than 1mm), low working voltage (3-10V) and the like, so the status in the display field is increasingly important.
OLED light emitting devices generally have a sandwich structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. The Hole Transport Layer (HTL) is responsible for adjusting the injection rate and injection amount of holes, and the Electron Transport Layer (ETL) is responsible for adjusting the injection rate and injection amount of electrons. The electron transport material plays an extremely important role in the OLED, and the transport material with high electron mobility can enable electrons and holes of the device to be injected approximately in balance, so that the probability of exciton formation is increased, the leakage current formed by the fact that holes are transported to a cathode through the inside of the device due to the fact that the number of the holes is excessive in the device is reduced, and the light emitting brightness and the efficiency of the device are improved.
Disclosure of Invention
In view of the above, the present invention provides a dibenzopyran spiro-based organic light-emitting compound, a preparation method thereof and an application thereof, wherein an organic electroluminescent device prepared from the organic light-emitting compound has high luminous efficiency.
The invention provides a dibenzopyran spiro organic luminescent compound, which has a structure shown in a formula I:
Figure BDA0002808158310000011
a and b are independently selected from 0 or 1 and cannot be 0 at the same time;
the Z1-Z6 are independently selected from C or N and at least contain one N;
x is selected from-O-, -S-, -Si (R)5R6)-、-C(R7R8) -or-NR9-；
The R is1～R9Each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted 3-to 30-membered cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted 3-to 30-membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryloxy; and one or more of a C3-C30 aliphatic ring or a 3-to 30-membered aromatic ring, which is bonded to an adjacent substituent(s) to form a monocyclic ring, the carbon atom(s) of which are replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur; the R is1～R4The number of (2) is 0-4;
ar is1And Ar2Independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted 3-30 membered) heteroarylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 aryloxy; substituted or unsubstituted C10-C30 spiro ring group, and one or more of C3-C30 aliphatic ring or C6-C30 aromatic ring which are connected with adjacent substituent groups to form a single ring, wherein carbon atoms are replaced by one or more of nitrogen, oxygen, sulfur and silicon heteroatoms; ar is1And Ar2The number of (A) is 0-4;
said L1And L2Independently selected from the group consisting of a connecting bond; or substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 3-30-membered heteroaryl, or substituted or unsubstituted C10-C60 condensed ring group, or substituted or unsubstituted C10-C60 spiro ring group.
Preferably, said R is1～R9Independently selected from methyl, ethyl, propyl, tert-butyl, alkoxy, alkylmercapto, aryloxy, phenyl, biphenyl, naphthyl, fluorenyl or spirocyclic group;
ar is1And Ar2Independently selected from naphthyl, anthryl, phenanthryl, phenyl, carbazole, methylphenyl, terphenyl, biphenyl, dibenzofuran, dibenzothiophene, fluorene, spiro, triazine, pyridine, imidazole, pyrimidine, phenanthroline, oxazole, thiazole and derivatives thereof.
Preferably, said L1Is selected from
Figure BDA0002808158310000021
Figure BDA0002808158310000022
Figure BDA0002808158310000031
A connecting bond,
Figure BDA0002808158310000032
Or
Figure BDA0002808158310000033
Ar is1Is selected from
Figure BDA0002808158310000034
Figure BDA0002808158310000035
Figure BDA0002808158310000036
Or
Figure BDA0002808158310000037
Said L2Is selected from
Figure BDA0002808158310000038
A connecting bond,
Figure BDA0002808158310000039
Figure BDA00028081583100000310
Or
Figure BDA00028081583100000311
Ar is2Is selected from
Figure BDA00028081583100000312
Figure BDA00028081583100000313
Or
Figure BDA00028081583100000314
Preferably, the dibenzopyran spiro-based organic light-emitting compound is specifically selected from any one of formulae 1 to 120.
The invention provides a preparation method of the dibenzopyran spiro organic luminescent compound in the technical scheme, which comprises the following steps:
and reacting the intermediate C with glacial acetic acid in the presence of concentrated sulfuric acid to obtain the dibenzopyran spiro-type organic light-emitting compound with the structure shown in the formula I.
Preferably, the intermediate C is prepared according to the following method:
and mixing the intermediate B, the reactant A and n-butyllithium, and reacting to obtain an intermediate C.
Preferably, the intermediate B is prepared according to the following method:
reacting a compound having formula 101 with a compound having formula 201 if a is 1 and B is 0 to give intermediate B;
Figure BDA0002808158310000041
formula 101;
Figure BDA0002808158310000042
formula 201;
reacting a compound having formula 102 with a compound having formula 202 when a is 0 and B is 1 to give intermediate B;
Figure BDA0002808158310000043
formula 102;
Figure BDA0002808158310000044
formula 202;
reacting a compound having formula 103 with a compound having formula 102, and further reacting with a compound having formula 301, if a is 1 and B is 1, to give intermediate B;
Figure BDA0002808158310000045
formula 103;
Figure BDA0002808158310000046
formula 301.
The present invention provides an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic compound layers interposed between the two electrodes;
at least one organic compound layer comprises the dibenzopyran spiro organic luminescent compound or the dibenzopyran spiro organic luminescent compound prepared by the preparation method.
The invention provides a dibenzopyran spiro organic luminescent compound which has a structure shown in a formula I. The oxygen atoms introduced into the parent nucleus of the compound increase the steric hindrance of the whole compound, and the asymmetric specific spatial structure is beneficial to reducing the intermolecular cohesion, reducing the crystallization possibility and improving the glass transition temperature; the pyridine, diazine or triazine side chain group containing N atoms is an electron-obtaining group, has good electron transport characteristics, improves the mobility of an electron transport material, and further ensures that the prepared organic electroluminescent device has higher luminous efficiency.
Detailed Description
The invention provides a dibenzopyran spiro organic luminescent compound, which has a structure shown in a formula I:
Figure BDA0002808158310000047
a and b are independently selected from 0 or 1 and cannot be 0 at the same time;
z is1～Z6Independently selected from C or N, and at least one N;
x is selected from O, S, Si (R)5R6)、C(R7R8) Or NR9；
The R is1～R9Each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted 3-to 30-membered cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted 3-to 30-membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryloxy; and one or more of a monocyclic ring, a C3-C30 aliphatic ring, or a 3-to 30-membered aromatic ring, which are bonded to adjacent substituents, the carbon atoms on the rings being replaced by at least one heteroatom selected from nitrogen, oxygen, and sulfur; the R is1～R4The number of (2) is 0-4;
ar is1And Ar2Independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted 3-30 membered) heteroarylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 aryloxy; substituted or unsubstituted C10-C30 spiro ring group, and one or more of C3-C30 aliphatic ring or C6-C30 aromatic ring which are connected with adjacent substituent groups to form a single ring, wherein carbon atoms are replaced by one or more of nitrogen, oxygen, sulfur and silicon heteroatoms; ar is1And Ar2The number of (2) is 0-4;
said L is1And L2Independently selected from the group consisting of a connecting bond; or through takingSubstituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30-membered heteroaryl, substituted or unsubstituted C10-C60 condensed ring group, or substituted or unsubstituted C10-C60 spiro ring group.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more of the above-shown substituents are bonded, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
In the present invention, said R1～R9Independently selected from methyl, ethyl, propyl, t-butyl, alkoxy, alkylmercapto, aryloxy, phenyl, biphenyl, naphthyl, fluorenyl or spirocyclic groups;
ar is1And Ar2Independently selected from naphthyl, anthryl, phenanthryl, phenyl, carbazole, methylphenyl, terphenyl, biphenyl, dibenzofuran, dibenzothiophene, fluorene, spiro, triazine, pyridine, imidazole, pyrimidine, phenanthroline, oxazole, thiazole and derivatives thereof.
In a specific embodiment, X is-O-, -S-, -C (CH)3)2-、-Si(CH3)2-, or
Figure BDA0002808158310000061
The R is1～R4Selected from H, CH3-O-、CH3-, or
Figure BDA0002808158310000062
Z is1Selected from N and/or H;
z is2Selected from N and/or H;
z is3Selected from N and/or H;
said L1Is selected from
Figure BDA0002808158310000063
Figure BDA0002808158310000064
A connecting bond,
Figure BDA0002808158310000065
Or
Figure BDA0002808158310000066
Ar is1Is selected from
Figure BDA0002808158310000067
Figure BDA0002808158310000068
Figure BDA0002808158310000069
Or
Figure BDA00028081583100000610
Ar is1The number of (a) is 0, 2, or 3;
z is4Selected from N and/or H;
z is5Selected from N and/or H;
z is6Selected from N and/or H;
said L2Is selected from
Figure BDA0002808158310000071
Connecting key、
Figure BDA0002808158310000072
Figure BDA0002808158310000073
Or
Figure BDA0002808158310000074
Ar is2Is selected from
Figure BDA0002808158310000075
Figure BDA0002808158310000076
Or
Figure BDA0002808158310000077
Ar is2The number of (2) is 0 or 2;
in the present invention, the dibenzopyran spiro-based organic light-emitting compound is specifically selected from any one of formulae 1 to 120.
The invention provides a preparation method of the dibenzopyran spiro organic luminescent compound in the technical scheme, which comprises the following steps:
reacting the intermediate C with glacial acetic acid in the presence of concentrated sulfuric acid to obtain a dibenzopyran spiro-type organic light-emitting compound with a structure shown in a formula I;
Figure BDA0002808158310000078
and (3) an intermediate C.
Preferably, glacial acetic acid (the adding volume of the glacial acetic acid is 5-8 times of the mole number of the intermediate C) is added into the intermediate C (1.0eq), the mixture is heated to 115-125 ℃, concentrated sulfuric acid is slowly dripped, the mixture is stirred for 4-6 min, the mixture is cooled to room temperature, the reaction is stopped, and the dibenzopyran spiro organic luminescent compound with the structure shown in the formula I is obtained after post-treatment. In the invention, preferably, the product obtained after the reaction is terminated is subjected to liquid separation, and an organic phase is collected, dried, filtered and removed with solvent to obtain a solid organic matter; and dissolving the solid organic matter, cooling to separate out solid, filtering, leaching and drying to obtain the dibenzopyran spiral organic luminescent compound with the structure shown in the formula I.
In the invention, the intermediate C is prepared according to the following method:
mixing the intermediate B, the reactant A and n-butyllithium, and reacting to obtain an intermediate C;
Figure BDA0002808158310000081
an intermediate B;
Figure BDA0002808158310000082
reactant A.
In the invention, the intermediate B (1.1eq) is mixed with anhydrous tetrahydrofuran, the reaction system is cooled to-75 to-80 ℃ under the nitrogen atmosphere, n-butyllithium n-BuLi (1.1eq) is added dropwise, and the mixture is stirred for 110 to 130 min; and dissolving the reactant A (1.0eq) in tetrahydrofuran, dropwise adding the reactant A into the system, heating to 20-30 ℃, stirring for 9.5-10.5 h at room temperature, stopping reaction, and performing aftertreatment to obtain an intermediate C.
In a particular embodiment of the invention, the reactant a is specifically selected from the group consisting of reactant a-1;
Figure BDA0002808158310000083
a reactant A-1;
in the present invention, the intermediate B is classified into intermediates B-I, intermediates B-II and intermediates B-III:
Figure BDA0002808158310000084
an intermediate B-I;
Figure BDA0002808158310000085
intermediate B-II;
Figure BDA0002808158310000086
intermediates B to III.
The intermediate B is prepared according to the following method:
reacting a compound having formula 101 with a compound having formula 201 if a is 1 and B is 0 to give intermediate B;
Figure BDA0002808158310000087
formula 101;
Figure BDA0002808158310000088
formula 201;
reacting a compound having formula 102 with a compound having formula 202 when a is 0 and B is 1 to give intermediate B;
Figure BDA0002808158310000089
formula 102;
Figure BDA00028081583100000810
formula 202;
reacting a compound having formula 103 with a compound having formula 102, and further reacting with a compound having formula 301, if a is 1 and B is 1, to give intermediate B;
Figure BDA0002808158310000091
formula 103;
Figure BDA0002808158310000092
and (3) formula 301.
In a particular embodiment of the invention, said intermediate B is preferably intermediate B-1, intermediate B-56, intermediate B-67, intermediate B-97:
Figure BDA0002808158310000093
intermediate B-1;
Figure BDA0002808158310000094
intermediate B-56;
Figure BDA0002808158310000095
intermediate B-67;
Figure BDA0002808158310000096
intermediate B-97;
the intermediate C is preferably intermediate C-1, intermediate C-56, intermediate C-67 or intermediate C-97:
Figure BDA0002808158310000097
intermediate C-1;
Figure BDA0002808158310000098
intermediate C-56;
Figure BDA0002808158310000099
intermediate C-67;
Figure BDA00028081583100000910
intermediate C-97.
The present invention provides an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic compound layers interposed between the two electrodes;
at least one organic compound layer comprises the dibenzopyran spiro organic luminescent compound or the dibenzopyran spiro organic luminescent compound prepared by the preparation method.
The first electrode and the second electrode preferably comprise at least one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer which are arranged in sequence.
The first electrode serves as an anode, which preferably comprises a material having a high work function, such as Ag, Pt or Au; preferably, the anode material is selected from conductive mixed metal oxides; particularly preferred is Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO). Preference is furthermore given to electrically conductive, doped organic materials, in particular electrically conductive, doped polymers. Since the lifetime of the device of the invention is shortened in the presence of water and/or air, the device is suitably (depending on the application) structured, provided with contacts and finally sealed. In a specific embodiment, the anode is selected from ITO transparent electrodes.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and has high hole mobility. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto. The material of the hole transport layer is selected from 4, 4' -tri [ 2-naphthyl phenylamino ] triphenylamine (2-TNATA); the thickness of the hole transport layer is specifically 80 nm.
The electron blocking layer may be disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, a material known in the art, for example, an arylamine-based organic material, may be used.
The material of the light emitting layer is a material capable of emitting visible light by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the received holes and electrons. In addition, the light emitting layer may include a host material and a dopant material; the mass ratio of the main material to the doping material is 90-99.5: 0.5-10; the doping material may include fluorescent doping and phosphorescent doping. The host material of the light-emitting layer is CBP, and the doping material is Ir (ppy)3(ii) a The doping ratio was 5 wt%.
The light emitting layer may emit red, green or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in a visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. The thickness of the light-emitting layer was 40 nm.
The metal of the phosphorescent dopant material comprises iridium, platinum, etcA phosphorescent material of a complex. For example, Ir (ppy)3Isogreen phosphorescent materials, FIrpic, FIr6Iso-blue phosphorescent material and Btp2Red phosphorescent materials such as ir (acac). As the fluorescent dopant material, a compound having an electron transporting action known in the art can be used.
As the hole-blocking layer material, a compound having a hole-blocking effect known in the art, for example, a phenanthroline derivative such as Bathocuproine (BCP), an oxazole derivative, a triazole derivative, a triazine derivative, or the like can be used, but the invention is not limited thereto.
When the organic layer includes an electron transport layer, the electron transport layer may include a dibenzopyran spiro-based compound represented by formula I.
The electron injection layer functions to promote electron injection. Has the ability of transporting electrons and prevents excitons generated in the light emitting layer from migrating to the hole injection layer. The electron injecting material used in the present invention includes fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing five-membered ring derivatives, and the like, but is not limited thereto. The layer thickness of the layer is preferably between 0.5 and 5 nm. In a specific embodiment, the electron injection layer is 1.0nm lithium hydroxyquinoline (Liq).
The second electrode as a cathode preferably contains a metal having a low work function, a metal alloy containing a plurality of metals such as alkaline earth metals, alkali metals, main group metals, or lanthanoid elements (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.), or a multilayer structure. The second electrode is preferably an Al electrode; the thickness of the Al electrode is 100 nm.
In a specific embodiment, the device structure is:
ITO/2-TNATA/TPD/CBP Ir (ppy) 3/TPBi/compound 1/Liq/Al.
The molecular structural formula of the related material is shown as follows:
Figure BDA0002808158310000111
the device of the invention can be used for an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
In order to further illustrate the present invention, the following examples are given to describe in detail a dibenzopyran spiro-based organic light emitting compound provided by the present invention, and a preparation method and applications thereof, but they should not be construed as limiting the scope of the present invention.
Example 1: synthesis of Compound 1
Figure BDA0002808158310000121
(1) Intermediate B-1(55mmoL) was added to a three-necked flask, 300mL of anhydrous tetrahydrofuran was added, nitrogen was substituted three times, and then the reaction system was cooled to-78 deg.C, and (2.5M) n-BuLi (55mmoL) was added dropwise, and stirred at-78 deg.C for 2 hours. Dissolving the reactant A-1(55mol) in tetrahydrofuran, dropwise adding the reactant A-1 into a reaction system, and heating to room temperature and stirring for 10 hours after dropwise adding. Distilled water was added to terminate the reaction, and the organic phase was collected by liquid separation, dried over anhydrous magnesium sulfate. The remaining water was removed, anhydrous magnesium sulfate was removed by filtration, and the organic phase was passed through a rotary evaporator to remove the solvent to obtain a solid organic substance. After the concentration is finished, 100mL of ethyl acetate and 500mL of ethanol are added into the mixture, the mixture is heated to 80 ℃ for reflux, stirred for 3h, and filtered to obtain a solid, a filter cake is rinsed by 100mL of petroleum ether and is placed into a 65 ℃ oven to be dried for 12h, and the intermediate C-1(24.5g, yield: 73%) is obtained.
(2) Adding the intermediate C-1(35mmol) into a three-neck flask, adding 210mL of glacial acetic acid, heating to 120 ℃, slowly dropwise adding 5mL of concentrated sulfuric acid by using a burette, and stirring for 5 min. Cooling to room temperature, adding 100mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with 200mL of dichloromethane for three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the residual water, filtering to remove the anhydrous magnesium sulfate, removing the solvent from the organic phase through a rotary evaporator to obtain a solid organic matter, adding the solid organic matter into 200mL of toluene, heating to 100 ℃ to completely dissolve the solid organic matter, gradually reducing the temperature until most of the solid is separated out, filtering, leaching the filter cake with 200mL of petroleum ether, and drying in a 65 ℃ oven for 12h to obtain the compound 1(19.5g, yield: 85%).
The detection analysis of the obtained compound 1 was carried out, and the results were as follows:
mass spectrometry test: a theoretical value of 655.23; the test value was 655.85.
Elemental analysis:
theoretical value: c, 84.25; h, 4.46; n, 6.41; o,4.88
Test paper: c, 84.23; h, 4.47; n, 6.43; and O, 4.86.
Example 2: synthesis of Compound 56
Figure BDA0002808158310000131
(1) Intermediate B-56(55mmoL) was added to a three-necked flask, 300mL of anhydrous tetrahydrofuran was added, nitrogen was substituted three times, and then the reaction system was cooled to-78 deg.C, and (2.5M) n-BuLi (55mmoL) was added dropwise, and stirred at-78 deg.C for 2 hours. Dissolving the reactant A-56(55mol) in tetrahydrofuran, dropwise adding the reactant A-56 into the reaction system, and heating to room temperature and stirring for 10 hours after dropwise adding. Distilled water was added to terminate the reaction, and the organic phase was collected by liquid separation, dried over anhydrous magnesium sulfate. The remaining water was removed, anhydrous magnesium sulfate was removed by filtration, and the organic phase was passed through a rotary evaporator to remove the solvent to obtain a solid organic substance. After the concentration is finished, 100mL of ethyl acetate and 500mL of ethanol are added into the mixture, the mixture is heated to 80 ℃ for reflux, stirred for 3h, and filtered to obtain a solid, a filter cake is rinsed by 100mL of petroleum ether and is placed into a 65 ℃ oven to be dried for 12h, and the intermediate C-56(33.3g, yield: 78%) is obtained.
(2) Adding the intermediate C-56(35mmol) into a three-neck flask, adding 210mL of glacial acetic acid, heating to 120 ℃, slowly dropwise adding 5mL of concentrated sulfuric acid by using a burette, and stirring for 5 min. Cooling to room temperature, adding 100mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with 200mL of dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the residual water, filtering to remove the anhydrous magnesium sulfate, removing the solvent from the organic phase by a rotary evaporator to obtain a solid organic matter, adding the solid organic matter into 200mL of toluene, heating to 100 ℃ to completely dissolve the solid organic matter, gradually reducing the temperature until most of the solid is separated out, filtering, leaching the filter cake with 200mL of petroleum ether, and drying in a 65 ℃ oven for 12h to obtain compound 56(25.5g, yield: 87%).
The compound 56 thus obtained was subjected to assay, and the results were as follows:
mass spectrometry test: a theoretical value of 836.32; the test value was 836.64.
Elemental analysis:
the theoretical values are: c, 84.67; h, 4.82; n, 6.69; o, 3.82;
the test values are: c, 84.68; h, 4.81; n, 6.68; and O, 3.82.
Example 3: synthesis of Compound 67
Figure BDA0002808158310000141
(1) Intermediate B-67(55mmoL) was added to a three-necked flask, 300mL of anhydrous tetrahydrofuran was added, nitrogen was substituted three times, and then the reaction system was cooled to-78 deg.C, and (2.5M) n-BuLi (55mmoL) was added dropwise, and stirred at-78 deg.C for 2 hours. Dissolving a reactant A-67(50mol) in tetrahydrofuran, dropwise adding the reactant A-67 to a reaction system, and heating to room temperature and stirring for 10 hours after dropwise adding. Distilled water was added to terminate the reaction, and the organic phase was collected by liquid separation and dried with anhydrous magnesium sulfate. The remaining water was removed, anhydrous magnesium sulfate was removed by filtration, and the organic phase was passed through a rotary evaporator to remove the solvent to obtain a solid organic substance. After the concentration is finished, 100mL of ethyl acetate and 500mL of ethanol are added into the mixture, the mixture is heated to 80 ℃ for reflux, stirred for 3h, and filtered to obtain a solid, a filter cake is rinsed by 100mL of petroleum ether and is placed into a 65 ℃ oven to be dried for 12h, and the intermediate C-67(26.2g, yield: 75%) is obtained.
(2) Adding the intermediate C-67(35mmol) into a three-neck flask, adding 210mL of glacial acetic acid, heating to 120 ℃, slowly dropwise adding 5mL of concentrated sulfuric acid by using a burette, and stirring for 5 min. Cooling to room temperature, adding 100mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with 200mL of dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the residual water, filtering to remove the anhydrous magnesium sulfate, removing the solvent from the organic phase by a rotary evaporator to obtain a solid organic matter, adding the solid organic matter into 200mL of toluene, heating to 100 ℃ to completely dissolve the solid organic matter, gradually reducing the temperature until most of the solid is separated out, filtering, leaching the filter cake with 200mL of petroleum ether, and drying in a 65 ℃ oven for 12h to obtain compound 67(20.0g, yield: 84%).
The compound 67 thus obtained was subjected to detection analysis, and the results were as follows:
mass spectrometry test: a theoretical value of 680.28; the test value was 680.74.
Elemental analysis:
the theoretical values are: c, 88.21; h, 5.33; n, 4.11; o, 2.35;
the test values are: c, 88.22; h, 5.34; n, 4.12; o, 2.33.
Example 4: synthesis of Compound 97
Figure BDA0002808158310000151
(1) Intermediate B-97(55mmoL) was added to a three-necked flask, 300mL of anhydrous tetrahydrofuran was added, nitrogen was substituted three times, and then the reaction system was cooled to-78 deg.C, and (2.5M) n-BuLi (55mmoL) was added dropwise, and stirred at-78 deg.C for 2 hours. Dissolving a reactant A-97(50mol) in tetrahydrofuran, dropwise adding the reactant A-97 into a reaction system, and heating to room temperature and stirring for 10 hours after dropwise adding. Distilled water was added to terminate the reaction, and the organic phase was collected by liquid separation, dried over anhydrous magnesium sulfate. The remaining water was removed, anhydrous magnesium sulfate was removed by filtration, and the organic phase was passed through a rotary evaporator to remove the solvent to obtain a solid organic substance. After the concentration is finished, 100mL of ethyl acetate and 500mL of ethanol are added into the mixture, the mixture is heated to 80 ℃ for reflux, stirred for 3h, and filtered to obtain a solid, a filter cake is rinsed by 100mL of petroleum ether and is placed into a 65 ℃ oven to be dried for 12h, and the intermediate C-97(28.3g, yield: 73%) is obtained.
(2) Adding the intermediate C-97(35mmol) into a three-neck flask, adding 210mL of glacial acetic acid, heating to 120 ℃, slowly dropwise adding 5mL of concentrated sulfuric acid by using a burette, and stirring for 5 min. Cooling to room temperature, adding 100mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with 200mL of dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the residual water, filtering to remove the anhydrous magnesium sulfate, removing the solvent from the organic phase by a rotary evaporator to obtain a solid organic matter, adding the solid organic matter into 200mL of toluene, heating to 100 ℃ to completely dissolve the solid organic matter, gradually reducing the temperature until most of the solid is separated out, filtering, leaching the filter cake with 200mL of petroleum ether, and drying in a 65 ℃ oven for 12h to obtain compound 97(22.8g, yield: 86%).
The compound 97 obtained was subjected to detection analysis, and the results were as follows:
mass spectrometry test: a theoretical value of 757.31; the test value was 757.72.
Elemental analysis:
the theoretical values are: c, 87.16; h, 5.19; n, 5.54; o, 2.11;
the test values are: c, 87.16; h, 5.18; n, 5.54; o, 2.12.
Example 5 to example 24
Synthesis, mass spectra and molecular formulas for compound 2, compound 5, compound 9, compound 17, compound 24, compound 30, compound 36, compound 40, compound 48, compound 55, compound 56, compound 60, compound 64, compound 67, compound 70, compound 78, compound 84, compound 89, compound 92, compound 97, compound 100, compound 105, compound 112 are shown in table 1 below with reference to the synthetic methods of examples 1 to 4:
in addition, other compounds of the present application can be obtained by the synthetic methods according to the above-mentioned examples, and therefore, they are not illustrated herein.
TABLE 1 Mass Spectrometry or molecular formula of other Compounds
Figure BDA0002808158310000161
Figure BDA0002808158310000171
Device example 1 organic electroluminescent device preparation:
the ITO glass substrate with the Fisher company coating thickness of 150nm is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30min, the ITO glass substrate is repeatedly cleaned for 2 times and ultrasonic cleaning is carried out for 10min, after the distilled water cleaning is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning and then dried, the ITO glass substrate is transferred into a plasma cleaning machine, the ITO glass substrate is cleaned for 5min, and the ITO glass substrate is sent into an evaporation machine.
4, 4' -tri [ 2-naphthyl phenylamino ] with the thickness of 80nm is evaporated on the prepared ITO transparent electrode by using a vacuum evaporation device]Triphenylamine (2-TNATA) as a hole injection layer. TPD having a thickness of 30nm was vacuum-deposited on the formed hole injection layer to form a hole transport layer. After the evaporation of the hole transport material is finished, the light-emitting layer of the OLED light-emitting device is manufactured, and the structure of the light-emitting layer comprises CBP (cubic boron nitride) used as a main material for the OLED light-emitting layer and Ir (ppy)3As the doping material, the doping ratio of the doping material was 5% by weight, and the thickness of the light-emitting layer was 40 nm.
Vacuum evaporating 10nmTPBi as hole blocking layer and compound 1 as electron transport layer on the luminescent layer; lithium hydroxyquinoline (Liq) was vacuum-deposited on the electron transport layer to a thickness of 1.0nm as an electron injection layer. On the electron injection layer, an Al electrode layer having a film thickness of 100nm was formed, and this layer was used as a cathode layer.
The device structure is as follows: ITO/2-TNATA/TPD/CBP Ir (ppy)3TPBi/Compound 1/Liq/Al.
After the OLED light emitting device was completed as described above, the anode and cathode were connected by a known driving circuit, and the current efficiency of the device and the lifetime of the device were measured. After the electroluminescent device is manufactured according to the steps, the driving voltage, the luminous efficiency and the service life of the device are measured.
Device example 2 to device example 24
By referring to the above-mentioned methods, compound 1 used in device example 1 was replaced with compound 2, compound 5, compound 9, compound 17, compound 24, compound 30, compound 36, compound 40, compound 48, compound 55, compound 56, compound 60, compound 64, compound 67, compound 70, compound 78, compound 84, compound 89, compound 92, compound 97, compound 100, compound 105, and compound 112, respectively, as an electron transporting layer, to prepare corresponding organic electroluminescent devices.
[ device comparative example 1]
An organic electroluminescent device was prepared in the same manner as in device example 1, and the structure of the compound of the electron transport layer was as follows:
Figure BDA0002808158310000181
comparative compound 1;
Figure BDA0002808158310000182
comparative compound 2;
the organic electroluminescent device was applied with forward DC bias voltage, and measured for organic electroluminescent characteristics with a PR-650 photometric measuring device of Photo Research corporation, and the luminance was 8000cd/m2The life span of T95 was measured using a life span measuring device of McScience, Inc., and the results are shown in Table 2: .
Table 2: test results of light emitting characteristics of device examples 1 to 24 and device comparative examples 1 to 2 of the present invention
Figure BDA0002808158310000183
Figure BDA0002808158310000191
Compared with the comparative example 1, the driving voltage is reduced by 1.5-2.2V, the luminous efficiency is improved by 9.2-25.3%, and the service life of the device is improved by about 2 times. From the results of the above table 2, it can be confirmed that the organic electroluminescent device prepared using the compound provided by the present invention as an electron transport material exhibits high luminous efficiency and long life and reduced driving voltage.
Compared with comparative example 2 with a similar structure, the main difference between the two is that heteroatom oxygen is introduced, the symmetry of a mother nucleus is damaged, on one hand, the steric hindrance of the whole compound is increased, the glass transition temperature is increased by about 10 ℃, the driving voltage is reduced by 0.7-1.4V, the efficiency is increased by 6.8-14.2%, and particularly the service life is prolonged by about 200 h.
As can be seen from the above examples, the present invention provides a dibenzopyran spiro-based organic light-emitting compound having a structure of formula I. The oxygen atoms introduced into the parent nucleus of the compound increase the steric hindrance of the whole compound, and the asymmetric specific spatial structure is beneficial to reducing the intermolecular cohesion, reducing the crystallization possibility and improving the glass transition temperature; the pyridine, diazine or triazine side chain group containing N atoms is an electron-obtaining group, has good electron transport characteristics, improves the mobility of an electron transport material, and further ensures that the prepared organic electroluminescent device has higher luminous efficiency. The experimental results show that: the luminous efficiency of the device is 42.1-50.5 cd/A; the service life of T95 is 756-847 h; the glass transition temperature is 123-131 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A dibenzopyran spiro-based organic light-emitting compound having the structure of formula I:
Figure FDA0003553363400000011
a and b are independently selected from 0 or 1 and cannot be 0 at the same time;
z is1～Z6Independently selected from C or N, and at least one N;
x is selected from O, S, Si (R)5R6)、C(R7R8) Or NR9；
The R is1～R9Independently selected from methyl, ethyl, propylTert-butyl, C1-C30 alkoxy, C6-C60 aryloxy, phenyl, biphenyl, naphthyl and fluorenyl;
ar is1Selected from the group consisting of naphthyl, anthryl, phenanthryl, phenyl, carbazole, methylphenyl, terphenyl, biphenyl, dibenzofuran, dibenzothiophene, fluorene, triazine, pyridine, imidazole, pyrimidine, phenanthroline, oxazole, thiazole, phenanthroline, and mixtures thereof,
Figure FDA0003553363400000012
Figure FDA0003553363400000013
Ar is2Selected from the group consisting of naphthyl, anthryl, phenanthryl, phenyl, carbazole, methylphenyl, terphenyl, biphenyl, dibenzofuran, dibenzothiophene, fluorene, triazine, pyridine, imidazole, pyrimidine, phenanthroline, oxazole, thiazole, phenanthroline, and mixtures thereof,
Figure FDA0003553363400000014
Said L1And L2Independently selected from the group consisting of a connecting bond; or a C6-C30 aryl group, or a 3-to 30-membered heteroaryl group.
2. The dibenzopyran spiro-based organic light-emitting compound according to claim 1, wherein said L is1Is selected from
Figure FDA0003553363400000021
Figure FDA0003553363400000022
A connecting bond,
Figure FDA0003553363400000023
Ar is1Is selected from
Figure FDA0003553363400000024
Figure FDA0003553363400000025
Said L2Is selected from
Figure FDA0003553363400000026
A connecting bond,
Figure FDA0003553363400000027
Figure FDA0003553363400000028
Ar is2Is selected from
Figure FDA0003553363400000029
3. The dibenzopyran spiro-based organic light-emitting compound according to claim 1, wherein the dibenzopyran spiro-based organic light-emitting compound is specifically selected from any one of formula 1 to formula 120:
Figure FDA0003553363400000031
Figure FDA0003553363400000041
Figure FDA0003553363400000051
Figure FDA0003553363400000061
Figure FDA0003553363400000071
Figure FDA0003553363400000081
4. a method for producing the dibenzopyran spiro-based organic light-emitting compound according to any one of claims 1 to 3, comprising the steps of:
reacting the intermediate C with glacial acetic acid in the presence of concentrated sulfuric acid to obtain a dibenzopyran spiro-type organic light-emitting compound with a structure shown in a formula I;
Figure FDA0003553363400000091
5. the process according to claim 4, wherein intermediate C is prepared by the following process:
mixing the intermediate B, the reactant A and n-butyllithium, and reacting to obtain an intermediate C;
Figure FDA0003553363400000092
Figure FDA0003553363400000093
6. the process according to claim 5, wherein the intermediate B is prepared by the following method:
reacting a compound having formula 101 with a compound having formula 201 if a is 1 and B is 0 to give intermediate B;
Figure FDA0003553363400000094
reacting a compound having formula 102 with a compound having formula 202 when a is 0 and B is 1 to give intermediate B;
Figure FDA0003553363400000101
(ii) when a is 1 and B is 1, reacting a compound having formula 103 with a compound having formula 201, and further reacting with a compound having formula 301 to give intermediate B;
Figure FDA0003553363400000102
7. an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic compound layers interposed between the two electrodes;
at least one organic compound layer contains the dibenzopyran spiro-based organic light-emitting compound according to any one of claims 1 to 3 or the dibenzopyran spiro-based organic light-emitting compound prepared by the preparation method according to any one of claims 4 to 6.
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