CN108083969B - Spiroindene compounds, their preparation and use - Google Patents

Spiroindene compounds, their preparation and use Download PDF

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CN108083969B
CN108083969B CN201711398698.7A CN201711398698A CN108083969B CN 108083969 B CN108083969 B CN 108083969B CN 201711398698 A CN201711398698 A CN 201711398698A CN 108083969 B CN108083969 B CN 108083969B
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曾泽兵
陈娴
周志彪
向建南
罗胜联
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Changsha Dalton Electronic Materials Co ltd
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Abstract

The invention discloses an organic luminescent material with reversible photochromic performance. The organic functional material is a series of spiroindene compounds, and the compounds can undergo photochromism in a solution and a solid state after being irradiated by ultraviolet light, namely, the color can be changed into orange yellow or pink from the primary color, and the compounds can recover the primary color after being faded. In addition, the compound disclosed by the invention has excellent fluorescence performance in a visible light wavelength range, the emission wavelength of the compound can be regulated and controlled through conjugate modification and substituent modification, the fluorescence quantum yield is high, the light-emitting brightness is high, and the compound can be applied to the manufacturing of organic light-emitting diode elements.

Description

Spiroindene compounds, their preparation and use
Technical Field
The invention relates to the field of functional materials, in particular to an organic luminescent material with photochromic property.
Background
The spiro compound has a rigid structure and a stable structure, and has important application in the aspects of medicines, pesticides, luminescent materials, polymer adhesives and the like. In the biological and medical fields, many spiro compounds are organic intermediates for medicines and pesticides, and have been confirmed to have physiological and biological activities. In the field of materials, the spiro compound is the main type of organic molecular luminescent materials, and can be widely applied to the fields of organic electroluminescence, organic field effect transistors, organic integrated circuits, organic thin film transistors, nonlinear optics, solar cells, biosensing and the like.
The photochromic phenomenon is a phenomenon that a compound can generate a photochemical reaction under illumination of a certain wavelength to generate another product, the absorption spectrum of the compound can be obviously changed due to the change of the structure of the compound to cause color change, and the compound can be restored to the original state under the illumination of another wavelength (or under the action of heat). The photochromic material has potential application prospect in many fields, such as high-tech fields of information storage, optical filters, switches, displays, liquid crystal materials, nonlinear optical materials and the like, and industrial and civil fields of glasses, clothes, printing, anti-counterfeiting and the like.
Some organic photochromic materials are disclosed in the prior art, for example, chinese patent publication No. 1699315 discloses a dibenzofuran spiro monomer photochromic material. Chinese patent publication No. CN 102015970a discloses a single-phase photochromic composition which is liquid at 20 ℃ and comprises: (a) at least one photochromic dye selected from: spirooxazines, spiroindoline [2, 3' ] benzoxazines, benzopyrans, homoazaadamantane spirooxazines, spirofluorene- (2H) -benzopyrans, naphtho [2, 1-b ] pyrans and naphtho [1, 2-b ] pyrans, and (b) ionic solvents. Chinese patent publication No. 1247604 discloses a photochromic heterocyclic fused indenonaphthopyran compound. At present, most photochromic materials have poor fatigue resistance, slow response speed, poor thermal stability, easy oxidative degradation, loss of color-changing property and the like.
On the other hand, Organic Light Emitting Diodes (OLEDs) are gradually coming into the field of vision of people as a new display technology. Compared with the traditional display technology, the display device has remarkable advantages in the aspects of voltage characteristics, luminous efficiency, luminous brightness, response speed, device weight, viewing angle and the like, and has wide application prospect. Organic electroluminescent display materials have excellent properties not found in inorganic luminescent materials and many liquid crystal display materials: for example, the color selection range of the organic light-emitting material is very wide, and full color display from blue light to red light can be realized; the luminous brightness and luminous efficiency are high; the organic light-emitting device has the advantages of high response speed, wide visual angle, low driving voltage, simple preparation process, no vibration influence, capability of realizing flexible display and the like. Organic electroluminescent materials will be the most competitive next generation display materials.
In the research of the OLED, a blue light emitting material is only necessary, because the blue light emitting material itself can be used as a light emitting layer to prepare a blue light emitting material OLED which is one of three primary colors, and in addition, other light emitting materials can be doped in the blue light emitting material, so that a green and red light emitting device can be obtained, and full color display can be realized. Therefore, the development of efficient and stable blue light materials is of the most important significance. However, the blue light emitting material has the disadvantages of low light emitting efficiency, low color purity, poor thermal stability, short colorization life, and the like, and these critical problems are not effectively solved, thereby affecting the technical research and industrialization development steps of full-color OLEDs and white light devices.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a spiroindene compound, and aims to provide a monomolecular photochromic compound and an organic luminescent material with excellent performance.
The second purpose of the invention is to provide a preparation method of the spiroindene compound.
The third purpose of the invention is to provide an application method of the spiroindene compound.
A spiroindene compound having the general structural formula of formula 1:
Figure BDA0001517737460000021
in the formula 1, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Independently of H, -Cl, -Br, -I, C1-C24Alkyl radical, C3-C24Cycloalkyl radical, C6-C24Aryl or substituted aryl, halogenated C1-C24Alkyl, halogenated C3-C24Cycloalkyl, halogenated C1-C24Alkoxy, -CN or C1-C24An alkoxy group;
or, R1、R2、R3And the substituents adjacent to R4 are fused with the B benzene ring to form a fused ring structure; r5、R6、R7And R8Adjacent substituent groups are condensed with the A benzene ring to form a condensed ring structure;
ar is1、Ar2Independently is C4～C20Aryl or heterocyclic aryl of (a).
The spiroindene compound is a spirocyclic aromatic compound, has a large conjugated system and a special spirocyclic conjugated effect, has high glass transition temperature due to a ring rigid structure, has good thermal stability, and can be effectively applied to photochromic materials. In the compound, an included angle between two rings in a structure of the compound containing the spiroindene is about 90 degrees, the stacking is reduced, the thermal stability is good, a good amorphous film can be formed, in addition, the material containing the spirofluorene frame structure also has high luminous quantum efficiency, and the application of the material containing the spirofluorene frame structure to an OELD can improve the morphological stability, the thermal stability, the stability of carrier migration, good intersolubility and the like of a display material, so that the spiroindene compound is a blue light material with good application prospect. The synthesis process is simple, the large-scale production is easy, and the industrial prospect is good.
Ar1、Ar2Independently, the aromatic group may be a heterocyclic aromatic group, for example, a heteroatom-hybridized aromatic group such as O, N, S. The aryl or heterocyclic aryl group is, for example, a five-membered or six-membered aromatic group.
Preferably, Ar is1、Ar2Is phenyl or thiophene; or halogen, C1～C6Alkyl radical, C1～C6Phenyl substituted with at least one of alkoxy, phenyl, substituted phenyl, or thiophene.
Further preferably, Ar1、Ar2Is phenyl.
Preferably, R9、R10、R11、R12Is H.
A preferred structure of the invention, R1、R2、R3、R4、R5、R6、R7、R8Independently H, Br, -CN, C1-C24Alkoxy radical, C6-C24Aryl or substituted aryl.
Preferably, R1、R3、R4、R5、R6、R8Is H; r2、R7Independently H, Br, -CN, C1-C24Alkoxy radical, C6-C24Aryl or substituted aryl.
Preferably, R1、R2、R3And R4Adjacent substituents being condensed with the B phenyl ring to form C containing the B phenyl ring10～C30A fused ring structure of (1). The aromatic C in the fused ring structure may be hybridized with a heteroatom, such as N, O, S.
Further preferably, R1、R2Together with the benzene ring of B to form a naphthalene ring structure; or, R2、R3And the two are condensed together with the B benzene ring to form a condensed ring structure consisting of 2-4 benzene rings including the B benzene ring.
Preferably, R5、R6、R7And R8The adjacent substituents being condensed with the A phenyl ring to form C containing the A phenyl ring10～C30A fused ring structure of (1).
Further preferably, R7、R8Together with A benzene ring to form a naphthalene ring structure; or, R6、R7And the two are condensed together with a benzene ring B to form a condensed ring structure consisting of 2-4 benzene rings including the benzene ring A.
Preferably, at least one aromatic H in the fused ring structure is represented by-Cl, -Br, -I, -CN, C1-C24Alkyl radical, C3-C24Cycloalkyl radical, C1-C24Alkoxy radical, C6-C24Aryl radicalsOr substituted aryl, halo C1-C24Alkyl, halo C3-C24Cycloalkyl, halo C1-C24Substituents in alkoxy groups.
Preferably, the spiroindene compound has the following preferred structure:
Figure BDA0001517737460000041
Figure BDA0001517737460000051
wherein R is13、R14Independently of H, Cl, Br, -CN, phenyl or C1～C6An alkoxy group. More preferably, the spiroindene compound has the following structural formula:
Figure BDA0001517737460000052
Figure BDA0001517737460000061
Figure BDA0001517737460000071
the invention also discloses a preparation method of the spiroindene compound, which is characterized by comprising the following steps:
step (1): reacting a compound shown in a formula 2, alkyl lithium and a compound shown in a formula 3 to obtain a compound shown in a formula 4;
step (2): reacting the compound shown in the formula 4 with a reducing agent to obtain a compound shown in a formula 1;
Figure BDA0001517737460000072
the substituents in formulas 2 to 4 are selected in the same range as the substituents in formula 1.
Preferably, in the step (1), the compound of formula 2 and alkyl lithium are reacted in a molar ratio of 1: 1-3 in advance; then adding a compound of formula 3; continuing the reaction, quenching the reaction after the reaction is finished, and removing the solvent to obtain the compound shown in the formula 4.
In the step (1), the reaction is carried out in a protective atmosphere; the preferred reaction solvent is THF (tetrahydrofuran).
Preferably, the alkyllithium is n-butyllithium.
The compound of formula 3 corresponds to an excess of the compound of formula 2, preferably the ratio of the molar amount of the compound of formula 3 to the molar amount of the compound of formula 2 is 1.2: 1.
After the reaction of step (1), the reaction is quenched with a small amount of water, followed by removal of the solvent and purification by chromatography, and step (2) is performed.
Preferably, in the step (2), the molar ratio of the compound of formula 4 to the reducing agent is 1: 4-8.
Preferably, in step (2), the reaction temperature is room temperature.
In the step (2), the reaction solvent is preferably a water-insoluble solvent such as methylene chloride.
Preferably, in the step (2), the reducing agent is stannous chloride.
A more preferable preparation method is that triphenylbromoethylene and n-butyllithium are reacted for one hour at a molar ratio of 1: 1.2, and then fluorenone derivative in an amount of 1.2 times the molar amount of triphenylbromoethylene is added to react for 8 hours to obtain a hydroxyl precursor compound, and the reaction is carried out in an anhydrous solvent. The obtained hydroxyl precursor compound and a reducing agent are stirred in an organic solvent at the molar ratio of 1: 5 for 3-5 hours at normal temperature to synthesize the product with the structural formula 1.
The invention also provides application of the spiroindene compound as a photochromic material or a luminescent material. In the invention, different properties can be shown according to different substituents, and the reaction is researched, when A, B is a benzene ring, R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Independently of H, -Cl, -Br, -I, C1-C24Alkyl radical, C3-C24Cycloalkyl radical, C6-C24Aryl or substituted aryl, halogenated C1-C24Alkyl, halogenated C3-C24A cycloalkyl group; or, R1、R2、R3And R4Adjacent substituent groups are condensed with the benzene ring B to form a condensed ring structure; r5、R6Rx and R8Adjacent substituent groups are condensed with the A benzene ring to form a condensed ring structure; the compound of formula 1 (also called as spiroindene photochromic compound) of the substituent group shows good photochromic performance, and is particularly suitable for being used as a photochromic material to prepare a luminescent material.
The monomolecular organic functional material spiro compound (spiroindene photochromic compound) provided by the invention has photochromic property. Under illumination, the compound can generate photochromism in both solution and solid state, namely, the color can be changed into orange yellow or pink from the primary color, and the compound can restore the primary color after the illumination is faded. . In addition, the compounds can regulate and control the range of emission wavelength by changing conjugation and introducing different substituents, so that the compounds can be used as blue light, green light and red light materials, have high color purity, can meet the requirement of full-color display, and have great potential in the field of electroluminescence.
The application of the spiroindene photochromic compound is to use the spiroindene compound as a photochromic active material in the high-tech fields of intelligent materials, information storage, displays, nonlinear optical materials and the like; in addition, the compound has high fluorescence quantum yield and high luminous brightness, and can be used as an organic light-emitting material to be applied to an organic light-emitting diode.
When A, B is a benzene ring, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12At least one radical being halogeno C1-C24Alkoxy, -CN or C1-C24An alkoxy group; the substituted group of the compound of formula 1 (The invention is also called as spiroindene organic luminescent compound) shows good luminescent property and is particularly suitable for serving as OLED material.
Preferably, the spiroindene organic luminescent compound R1、R3、R4、R5、R6、R8Is H; r2、R7Independently of one another is-CN or C1-C24An alkoxy group.
Advantageous effects
The spiro compound provided by the invention is mainly characterized in that the compound has photochromic performance and can be used in high-tech fields such as intelligent materials, information storage, nonlinear optical materials and the like. In addition, the compound has excellent fluorescence performance in the visible light wavelength range, and the emission wavelength can be regulated and controlled by changing conjugation and introducing substituent groups. The compound has high fluorescence quantum yield, high solid fluorescence quantum yield up to over 90 percent and high luminous brightness, and can be used as an organic luminescent material to be applied to the aspects of organic light-emitting diodes, displays and the like. The compound has simple synthesis process, easy large-scale production and good industrial application prospect.
Drawings
FIG. 1 shows the NMR spectrum of Compound 1-A
FIG. 2 is a nuclear magnetic resonance carbon spectrum of Compound 1-A
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of Compound 1-B
FIG. 4 is a nuclear magnetic resonance carbon spectrum of Compound 1-B
FIG. 5 is a UV-VIS spectrum of 1-A, 1-B, 1-C before UV illumination;
FIG. 6 is a chart of UV-VIS spectra after UV illumination of 1-A, 1-B, and 1-C;
FIG. 7 shows fluorescence emission spectra of 1-A, 1-B, 1-C, 1-D, and 1-E;
FIG. 8 is a diagram of a photochromic experiment of compound 1-A.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
Synthesis of Compound 1-A
(1) Synthesis of 9- (1, 2, 2-triphenylvinyl) -9H-fluoren-9-ol
Under the protection of inert gas, 2g (0.006mol) of triphenylbromoethylene is added into a 100mL Schucker flask, 120mL of anhydrous tetrahydrofuran solvent is injected, the mixture is stirred for 15min after being dissolved, 2.8mL (0.007mol, 2.5mol/L) of n-butyllithium hexane solution is injected, 1.26g (0.007mol) of 9H-fluoren-9-one is added after stirring reaction for 1 hour, and the reaction is continued for 8 hours. After the reaction, 0.1mL of water was injected to quench the reaction, and the solvent was dried by spinning and purified by chromatography to proceed the next reaction.
(2) Preparation of Compounds of formula 1-A
Under the protection of inert gas, 0.0011mol of the crude product is added into a 100mL double-mouth bottle, and 30mL of dichloromethane solvent and 0.0056mol of stannous chloride are added. Reacting for three hours at normal temperature, filtering, removing the solvent, and recrystallizing to obtain the compound of the formula 1-A.
Example 2
Synthesis of Compound 1-B
The specific procedure is the same as example 1, except that 9H-fluorene-9-one as the raw material in (1) is changed to 11H-benzo [ b ] fluorene-11-one
Example 3
Synthesis of Compound 1-C
The specific procedure is the same as example 1, except that 9H-fluoren-9-one as the raw material in (1) is changed to 11H-benzo [ a ] fluoren-11-one.
Example 4
Synthesis of Compound 1-D
The specific procedure is the same as in example 1, except that 9H-fluoren-9-one as the raw material in (1) is changed to 2, 7-dimethoxy-9H-fluoren-9-one.
Example 5
Synthesis of Compound 1-E
The specific procedure is the same as example 1, except that 9H-fluoren-9-one as the raw material in (1) is changed to 2, 7-dicyano-9H-fluoren-9-one.
Example 6
Synthesis of Compound 1-F
The specific procedure is the same as example 1, only the raw material 9H-fluorene-9-one in (1) is changed to 2-bromo-9H-fluorene-9-one
Example 7
The specific procedure for synthesizing the compounds 1 to G was the same as in example 1 except that the raw material fluorenone in (1) was changed to 2, 7-dibromo-9H-fluoren-9-one.
Example 8
Synthesis of Compound 1-H
The specific procedure is the same as example 1, only the raw material fluorenone in (1) is changed to 2, 7-diphenyl-9H-fluoren-9-one.
Example 9
Photochromic experiment of Compound 1-A
Weighing 10mg of the compound 1-A, dissolving in anhydrous toluene to prepare a solution with the concentration of 0.01mol/L, wherein the solution is colorless under visible light (left in the figure); after 30s of irradiation with UV light at 254nm, the solution turned orange-yellow (right of the figure). When the solution is placed under visible light or in dark environment again, the orange solution fades to be colorless.
To further prove the photochromic properties of the compounds, the inventors respectively test the ultraviolet-visible absorption spectra of the compounds before and after ultraviolet irradiation (for photochromic experiments of other compounds, refer to example 9), the spectra are shown in fig. 5 and 6, and the spectra 5 and 6 show that: the compound is absorbed in an ultraviolet light wave band before ultraviolet light irradiation, and after the ultraviolet light irradiation, the absorption wavelength is red shifted and is mainly absorbed in a visible light region. Meanwhile, the color of the compound is changed from colorless to orange yellow. The substances are proved to have photochromic properties.
Taking compound 1-A as an example, the occurrence of the photochromic reaction can be represented as:
Figure BDA0001517737460000111
in addition, the present inventors also tested the fluorescence emission spectra of the compounds, as shown in fig. 7: from the fluorescence emission spectrum of the compound, it can be known that: the emission wavelength of the compound is in the visible light region.
In order to further verify the application of the compound in the organic luminescent material, the inventor measures and calculates the solid-state fluorescence quantum yield of the compound, the result is up to more than 90%, the luminous efficiency is high, and the compound has good organic luminescent characteristics and has huge application prospect in the organic solid luminescent material.
The compound is characterized by a series of compounds: the compound has high luminous efficiency, the emission wavelength is positioned in a visible light region, the specific waveband can be regulated and controlled by connecting different substituents, the compound can be used as an organic solid luminescent material, the color purity is high, the thermal stability is good, and the compound has huge potential in OLED application.

Claims (19)

1. A method for preparing a spiroindene compound, which is characterized by comprising the following steps:
step (1): reacting a compound shown in a formula 2, alkyl lithium and a compound shown in a formula 3 to obtain a compound shown in a formula 4;
step (2): reacting the compound shown in the formula 4 with a reducing agent to obtain a spiroindene compound shown in the structural general formula 1;
Figure FDA0002599784610000011
R1、R2、R3、R4、R5、R6、R7、R8independently of H, -Cl, -Br, -I, C1-C24Alkyl radical, C3-C24Cycloalkyl radical, C6-C24Aryl, halogenated C1-C24Alkyl, halogenated C3-C24Cycloalkyl, halogenated C1-C24Alkoxy, -CN or C1-C24An alkoxy group;
R9、R10、R11、R12is alone H, C1-C24Alkyl radical, C3-C24Cycloalkyl radical, C6-C24Aryl, -CN or C1-C24An alkoxy group;
or, R1、R2、R3And R4Adjacent substituents are toB, benzene rings are condensed to form a condensed ring structure; r5、R6、R7And R8Adjacent substituent groups are condensed with the A benzene ring to form a condensed ring structure;
Ar1、Ar2is phenyl or thiophene; or C1～C6Alkyl radical, C1～C6Phenyl substituted with at least one of alkoxy, phenyl or thiophene;
the reducing agent is stannous chloride.
2. The process for preparing a spiroindene compound of claim 1, wherein Ar is Ar1、Ar2Is phenyl.
3. A process for the preparation of the spiroindene compound of claim 1 wherein R9、R10、R11、R12Is H.
4. A process for the preparation of a spiroindene compound according to any of claims 1 to 3 wherein R1、R2、R3And R4Adjacent substituents being condensed with the B phenyl ring to form C containing the B phenyl ring10～C30A fused ring structure of (a);
and/or, R5、R6、R7And R8The adjacent substituents being condensed with the A phenyl ring to form C containing the A phenyl ring10～C30A fused ring structure of (1).
5. A process for the preparation of the spiroindene compound of claim 4 wherein R1、R2Together with the benzene ring of B to form a naphthalene ring structure; or, R2、R3And the two are condensed together with the B benzene ring to form a condensed ring structure consisting of 2-4 benzene rings including the B benzene ring.
6. A process for the preparation of the spiroindene compound of claim 4 wherein R7、R8Together with the benzene ring of A, are fused,forming a naphthalene ring structure; or, R6、R7The A benzene rings are condensed together to form a condensed ring structure consisting of 2-4 benzene rings including the A benzene rings.
7. A process for the preparation of spiroindene compounds of claim 1 wherein at least one aromatic H in the fused ring structure is selected from the group consisting of-Cl, -Br, -I, -CN, C1-C24Alkyl radical, C3-C24Cycloalkyl radical, C1-C24Alkoxy radical, C6-C24Aryl, halo C1-C24Alkyl, halo C3-C24Cycloalkyl, halo C1-C24Substituents in alkoxy groups.
8. A process for the preparation of a spiroindene compound of claim 1 wherein the spiroindene compound of formula 1 has any of the following structures:
Figure FDA0002599784610000031
Figure FDA0002599784610000041
wherein R is13、R14Independently of H, Cl, Br, -CN, phenyl or C1～C6An alkoxy group.
9. The method for preparing a spiroindene compound according to claim 1, wherein the spiroindene compound of formula 1 is a compound having the following structural formula:
Figure FDA0002599784610000042
Figure FDA0002599784610000051
Figure FDA0002599784610000061
10. a process for preparing a spiroindene compound according to claim 1, characterized in that in step (1), the compound of formula 2 and the alkyllithium are reacted in a molar ratio of 1:1 to 3 in advance; then adding a compound of formula 3; continuing the reaction, quenching the reaction after the reaction is finished, and removing the solvent to obtain the compound shown in the formula 4.
11. The process for preparing a spiroindene compound according to claim 1, wherein in step (1), the reaction is carried out under a protective atmosphere.
12. The process for preparing a spiroindene compound according to claim 1, wherein in step (1), the reaction solvent is tetrahydrofuran.
13. A process for the preparation of a spiroindene compound according to claim 1 wherein the alkyl lithium is n-butyl lithium.
14. A process for the preparation of a spiroindene compound according to claim 1 wherein the compound of formula 3 is in excess relative to the compound of formula 2.
15. A process for the preparation of a spiroindene compound according to claim 1 wherein the ratio of the molar amount of the compound of formula 3 to the molar amount of the compound of formula 2 is 1.2: 1.
16. The method for preparing the spiroindene compound of claim 1, wherein in the step (2), the molar ratio of the compound of formula 4 to the reducing agent is 1: 4-8.
17. The process for producing a spiroindene compound according to claim 1, wherein in the step (2), the reaction temperature is room temperature.
18. The process for producing a spiroindene compound according to claim 1, wherein in the step (2), the reaction solvent is a water-insoluble solvent.
19. The process for producing a spiroindene compound according to claim 1, wherein in the step (2), the reaction solvent is methylene chloride.
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