CN101597489B - Organic, inorganic hybrid green-light material having a network structure, preparation and use thereof - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid green light-emitting material with a network structure and its preparation and application. Group part and capping organic molecule, its molar ratio is 1:n:m-2n, n=1～7, 1≤n≤m/2; Its preparation is the terminal functional silsesquioxane POSS and terminal bifunctional Luminescent molecules, with a molar ratio of 1:n, are catalyzed by cuprous salts, using methods such as click chemistry to prepare controllable network-shaped organic-inorganic hybrid green light-emitting materials. The green light material is used in various displays, optical communications, interior decoration light sources, three-dimensional storage, optical modulation, solar cells and other fields. The green light material of the invention has the characteristics of easy structure design and control, simple preparation process, environment-friendly, good film-forming property and the like.

Description

A network-shaped organic-inorganic hybrid green light material and its preparation and application

technical field

The invention belongs to the field of green light-emitting materials and their preparation and application, in particular to an organic-inorganic hybrid green light material with a network structure and its preparation and application.

Background technique

The emergence of organic light-emitting devices (Organic Light-Emitting Device, OLED) has brought a huge impact to the display technology. Compared with other display technologies, OLED has significant advantages such as wide viewing angle, low energy consumption, fast response speed, ultra-thin, ultra-light, and easy molding and processing. Extensive attention and in-depth research.

As one of the three primary colors, green light materials have developed rapidly in recent years. For example, Chinese patent CN1381543A discloses an energy-transfer main chain polymer luminescent material, which realizes green light emission by controlling the content of naphthalimide derivatives. Chinese patent CN101172963A discloses a class of arylamine-substituted carbazole derivatives. In addition to emitting green light, the material also has good carrier transport properties. Chinese patent CN1618926A discloses a class of organic electroluminescent green light-emitting materials, which are iridium coordination compounds containing heterocycles. Chinese patent CN101161763A discloses a coumarin-based green light organic electroluminescent material containing enolate side groups. Due to the presence of enolate, the material has ultraviolet curing activity. Chinese patent CN1184177C discloses a green light material of dinaphthopyrene compound. Although OLED materials have broad application prospects, there are still the following shortcomings:

1. The stability of small-molecule organic electroluminescent materials is not enough. With the use of the device, molecular aggregation, crystallization or decomposition will occur, resulting in fluorescence quenching and other color coordinate drift, and short service life;

2. Although the polymer organic electroluminescent material (PLED) can improve a certain stability, its separation and purification have not yet reached the level of small molecules, resulting in low luminous purity of the material;

3. When preparing devices, it is often used as a doping object, and the dispersion is uneven, resulting in uneven light emission.

In order to solve the above problems and obtain organic electroluminescent green light-emitting materials with excellent performance, the method of organic-inorganic hybridization can not only better combine the respective advantages of organic materials and inorganic materials, but also make the materials not only have excellent processing properties of organic materials performance, good toughness, while retaining the heat resistance, oxidation resistance and excellent mechanical properties of inorganic materials, and can effectively reduce the association of organic molecules, reduce the energy barrier between the organic layer and the electrode, and improve the electron and hole Injection efficiency, thereby improving the brightness, efficiency and lifetime of OLED devices.

Cage silsesquioxane (POSS) is a new type of nanostructure material that has emerged in recent years. Its molecular formula can be expressed as (RSiO _1.5 ) _m (m can generally be 6, 8, 10, 12, 14, etc.), With a cage structure, it is a hybrid compound composed of a rigid, structurally determined nanoscale inorganic core composed of silicon and oxygen and an organic group R connected by a covalent bond as the shell. Different reactive functional groups can be bonded on the surface of POSS polyhedrons by chemical methods, endowing POSS nanoparticles with multifunctionality and high reactivity, and combining organic and inorganic components at the molecular level. Compared with general polysiloxane, POSS with cage structure has better heat resistance and lower surface energy; compared with other inorganic nanoparticle modifiers such as nanoscale clay, silicon dioxide, titanium dioxide, Calcium carbonate, etc. POSS nanoparticles with a cage structure not only have the advantages of simple and effective synthesis process, large surface binding force, good monodispersity, low density, good thermal stability and no trace metal impurities. The most important thing is that the organic group is introduced into the Si vertex by chemical method, which truly realizes the hybridization of organic and inorganic at the molecular level, and the dispersion is good. In addition, although small-molecule organic light-emitting materials are easier to purify, due to the characteristics of polymer light-emitting materials, purification is difficult. Through the introduction of POSS, polymer materials that are easier to purify can be produced.

All in all, POSS, as a nanoparticle with a new structure, is attracting great attention from researchers at home and abroad. However, most of the current research is limited to the mechanical properties and thermal properties of materials, and there are relatively few studies on the functionality of materials. The research fields need to be further expanded, and there are few related patents. Chinese patent CN1651438A discloses a polysilsesquioxane-based compound having an organometallic complex and an organic electroluminescent device using it. Chinese patent CN101250402A is a three-color organic-inorganic silicon-based hybrid material with adjustable luminous color, which realizes the emission of red light, green light, and blue light by doping different metal ions. Xiao S. et al. (J.Pharm.Sci., 2002, 91:2182) prepared MEH-PPV-POSS and PFO-POSS composite materials end-capped by POSS, which have the same photoluminescence spectrum and electroluminescent spectrum in solution or sheet. Luminescence Spectrum. Lin W. et al. (Macromolecules, 2004, 37(7): 2335) synthesized a star-shaped hybrid PFO material, which reduced molecular aggregation and significantly improved the thermal properties and fluorescence quantum efficiency of the material, but the reaction route and post-treatment more complicated. Lee et al. (Macromol, 2004, 37(23): 8523) prepared organic-inorganic hybrid polyfluorenes with POSS as side groups through a series of reactions such as substitution, etherification, and hydrosilylation. The increase of the content is improved, especially the light color purity of electroluminescence is greatly improved. Jesse D.Froehlich et al. (Chem.Mater.2007, 19:4991) reported a multifunctional POSS organic-inorganic hybrid luminescent material, which effectively improved the thermal properties of the material, but the number of luminescent groups added to POSS And hybrid molecular structure is uncontrollable, the obtained luminescent material is a mixture of different numbers of luminescent groups, the energy transfer between each group is uncontrollable, and as a result, it is difficult to control the luminescence purity and luminescence wavelength.

Contents of the invention

The technical problem to be solved by the present invention is to provide a network-shaped organic-inorganic hybrid green light material and its preparation and application. The organic-inorganic hybrid green light material of the present invention can realize precise control of the number of organic light-emitting groups, Therefore, the effective adjustment of the purity of the luminous color is realized; the preparation process is simple, the raw material source is convenient, the reaction speed is fast, the cost is low, and the environment is friendly.

An organic-inorganic hybrid green light-emitting material with a network structure of the present invention mainly includes: a terminal functional silsesquioxane (POSS) core structure part, a terminal bifunctional green light-emitting organic group part and a capping Terminal organic molecules, the molar ratio of which is 1:n:m-2n, n=1-7, 1≤n≤m/2.

The simplified structural formula of the described silsesquioxane (POSS) core is (RSiO _3/2 ) m, m=6, 8, 10, 12, 14, etc., taking m=8 as an example, its structure is as shown in the figure,

表示烷基链或硅氧链。in,

Indicates an alkyl chain or a siloxane chain.

The organic-inorganic hybrid green light-emitting material with a network structure is characterized in that: the typical structure of the organic green light-emitting group includes coumarin derivatives, quinacridone derivatives, Hexabenzocene derivatives, aniline derivatives, azo metal complex derivatives, etc., their structures are shown in the figure,

表示烷基、烷氧基、取代或未取代芳基、芳烷基、芳氧基、杂芳基、杂环烷基或酯基；Among them, R ⁽¹⁾ and R ⁽²⁾ are hydrogen atom, halogen atom, cyano group, amino group, alkyl group, alkoxy group, substituted or unsubstituted aryl group, aralkyl group, aryloxy group, heteroaryl ring, ring Alkyl or ester groups;

represents an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, an aralkyl group, an aryloxy group, a heteroaryl group, a heterocycloalkyl group or an ester group;

The green light-emitting material is mainly obtained by click chemical reaction between functional POSS molecules and green light-emitting group molecules, mainly including two types of reactions,

或

结构；A. Reaction of functional POSS with terminal alkyne group with luminescent molecule with terminal azide group or reaction of functional POSS with terminal azide group with luminescent molecule with terminal alkyne to form

or

structure;

或结构；B. Functional POSS with terminal alkenyl reacts with luminescent molecules with terminal sulfhydryls or functional POSS with terminal sulfhydryls reacts with luminescent molecules with terminal alkenes to form

or structure;

The molecular formula of the molecular material of the green light-emitting material is [R' _n R" _m-2n (SiO _3/2 ) _m ] _x , wherein m=6, 8, 10, 12, 14, etc., 1 ≤n≤m/2, R' is an organic luminescent small molecular chain, R" is a capped organic molecular chain;

Taking m=8, n=4, type A reaction as an example, the partial amplification of the organic-inorganic hybrid green light-emitting material molecule with network structure is as follows:

Taking m=8, n=4, type B reaction as an example, the partial amplification of the organic-inorganic hybrid green light-emitting material molecule with network structure is shown as follows:

为烷基链；in,

is an alkyl chain;

The organic-inorganic hybrid green light-emitting material with a network structure is characterized in that: the blocked organic molecule has the following structure:

in, is a flexible or rigid stable optically inactive organic group;

The luminescence peak wavelength of the organic-inorganic hybrid green light material based on silsesquioxane is between 500nm and 560nm, the temperature range for 50% thermal weight loss is 450°C-480°C, and the melting point range is 130-200°C.

A method for preparing an organic-inorganic hybrid green light-emitting material with a network structure of the present invention comprises the following steps:

Type a reaction:

Method 1: Dissolve terminal alkyne (terminal azide) functional POSS, terminal azide (terminal alkyne) bifunctional luminescent molecule and cuprous catalyst in an organic solvent, and the ratio of terminal functional POSS to terminal bifunctional luminescent molecule is 1: n, 1≤n≤m/2, where m is the number of Si in a single POSS core structure, m=6, 8, 10, 12, 14, etc.; under the protection of _N2 , react at 20-70°C for 8-24h , add a capping group with the corresponding functional end and click to cap, the feeding ratio is m-2n times that of the terminal functional POSS, continue to react for 8 to 24 hours under the same conditions, and then use CHCl ₃ , MeOH, H ₂ O, THF in sequence , washed with Et ₂ O, and dried in vacuum at 40°C for 12 hours to obtain the target product;

Or method 2: dissolve terminal alkyne (terminal azide) functional POSS, terminal azide (terminal alkyne) bifunctional luminescent molecules, monofunctional capping groups with corresponding functional ends, and cuprous catalysts in organic solvents, The terminal functional POSS, the terminal bifunctional luminescent molecule and the monofunctional capping group are according to the feeding ratio of 1:n:(m-2n), 1≤n≤m/2, where m is the number of Si in a single POSS core structure , m=6, 8, 10, 12, 14, etc.; under N ₂ protection, react at 20-70°C for 8-24h, then wash with CHCl ₃ , MeOH, H ₂ O, THF, Et ₂ O, 40°C Vacuum dried for 12 hours to obtain the target product.

Type b reactions:

Method 1: Dissolve the above-mentioned terminal olefin (terminal mercapto) functional POSS, terminal mercapto (terminal olefin) bis-monofunctional luminescent molecule raw material and cuprous catalyst in an organic solvent, and the feed ratio of terminal functional POSS to terminal monofunctional luminescent molecule is 1: n, 1≤n≤m/2, where m is the number of Si in a single POSS core structure, m=6, 8, 10, 12, 14, etc.; under ultraviolet light, react at 0-40°C for 2-10h, add The capping group with the corresponding functional terminal is click-capped, and the feeding ratio is m-2n times that of the terminal functional POSS. The reaction is continued for 2 to 10 hours under the same conditions, and then CHCl ₃ , MeOH, H ₂ O, THF, Et ₂ O washing, and vacuum drying at 40°C for 12 hours to obtain the target product;

Or method two: dissolve the above-mentioned terminal thiol (terminal mercapto) functional POSS, terminal mercapto (terminal ene) monofunctional luminescent molecule and a monofunctional capping group with a corresponding functional end and a cuprous catalyst in an organic solvent, and the terminal function The feed ratio of POSS, terminal bifunctional luminescent molecules and monofunctional capping groups is 1:n:(m-2n), 1≤n≤m/2, where m is the number of Si in a single POSS core structure, m =6, 8, 10, 12, 14, etc.; under ultraviolet light, react at 0-40°C for 2-10h, then wash with CHCl ₃ , MeOH, H ₂ O, THF, Et ₂ O in sequence, and dry in vacuum at 40°C for 12 hours obtain the target product.

The cuprous catalyst includes reducing agents such as cuprous salts, divalent copper salts + sodium ascorbate, copper + amine hydrochlorides and other oxidants, and the dosage is 0.5-10% of the molar weight of terminal functional POSS;

The organic solvent is a conventional organic solvent such as DMF or DMSO.

The organic-inorganic hybrid green luminescent material with a network structure of the invention is applied to the preparation of various displays, signboards, optical communications and interior decoration light sources.

In the present invention, each green light-emitting group is introduced into monomers with alkenyl or mercapto groups at the end through Heck reaction, Witting reaction, Sonogashira reaction, Wohl-Ziegler reaction, etc., to obtain monofunctional or bifunctional light-emitting molecules, Moreover, the number of organic light-emitting groups can be precisely controlled by changing the feeding ratio, and then the luminous intensity and color purity can be effectively adjusted.

The silsesquioxane used in the present invention contains 8 functional groups, which can react with 8 green light-emitting molecular functional groups. When the proportion of green light-emitting molecular reactive functional groups is less than 8, in order to prevent The unreacted groups on the molecule are further cross-linked to improve the solubility or stability of the material, and are usually terminated with organic molecules containing flexible or rigid chains (the process is the same as that of hybrid materials).

Beneficial effect:

(1) The organic-inorganic hybrid green light material with a network structure of the present invention can realize precise control of the number of organic light-emitting groups, thereby realizing effective adjustment of the purity of light-emitting colors;

(2) The organic-inorganic hybrid green light material with network structure has the characteristics of good thermal stability, easy processing and molding, good film-forming property, high luminous efficiency, pure luminous color, and long service life of the light-emitting device;

(3) The preparation process is simple, the raw material source is convenient, the reaction speed is fast, the cost is low, and the environment is friendly.

Description of drawings

Fig. 1 is the fluorescence spectrogram of the product that embodiment 1 obtains in THF solution;

Fig. 2 is the current density-voltage curve figure of the thin film that embodiment 1 makes;

Fig. 3 is the efficiency-voltage figure of the thin film that embodiment 1 makes;

Fig. 4 is the brightness-voltage figure of the film that embodiment 1 makes;

Fig. 5 is the TGA curve chart of the product prepared in embodiment 1.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

Sodium azide POSS (139.32g 90mmol), compound 2 (see reaction formula 1) (43.25g 120mmol), n-hexyne (39.36g 480mmol) and CuI (1.71g 9mmol) were added in a three-necked flask, under _N2 atmosphere Add 10ml of DMF and stir at room temperature for 12 hours. After the initial product was filtered, it was washed successively with CHCl ₃ , MeOH, H ₂ O, THF, and Et ₂ O, and dried under vacuum at 40°C for 12 hours. The molecular formula of the product is: (C ₃₀ Si ₂ N ₈ O ₂ H ₂₈ ) ₁₂ (C ₉ SiN ₃ OH ₁₈ ) ₄₈ (Si ₈ O ₁₂ ) ₉ , the yield is 92%, and the emission peak wavelength is 540nm.

Chemical reaction formula 1:

Example 2

Vinyl POSS (56.97g 90mmol), compound 2 (see reaction formula 2) (45.17g 120mmol), 1-mercaptobutane (43.2g 480mmol) and CuI (1.71g 9mmol) were added in a three-necked flask, under N ₂ DMF10ml was added under atmosphere, and stirred at room temperature for 12 hours. After the initial product was filtered, it was washed successively with CHCl ₃ , MeOH, H ₂ O, THF, and Et ₂ O, and dried under vacuum at 40°C for 12 hours. The molecular formula of the product is: (C ₂₀ S ₂ N ₂ O ₂ H ₁₂ ) ₁₂ (C ₄ SH ₁₀ ) ₄₈ (Si ₈ O ₁₂ ) ₉ , the yield is 92%, and the emission peak wavelength is 553nm.

Chemical reaction formula 2:

Example 3

Add sodium azide POSS (139.32g 90mmol), compound 2 (see Reaction Formula 3) (43.25g 120mmol) and CuI (1.71g9mmol) into a three-necked flask, add DMF10ml under N ₂ atmosphere, and stir at room temperature for 12 hours. Add n-hexyne (39.36g 480mmol) and react under the same conditions for 12 hours. After the initial product was filtered, it was washed successively with CHCl ₃ , MeOH, H ₂ O, THF, and Et ₂ O, and dried under vacuum at 40°C for 12 hours. The molecular formula of the product is: (C ₃₀ Si ₂ N ₈ O ₂ H ₂₈ ) ₁₂ (C ₉ SiN ₃ OH ₁₈ ) ₄₈ (Si ₈ O ₁₂ ) ₉ , the yield is 92%, and the emission peak wavelength is 540nm.

Chemical reaction formula 3:

Claims (8)

1. A network-shaped organic-inorganic hybrid green light-emitting material, whose components include: terminal functional silsesquioxane core structure part, terminal bifunctional organic green light-emitting group part and end-capped organic molecule, the molar ratio of which is 1:n:m-2n, n=1~7, 1≤n≤m/2; The simplified structural formula of the terminal functional silsesquioxane core is (RSiO _3/2 )m, m=6, 8, 10, 12, 14, taking m=8 as an example, its structure is shown in the figure,

in,

Indicates an alkyl chain or a siloxane chain; The typical structure of the organic green light-emitting group includes coumarin derivatives, quinacridone derivatives, hexabenzocene derivatives, aniline derivatives, azo metal complex derivatives, Its structure is shown in the figure, Among them, R ⁽¹⁾ and R ⁽²⁾ are hydrogen atom, halogen atom, cyano group, amino group, alkyl group, alkoxy group, substituted or unsubstituted aryl group, aralkyl group, aryloxy group, heteroaryl ring, ring Alkyl or ester groups;

represents an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, an aralkyl group, an aryloxy group, a heteroaryl group, a heterocycloalkyl group or an ester group; Described capping organic molecule, its structure is as follows:

in, It is a flexible or rigid stable optically inactive organic group. 2. The organic-inorganic hybrid green luminescent material with a network structure according to claim 1, characterized in that: the green luminescent material is mainly composed of functional silsesquioxane molecules and organic green luminescent groups Molecules are obtained through click chemistry reactions, including two types of reactions: A. Functional silsesquioxane with terminal alkyne reacts with luminescent molecule with terminal azide or functional silsesquioxane with terminal azido reacts with luminescent molecule with terminal alkyne to form structure; B. The functional silsesquioxane with terminal alkenyl reacts with the luminescent molecule with terminal mercapto or the functional silsesquioxane with terminal mercapto reacts with the luminescent molecule with terminal alkene to form

structure. 3. The organic-inorganic hybrid green luminescent material with a network structure according to claim 1 or 2, characterized in that: the molecular formula of the molecular material of the green luminescent material is [R' _n R " _m-2n (SiO _3/2 ) _m ] _x , where m=6, 8, 10, 12, 14, 1≤n≤m/2, R' is the molecular chain of organic green light-emitting group, R" is Capped organic molecular chains; Taking m=8, n=4, type A reaction as an example, the molecular characteristic structure of the organic-inorganic hybrid green light-emitting material with network structure is as follows: Taking m=8, n=4, type B reaction as an example, the molecular characteristic structure of the organic-inorganic hybrid green light-emitting material with network structure is as follows:

in,

for the alkyl chain. 4. The organic-inorganic hybrid green luminescent material with network structure according to claim 1, characterized in that: the luminescence peak wavelength of the organic-inorganic hybrid green luminescent material with network structure is between 500nm and Between 580nm and 50% thermal weight loss, the temperature range is 450℃～480℃, and the melting point range is 130～200℃. 5. The preparation method of the organic-inorganic hybrid green light-emitting material of a kind of network structure as claimed in claim 1, comprises the following steps: Type A reactions: Dissolve terminal alkyne or terminal azido functional silsesquioxane, terminal azide or terminal alkyne bifunctional luminescent molecule and cuprous catalyst in an organic solvent, and the ratio of terminal functional silsesquioxane to terminal bifunctional luminescent molecule It is 1:n, 1≤n≤m/2, where m is the number of Si in a single silsesquioxane core structure, m=6, 8, 10, 12, 14; under the protection of _N2 , 20～ React at 70°C for 8 to 24 hours, add a capping group with a corresponding functional end and click to block the end, and the feeding ratio is m-2n times that of the terminal functional silsesquioxane. ₃ , washed with MeOH, H ₂ O, THF, Et ₂ O, and dried in vacuum at 40°C for 12 hours to obtain the target product; Or dissolve the terminal alkyne or terminal azido functional silsesquioxane, the terminal azide or terminal alkyne bifunctional luminescent molecule and the monofunctional capping group with the corresponding functional terminal and the cuprous catalyst in an organic solvent, and the terminal Functional silsesquioxane, terminal difunctional luminescent molecules and monofunctional capping groups are in a feed ratio of 1:n:(m-2n), 1≤n≤m/2, where a is a single silsesquioxane The number of Si with alkane core structure, m=6, 8, 10, 12, 14; under the protection of N ₂ , react at 20-70°C for 8-24 hours, and use CHCl ₃ , MeOH, H ₂ O, THF, Et _{2 in} sequence O washing, vacuum drying at 40°C for 12 hours to obtain the target product; Type B reactions: Dissolve the above-mentioned terminal olefin or terminal mercapto functional silsesquioxane, terminal mercapto or terminal olefin bifunctional luminescent molecule raw material and cuprous catalyst in an organic solvent, and the feed ratio of terminal functional silsesquioxane to terminal bifunctional luminescent molecule is 1:n, 1≤n≤m/2, where m is the number of Si in a single silsesquioxane core structure, m=6, 8, 10, 12, 14; UV light, react at 0-40°C 2~10h, add the end-capping group with the corresponding functional end and click end-blocking, the feeding ratio is m-2n times of the terminal functional silsesquioxane, continue the reaction under the same conditions for 2~10h, sequentially use CHCl ₃ , MeOH , H ₂ O, THF, Et ₂ O, and vacuum drying at 40°C for 12 hours to obtain the target product; Or dissolve the above-mentioned terminal olefin or terminal mercapto functional silsesquioxane, terminal mercapto or terminal olefin monofunctional luminescent molecule and a monofunctional capping group with a corresponding functional terminal and a cuprous catalyst in an organic solvent, and the terminal function doubles The material ratio of semisiloxane, terminal bifunctional luminescent molecule and monofunctional capping group is 1:n:(m-2n), 1≤n≤m/2, where a is a single silsesquioxane core The number of Si in the structure, m=6, 8, 10, 12, 14; under ultraviolet light, react at 0-40°C for 2-10 hours, wash with CHCl ₃ , MeOH, H ₂ O, THF, Et ₂ O in turn, 40 °C and vacuum dried for 12 hours to obtain the target product. 6. The preparation method of an organic-inorganic hybrid green light-emitting material with a network structure according to claim 5, characterized in that: the catalyst cuprous includes cuprous salt, divalent cupric salt+sodium ascorbate reduction Agent, copper + amine hydrochloride oxidant, the dosage is 0.5-10% of the molar weight of terminal functional silsesquioxane. 7 . The method for preparing a network-structured organic-inorganic hybrid green light-emitting material according to claim 5 , wherein the organic solvent is DMF or DMSO. 8. The organic-inorganic hybrid green luminescent material with a network structure as claimed in claim 1 is applied to the preparation of various displays, signboards, optical communications, and interior decoration light sources.

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