阅读说明：本技术 一种有机纳米格及其制备方法 (Organic nano grid and preparation method thereof ) 是由 张广维 高闯 向佳茵 解令海 黄维 黄威 于 2020-07-30 设计创作，主要内容包括：本发明公开了一种有机纳米格及其制备方法,该纳米格材料是以二苯基或芴基为角顶端基团的一类有机纳米框架材料,具有规整“口”型结构,可作为半导体材料应用于有机电子器件,该材料的结构通式如式(Ⅰ)所示：<Image he="725" wi="623" file="DDA0002609011750000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>此类结构具有如下特点：(1)合成步骤简单高效,原料低廉环保；(2)无同分异构体,简单重结晶即可分离；(3)结构规整,形状持久性及尺寸选择性；(4)孔腔大小可调节具有良好的糅合性。该类有机框架材料具有良好光电性能和供受电子能力,可应用于信息存储、发光二极管和光伏电池等有机半导体器件,以及温度响应、离子识别、爆炸物检测等传感器领域。(The invention discloses an organic nano grid and a preparation method thereof, the nano grid material is an organic nano framework material taking diphenyl or fluorenyl as a corner top group, has a regular 'mouth' type structure, can be used as a semiconductor material to be applied to organic electronic devices, and has a structural general formula shown as a formula (I): such a structure has the following features: (1) the synthesis steps are simple and efficient, and the raw materials are cheap and environment-friendly; (2) the isomer is not contained, and the product can be separated by simple recrystallization; (3) the structure is regular, the shape is durable and the size is selective; (4) the pore size can be adjusted, and the pore size has good mashup. The organic frame material has good photoelectric property and electron supply capability, can be applied to organic semiconductor devices such as information storage, light-emitting diodes and photovoltaic cells, and can be used for temperature response, ion identification, explosive detection and the likeThe field of sensors.)

1. An organic nanogel, comprising: the structural general formula of the organic nano grid is shown as the formula (I):

in the formula: ar, Ar₁Is one of the following structures:

in the formula: x is C, S, N, Se or O, R is H or a straight chain, branched chain, cyclic alkyl chain or benzene ring with 1-22 carbon atoms.

2. A method for preparing an organic nanogel according to claim 1, wherein: the method specifically comprises the following steps:

step a, adding magnesium particles and iodine particles into a container, sealing, protecting with nitrogen, adding a tetrahydrofuran solution of dibromoarene Ar into the container, heating and initiating, wherein the solution is successfully initiated by brown-white transition; continuing to react to generate a Grignard reagent of the dibromo compound, adding the Grignard reagent of the dibromo compound into a tetrahydrofuran solution of benzophenone or fluorenone, and reacting under a sealed nitrogen atmosphere to prepare a di-tert-alcohol derivative;

step b, mixing the di-tert-alcohol derivative obtained in the step a and aromatic hydrocarbonAr₁And (3) uniformly mixing the materials in ultra-dry dichloromethane, adding a catalyst, and reacting at room temperature to obtain the organic nanogel.

3. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: the molar ratio of the raw materials used in the step a is as follows: dibromo aromatic hydrocarbon Ar, benzophenone or fluorenone, magnesium particles and iodine particles are 1 mol: 3 mol: 0.006 mol.

4. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: in the tetrahydrofuran solution of the dibromo aromatic hydrocarbon Ar in the step a, the using amount ratio of the dibromo aromatic hydrocarbon Ar to the tetrahydrofuran is 1 g: 50 mL.

5. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: and (b) reacting for 2h at 50 ℃ in the step a to generate the Grignard reagent of the dibromo compound.

6. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: the reaction is carried out at 90 ℃ for 12h in the step a to prepare the di-tert-alcohol derivative.

7. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: the catalyst in the step b is methanesulfonic acid.

8. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: the molar ratio of the raw materials used in the step b is as follows: di-tertiary alcohol derivative aromatic hydrocarbon Ar₁The catalyst is 1 mol: 2.5 mol.

9. The method for preparing an organic nanogel according to claim 2, wherein the method comprises the steps of: and the reaction time of the step b is 3-48 h.

Technical Field

The invention belongs to the field of organic semiconductor materials, and particularly relates to an organic nanogel and a preparation method thereof.

Background

Macrocyclic chemistry has really attracted extensive attention by chemists and biologists since the first synthesis of crown ether molecules by professor pedersen in 1967. The artificially synthesized macrocyclic compound mainly comprises cyclophane, cucurbituril, porphyrin, cyclodextrin and the like. The macrocyclic compounds are cage-type macrocyclic compounds formed by linking two or more aromatic compounds by short spacers, and the structure enables the macrocyclic compounds to have not only hydrophobic cavities consisting of aromatic rings, but also a plurality of reactive sites and a plurality of functional groups, so the macrocyclic compounds are widely applied to the fields of ion recognition, molecular devices, supramolecular self-assembly, fluorescent probes and the like. The structure has the advantages of macrocyclic effect, pre-organization effect, shape durability, size selectivity and the like, so that the rigid regular closed-loop compound has important research significance in the field of organic semiconductors.

The synthesis of macrocyclic compounds is mainly carried out in three ways, (1) high concentration dilution method, in which two reactants are mixed uniformly and then added dropwise into a very dilute environment for reaction, which was used for the synthesis of the macrocyclic compounds as early as 1965, the yield was only 3% at that time, and the yield reached 60% by 1999, which was also very practical until now. (2) Template method, which performs a cyclization reaction by forming a complex between an ion and a reactant, has a high cycle yield but introduction and removal of a template is difficult. (3) The hydrogen bonding method controls the configuration by introducing a specific substance and a reactant to form a hydrogen bond or other weak acting forces so as to play a ring closing role, has high yield and simple post-treatment, and becomes a main method for synthesizing a macrocyclic compound.

In 2014, a synthesis mode from bottom to top is provided for solving a sea topic group, a nanoscale closed-loop structure with regular rigidity is prepared, and the structure of the structure is of a 'solar' type and has good shape durability and size selectivity. It constructs a series of closed-loop structures such as ladder, windmill, and rhombohedral nanograms by skilled configuration matching techniques and simple Friedel-Crafts reactions, but the nanograms synthesized by the subject group have various isomers, resulting in difficulty in separation. A series of organic nano lattice structures and polymers constructed based on the fluorenyl group show great potential in the fields of organic electroluminescent display, information storage, super capacitors, sensors and the like, and become a new development direction. The nano grid aromatic hydrocarbon has good structure mixing property, light stability and regularity, and provides a valuable reference thought for synthesizing a series of closed-loop compounds.

Disclosure of Invention

In view of the above-mentioned prior art and the need for improvement, the present invention provides an organic nanogel and a method for preparing the same. The nano lattice material is a closed-loop rigid structure which is free of manual property, easy to separate, has a definite angle top end and a certain cavity, and has good thermal stability, spectral stability and electrochemical stability; the preparation method is simple, efficient, controllable in process, convenient for industrial production, low in material cost, easy to prepare and capable of being widely applied to wide-bandgap semiconductors.

The technical scheme is as follows: the invention relates to an organic nanogel, which has a structural general formula shown in formula (I):

in the formula: ar, Ar₁Is one of the following structures:

in the formula: x is C, S, N, Se or O, R is H or a straight chain, branched chain, cyclic alkyl chain or benzene ring with 1-22 carbon atoms.

The preparation method of the organic nanogold specifically comprises the following steps of:

step a, adding magnesium particles and iodine particles into a container, sealing, protecting with nitrogen, adding a tetrahydrofuran solution of dibromoarene Ar into the container, heating and initiating, wherein the solution is successfully initiated by brown-white transition; continuing to react to generate a Grignard reagent of the dibromo compound, adding the Grignard reagent of the dibromo compound into a tetrahydrofuran solution of benzophenone or fluorenone, and reacting under a sealed nitrogen atmosphere to prepare a di-tert-alcohol derivative;

step b, the di-tert-alcohol derivative obtained in the step a and aromatic hydrocarbon Ar₁And (3) uniformly mixing the materials in ultra-dry dichloromethane, adding a catalyst, and reacting at room temperature to obtain the organic nanogel.

Further, the molar ratio of the raw materials used in the step a is as follows: dibromo aromatic hydrocarbon Ar, benzophenone or fluorenone, magnesium particles and iodine particles are 1 mol: 3 mol: 0.006 mol.

Further, in the tetrahydrofuran solution of the dibromo-aromatic hydrocarbon Ar in the step a, the using amount ratio of the dibromo-aromatic hydrocarbon Ar to the tetrahydrofuran is 1 g: 50 mL.

Further, the Grignard reagent which generates the dibromo compound is reacted for 2 hours at 50 ℃ in the step a.

Further, the reaction is carried out at 90 ℃ for 12h in the step a to prepare the di-tert-alcohol derivative.

Further, the catalyst in the step b is methanesulfonic acid.

Further, the molar ratio of the raw materials used in the step b is as follows: di-tertiary alcohol derivative aromatic hydrocarbon Ar₁The catalyst is 1 mol: 2.5 mol.

Further, the reaction time of the step b is 3-48 h.

Has the advantages that: the isomer was confirmed to be absent by Nuclear Magnetic Resonance (NMR), and the separation was simple. The thermal stability of the material was tested by thermogravimetric analysis and differential thermal analysis. The spectral stability was characterized by uv-fluorescence spectroscopy. Regular structure, shape durability and size selectivity were confirmed by single crystal XRD.

The main advantages of the invention are:

(1) the synthetic steps are simple and efficient, the raw materials are cheap and environment-friendly, isomers are not generated, the separation can be realized through simple recrystallization, the structure is regular, the shape durability and the size selectivity are high, the pore size can be adjusted, and the good mixing property is realized.

(2) The large cavity and the large specific surface area have positive effects on the aspect of detecting explosives by the solid film.

(3) Meanwhile, the compound has a receptor group, and has an obvious effect on information storage.

Drawings

FIG. 1 is a single crystal structure of diphenylbiphenyl carbazole lattice;

FIG. 2 is a single crystal structure of diphenylmonobenzcarbazolium;

FIG. 3 is a nuclear magnetic hydrogen spectrum of diphenylbiphenyl carbazole lattice;

FIG. 4 is a nuclear magnetic hydrogen spectrum of diphenylmonobenzocarbazole lattice;

FIG. 5 is a nuclear magnetic hydrogen spectrum of fluorenyl biphenyl 9-phenyl carbazole lattice;

FIG. 6 is a nuclear magnetic hydrogen spectrum of a fluorenyl monobenzene 9-phenyl carbazole lattice;

FIG. 7 is a solution absorption and emission spectrum of diphenylbiphenyl carbazolium;

FIG. 8 is a solution absorption and emission spectrum of diphenylmonobenzcarbazolium.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and detailed description.

A preparation method of an organic nanogel specifically comprises the following steps:

step a, adding magnesium particles and iodine particles into a container, sealing, protecting with nitrogen, slowly adding a tetrahydrofuran solution of dibromoarene Ar into the container, heating and initiating, wherein the solution is successfully initiated by brown-white transition; continuing to react to generate a Grignard reagent of the dibromo compound, adding the Grignard reagent of the dibromo compound into a tetrahydrofuran solution of benzophenone or fluorenone, and reacting under a sealed nitrogen atmosphere to prepare a di-tert-alcohol derivative;

step b, the di-tert-alcohol derivative obtained in the step a and aromatic hydrocarbon Ar₁And (3) uniformly mixing the materials in ultra-dry dichloromethane, adding a catalyst, and reacting at room temperature to obtain the organic nanogel.

Ar, Ar₁Is one of the following structures:

wherein X is C, S, N, Se or O, and R is H or a straight chain, branched chain, cyclic alkyl chain with 1-22 carbon atoms or a benzene ring.