CN109970619B

CN109970619B - Indolethiodiene type metal complex and preparation method thereof

Info

Publication number: CN109970619B
Application number: CN201910387373.1A
Authority: CN
Inventors: 韩爱鸿; 刘蕊; 高雪; 张拓; 王依琳; 张洪波; 孙秋菊
Original assignee: Shenyang Normal University
Current assignee: Shenyang Normal University
Priority date: 2019-05-10
Filing date: 2019-05-10
Publication date: 2022-06-28
Anticipated expiration: 2039-05-10
Also published as: CN109970619A

Abstract

The invention relates to the technical field of dye-sensitized solar cell materials, in particular to an indole thio-diene type metal complex and a preparation method thereof; the method takes isatin as a starting material, introduces various substituent groups R on nitrogen atoms through chemical modification to obtain a chemically modified isatin intermediate, and then further reacts with phosphorus pentasulfide and a chloride of a divalent metal to obtain the indole thio-diene type metal complex. The invention breaks through the constraint that benzene ring or naphthalene ring groups adopted in the existing structure form an intermediate thiodiene type metal skeleton, and obtains the near infrared dye with a series of substituted indole thiodiene metal complex structures. The molecular structure of the dye intermediate isatin has the characteristic of a diketone structure, and after various modifications are carried out on nitrogen atoms, the dye intermediate isatin is directly complexed with metal to obtain a target compound, so that the process step of generating three wastes is avoided, and a new application of the dye intermediate isatin is developed.

Description

Indolylthiodiene type metal complex and preparation method thereof

Technical Field

The invention relates to the technical field of dye-sensitized solar cell materials, in particular to an indole thio-diene type metal complex and a preparation method thereof.

Background

The thiodiene type metal complex is a near infrared dye with wide application, and is more and more concerned due to excellent photo-thermal stability, stronger light absorption performance and electromagnetic property. At present, two synthetic methods, namely a benzoin route and a diketone route, are generally adopted for preparing the thiodiene type metal complex with a symmetrical structure, and the diketone route is generally adopted for preparing the thiodiene type metal complex, but in the preparation process, a large amount of acid-containing wastewater and solid residues are generated in the treatment process after reaction due to the utilization of raw materials such as oxalyl chloride, anhydrous aluminum trichloride and the like, so that the environment is harmed.

In order to overcome the defects in the diketone route, the application provides a novel synthetic route, a chemical product-isatin with easily available raw materials is utilized to design and prepare a thiodiene type metal complex with a novel structure, the compound keeps the characteristic of strong absorption of near-infrared dyes in the near-infrared region, and a novel application of the dye intermediate of the isatin is developed. The method utilizes the diketone functional group in the isatin molecular structure, avoids using oxalyl chloride and anhydrous aluminum trichloride in the process of preparing the thiodiene metal complex, reduces the discharge of three wastes, and is a clean process route with little pollution.

Disclosure of Invention

The invention aims to provide a thiodiene type metal complex with a novel structure, breaks through the constraint that a benzene ring or a naphthalene ring group is used for forming an intermediate thiodiene type metal skeleton in the existing structure, and obtains a series of near-infrared dyes with a substituted indole thiodiene metal complex structure.

The purpose of the invention can be realized by the following technical scheme:

the structure of the indolylthiodiene type metal complex is as follows:

wherein M represents Ni or Cu or Pt or Pd; r represents C₁-C₁₂Alkyl chains or acyl or substituted benzyl groups.

A method of preparing an indothiodiene-type metal complex comprising:

the method comprises the steps of taking isatin as a starting raw material, introducing various substituent groups R on nitrogen atoms through chemical modification to obtain a chemically modified isatin intermediate, and further reacting the chemically modified isatin intermediate with phosphorus pentasulfide and a chloride of a divalent metal to obtain the indole thiodiene type metal complex.

The invention has the beneficial effects that:

the process route of the invention is environment-friendly and easy to operate, greatly reduces the discharge of three wastes, saves energy and meets the requirement of green chemistry.

The indole thio-diene metal complex prepared by the invention has a novel structure, can keep strong absorption of near-infrared dye in a near-infrared region, and can increase the solubility of the near-infrared dye in an organic solvent, thereby facilitating the application of products.

The raw material isatin selected by the process is cheap and easy to obtain, so that the product has a good price advantage, and a new application of the isatin is developed.

Drawings

To facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.

FIG. 1 is a schematic diagram of the process of example 1;

FIG. 2 is an IR diagram of intermediate 1-octyl isatin according to the examples;

FIG. 3 is an IR chart of the product 1-octylindolium thiodiene nickel of the example;

FIG. 4 is a nuclear magnetic resonance hydrogen spectrum (1H-NMR) of intermediate 1-octyl isatin according to the example;

FIG. 5 is a nuclear magnetic resonance carbon spectrum (13C-NMR) of intermediate 1-octyl isatin according to the example;

FIG. 6 is a nuclear magnetic resonance hydrogen spectrum (1H-NMR) of octyl indole thiodiene nickel according to an example;

FIG. 7 is a graph showing the UV absorption of nickel octyl indole thiodiene according to example.

Detailed Description

Example 1:

the substituent R is n-octyl and the coordination metal is nickel, i.e. the following structure is taken as an example to illustrate the implementation process of the invention.

The reaction scheme is shown in figure 1, and the specific reaction scheme is as follows: placing the isatin, the acid-binding agent and a solvent DMF in a two-mouth bottle, carrying out ultrasonic oscillation to completely dissolve the substance isatin in the solvent, stirring for several minutes, adding bromo-n-octane, and stirring and heating in an oil bath kettle for reaction for 24 hours at the reaction temperature of 50-60 ℃. And after the reaction is finished, adding sufficient water to wash to remove generated salt, extracting with ethyl acetate, drying and concentrating the collected organic phase to obtain an orange red oily substance, and separating the mixture by a silica gel column separation method to obtain an intermediate 1-octyl isatin which is an orange solid. Further taking 1-octyl isatin, placing the 1-octyl isatin into a round bottom two-mouth bottle, adding dioxane to completely dissolve the 1-octyl isatin, then adding a catalyst and phosphorus pentasulfide into the bottle, and adding N ₂Stirring and heating the mixture in a constant-temperature oil bath kettle under protection, carrying out reflux reaction for 5 hours, cooling the reaction liquid to room temperature, transferring the supernatant liquid to another two-mouth bottle, introducing nitrogen for protection, dripping aqueous solution of nickel chloride when the temperature is raised to reflux, continuously refluxing for 3-5 hours, pouring the reaction mixture into a beaker filled with water after the two-mouth bottle is cooled to room temperature, and using CH to carry out reflux reaction₂Cl₂And extracting, drying and concentrating the collected organic phase to obtain black oily matter, and separating the oily matter through a column to obtain a blue-black solid octyl indole thio-diene nickel complex. The complex has strong absorption at about 920 nm. The structural characterization of the product and the intermediate is shown in FIGS. 2-7.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A preparation method of an indothiodiene type metal complex is characterized in that the indothiodiene type metal complex has the following structure:

wherein M represents Ni or Cu or Pt or Pd; r represents C₁-C₁₂Alkyl chains or acyl or substituted benzyl;

the preparation method comprises the following synthetic routes: