US-12624014-B2 - Fluorescent material containing thiophene sulfone-olefin structural unit and preparation method thereof

US12624014B2US 12624014 B2US12624014 B2US 12624014B2US-12624014-B2

Abstract

A fluorescent material containing a thiophene sulfone-olefin structural unit and a preparation method thereof are provided. In the preparation method, the thiophene sulfone compounds, olefins, oxidants and additives are dissolved in the tetrahydrofuran solvent, and are subjected to a reaction under the catalytic action of the palladium catalyst, and the alkenylated thiophene sulfone products with obvious fluorescence emission characteristics of liquid and solid can be obtained. The preparation method expands the range of substrates well, featuring good regional selectivity, high yield, mild reaction conditions and simple operation.

Inventors

Xiaolei Huang
Bingbin YANG
Yaoyao LU
Yaolin XIA
Xiaoyu Ma

Assignees

ZHEJIANG NORMAL UNIVERSITY

Dates

Publication Date: 20260512
Application Date: 20230915
Priority Date: 20221107

Claims (9)

1 . A fluorescent material containing a thiophene sulfone-olefin structural unit, wherein a structural formula of the fluorescent material containing the thiophene sulfone-olefin structural unit is as follows: in the structural formula, R 1 is one of H, alkyl, and alkoxy group; m=1-4; when m≠1, a plurality of R 1 s is separately selected as one of the H, the alkyl, and the alkoxy group; and R 2 is one of H, alkyl group, alkoxy group, and aryl group; n=1-5; when n≠1, a plurality of R 2 s is separately selected as one of the H, the alkyl group, the alkoxy group, and the aryl group.
2 . A preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 1 , comprising: in a presence of a palladium catalyst, subjecting a thiophene sulfone compound, olefin, an oxidant, and an additive to an oxyalkylene reaction in a solvent to obtain a reaction mixture, and after the oxyalkylene reaction is completed, performing a post-treatment on the reaction mixture to obtain the fluorescent material containing the thiophene sulfone-olefin structural unit; wherein a structural formula of the thiophene sulfone compound is shown in Formula (I): a structural formula of the olefin is shown in Formula (II): in the Formulas (I)-(II), R 1 is one of H, alkyl, and alkoxy group; m=1-4; when m≠1, a plurality of R 1 s is separately selected as one of the H, the alkyl, and the alkoxy group; and R 2 is one of H, alkyl group, alkoxy group, and aryl group; n=1-5; when n≠1, a plurality of R 2 s is separately selected as one of the H, the alkyl group, the alkoxy group, and the aryl group.
3 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein a molar ratio of the thiophene sulfone compound to the olefin is 1:(1-3).
4 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein the oxidant is one or more of a silver carbonate, a silver acetate, a silver oxide, and/or a silver pivalate; and a molar ratio of the thiophene sulfone compound to the oxidant is 1:(1-5).
5 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein the additive is one or more of PivOH, AcOH, and/or CF 3 COOH; and a molar ratio of the thiophene sulfone compound to the additive is 1:(3-5).
6 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein the solvent is at least one of toluene, 1, 2-dichloroethane, 1, 4-dioxane, dimethyl sulfoxide, and/or tetrahydrofuran (THF).
7 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein the palladium catalyst is Pd(OAc) 2 (CAS:3375-31-3); and an amount of the palladium catalyst is 1-5 mol % of an amount of the thiophene sulfone compound.
8 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein a reaction temperature of the oxyalkylene reaction is 80-120° C.
9 . The preparation method of the fluorescent material containing the thiophene sulfone-olefin structural unit according to claim 2 , wherein after the oxyalkylene reaction is completed, performing the post-treatment comprises: allowing the reaction mixture to pass through a layer of diatomaceous earth and washing with ethyl acetate to obtain a washing solution, using ethyl acetate/petroleum ether as an eluent and purifying the washing solution by a silica gel column chromatography to obtain the fluorescent material containing the thiophene sulfone-olefin structural unit.

Description

CROSS REFERENCE TO THE RELATED APPLICATIONS This application is based upon and claims priority to Chinese Patent Application No. 202211386879.9, filed on Nov. 7, 2022, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD The present invention belongs to the technical field of organic synthesis, and particularly relates to a fluorescent material containing a thiophene sulfone-olefin structural unit and a preparation method thereof. BACKGROUND In recent years; broad application prospects of the thiophene sulfone (S,S-dioxide) skeletons in the field of organic optoelectronic materials have aroused great interest of chemists in synthesis and modification of organic n-conjugated molecules containing thiophene sulfone structural units. For example, Navarrete conducted a Raman spectroscopic analysis of the thiophene sulfone S, S-dioxide-1 in 2005. Compared with a linear and uniform conjugated tertiary thiophene, the introduction of the thiophene sulfone structure led to the division of electronic structure, and the change of this electronic effect makes the design and synthesis of relevant organic material molecules with photoelectric properties feasible; Fattori reported a bithiophene oligomer S, S-dioxide-2 containing a thiophene sulfone structure; which exhibits high photoluminescence quantum efficiency (about 11%) and high oxidation potential (−3.41 eV) in the aggregate state; Leclerc reported a copolymer of fluorene and thiophene Poly-S,S-Dioxide-1, where the introduction of a thiophene oxide led to the formation of an energy gap (2.0 eV), and its luminescence peak wavelength can reach 708 nm, and it is located in the red light region; Yang Wei et al. synthesized blue polymer materials Poly-S,S-Dioxide-2 by using fluorene to copolymerize with sulfur oxyfluorene unit with strong electron affinity, thereby avoiding the problem that classical polyfluorene blue polymer is prone to suffer green light emission under heating conditions. Some examples of organic photoelectric materials containing thiophene sulfone structural units are as follows: Traditional synthesis methods of thiophene sulfone fluorescent molecules mainly include oxidation, Diels-Alder reaction, C—X/C—M (M=Sn, B), and the like. These methods have some problems to varying degrees, such as poor functional group tolerance, limited substrate range, and poor environmental friendliness. Therefore, it is of great significance to design a more general and efficient method to synthesize the thiophene sulfone fluorescent molecules. SUMMARY In order to solve the problems in the prior art, the present invention provides a novel fluorescent material containing a thiophene sulfone-olefin structural unit with obvious fluorescence emission characteristics. The present invention further provides a preparation method of a fluorescent material containing a thiophene sulfone-olefin structural unit. The reaction process of the preparation method is realized by an oxidized Heck reaction based on C—H bond activation, featuring simple operation, mild reaction conditions, high selectivity of target products and high yield. In the past decade, the C—H bond activation functionalizati on method has been widely, used in the synthesis of drugs, natural products and organic functional material molecules thanks to its good atom and economic steps and environmental friendliness. Based on the oxidized Heck reaction strategy activated by the C—H bond, the present invention designs the following reaction: thiophene sulfone compounds, olefins, oxidants and additives are dissolved in an organic phase (solvent), and Pd(OAc)2 is used as a catalyst to obtain a new class of a fluorescent material containing a thiophene sulfone-olefin structural unit. Photophysical properties of the material are initially characterized. The results show that the material prepared by the above preparation method has obvious fluorescence emission characteristics. Compared with the traditional transition metal-catalyzed (hetero) arene C—X/C—Sn coupling reaction, the method has the advantages of simple operation, environment protection, high selectivity and good yield. A fluorescent material containing a thiophene sulfone-olefin structural unit, the structural formula of the fluorescent material containing the thiophene sulfone-olefin structural unit is as follows: In Formula (III), R1 is one of H, alkyl, halogen, ester group, alkoxy group or trifluoromethyl group; m=1-4; when m≠1, a plurality of R1s are separately selected as one of H, alkyl, halogen, ester group, alkoxy group and trifluoromethyl group. In Formula (III), R1 is one of H, alkyl, halogen, ester group, alkoxy group or trifluoromethyl group; m=1-4; when m≠1, a plurality of R1s are separately selected as one of H, alkyl, halogen, ester group, alkoxy group and trifluoromethyl group. R2 is one of H, alkyl group, alkoxy group or aryl group; n=1-5; when, a plurality of R2s are separately selected as one of H, alkyl group,