Structural and electronic tuning of single-benzene fluorophores with simple methylations

IF 4.1 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2024-10-29 DOI:10.1016/j.dyepig.2024.112523

Dopil Kim , Sangho Lee , Haein Kim , Jun Yeong Kim , Yoseph Kim , Youngjo Kim , Myung Hwan Park , Dokyoung Kim , Jaesung Kwak , Dongwook Kim , Min Kim

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Abstract

Recent advancements in the development of low molecular-weight fluorophores have led to the study of a single-benzene fluorophore (SBF) containing both electron-withdrawing and electron-donating groups within an aromatic ring, resulting in unique photophysical properties. In this study, we explored the modulation of emissions by adjusting the electron-donating properties via the simple methylation of the 2,5-diamino or 2,5-dihydroxy terephthalate structure. Introducing additional functional groups under both symmetrical and unsymmetrical conditions demonstrated changes in the photophysical properties, which was not only owing to the structural variations in the location and number of methyl groups but also due to alterations in the electron-donating properties. The observed effects appeared to be owing to the interactions between the amine and ester groups, as confirmed via single-crystal X-ray diffraction. Finally, hydrolysis of the ester to the corresponding carboxylic acid resulted in various emission wavelengths at different pH values via protonation and deprotonation. This study provides valuable insights for predicting the structural and electronic effects of additional functional groups in SBF.

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通过简单甲基化调整单苯荧光团的结构和电子特性

近年来，随着低分子量荧光团研发的不断进步，人们开始研究一种单苯荧光团（SBF），这种荧光团在一个芳香环中同时含有电子吸收基团和电子供体基团，因而具有独特的光物理特性。在这项研究中，我们通过对 2,5- 二氨基或 2,5- 二羟基对苯二甲酸酯结构进行简单的甲基化，探索了通过调整电子捐赠特性来调节发射的方法。在对称和不对称条件下引入额外的官能团会导致光物理特性发生变化，这不仅是由于甲基的位置和数量的结构变化，也是由于电子捐赠特性的改变。单晶 X 射线衍射证实，观察到的影响似乎是由于胺和酯基团之间的相互作用造成的。最后，通过质子化和去质子化作用，将酯水解为相应的羧酸会在不同的 pH 值下产生不同的发射波长。这项研究为预测 SBF 中其他官能团的结构和电子效应提供了宝贵的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.