文献类型：期刊文献

英文题名：Bent-to-planar Si-/P-rhodamine fluorophores: systematic electronic modification

作者：Lian, Dongsheng[1];Ma, Ying[1];Li, Weicheng[1];Wang, Shuairu[1];Sun, Chuyang[1];Yan, Chenxu[1];Lian, Cheng[1];Zhu, Wei-Hong[1];Guo, Zhiqian[1,2]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Key Lab Adv Mat,Inst Fine Chem,Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Bioreactor Engn, Shanghai Frontier Sci Res Base Optogenet Tech Cell, Shanghai 200237, Peoples R China

年份：2026

卷号：255

外文期刊名：DYES AND PIGMENTS

收录：;EI(收录号：20262821083873);Scopus(收录号：2-s2.0-105044095951);WOS:【SCI-EXPANDED(收录号:WOS:001823432600001)】；

基金：This work was supported by NSFC/China (22225805, T2488302, 32394001, 32121005, and 22378122), Shanghai Frontier Science Research Base of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission, grant 2021 Sci & Tech 03-28), Science and Technology Commission of Shanghai Municipality (24DX1400200), Shanghai Science and Technology Committee (23J21901600, 23ZR1416600, 25ZR1402326) .

语种：英文

外文关键词：Near-infrared; Xanthone; Rhodamine; Fluorophores; C-N coupling

摘要：Rhodamine dyes have garnered extensive interest owing to their outstanding fluorescence properties. However, while conventional rhodamines and many heteroatom-substituted (Si, S, P--O) analogs have been developed with emission extending to the near-infrared region, their synthesis often suffers from lengthy routes, low yields of key steps, and limited structural tunability, which still restrict their flexible wavelength modulation and practical bioimaging applications. This inherent limitation greatly hampers their utility in bioimaging applications. Herein, we report the systematic modulation of Si-and P-rhodamine fluorophores through substitution with an electron-withdrawing fluorine atom at the 2, 7-position and diverse electron-donating groups at the 3, 6position side chain. Our results demonstrate that incorporation of fluorine into the rhodamine skeleton results in a pronounced blue shift in both absorption and emission spectra. In contrast, the donor substituents and their specific connection modes to the side chain-particularly the bonding nature-critically govern the photo-physical characteristics of these dyes. We further reveal that the emissive behavior of Si-/P-rhodamine fluorophores is highly sensitive to both the donor linkage mode and acidification triggered by (COCl)2. Notably, meso-chlorination triggered by (COCl)2 induces a bent-to-planar conformational transition and significant bathochromic shift, and this efficient transformation occurs exclusively when donor moieties are attached to the xanthone scaffold through bilateral C-N bonds, which is critical for enabling high electron delocalization and activation of the meso-carbonyl group.