Lactonization of dyes promoted by a coordination cage facilitates cavity-induced chromism as ion mobile detector  

作　　者：Liangliang Zhang Yu Liang Zhifeng Xiao Yuxuan Meng Jinyi Huang Xi Lin Ji Li Hong-Cai Zhou Yu Fang 

机构地区：[1]Strait Institute of Flexible Electronics(SIFE,Future Technologies),Fujian Normal University and Strait Laboratory of Flexible Electronics(SLoFE),Fuzhou 350017,China [2]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,China [3]Department of Chemistry,Texas A&M University,College Station,Texas 77842-3012,USA [4]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [5]Frontiers Science Center for Flexible Electronics(FSCFE),MIIT Key Laboratory of Flexible Electronics(KLoFE),Northwestern Polytechnical University,Xi’an 710072,China

出　　处：《Science China Chemistry》2024年第5期1554-1560,共7页中国科学（化学英文版）

基　　金：supported by the Fujian Province Natural Science Foundation (2023J01294);the Natural Science Basic Research Program of Shaanxi (2023-JC-YB-088);the National Natural Science Foundation of China (21501133, 22371067);the China Hunan Provincial Science&Technology Department (2020RC3020, 2021JJ20021,2023JJ40119)。

摘　　要：Dye molecules often change colors(so-called “chromism”) according to the environment variation. However, they are rarely induced by a catalytic amount of cavity. Through encapsulation in the cavity of a porous coordination cage(PCC-2), Rhodamine B(1) is transformed from red quinonoid form(1q) into colorless lactone form(1l) in aprotic polar solutions. The μ4-OH groups in the cavity of PCC-2 are shown to stabilize the uncommon zwitterion intermediate(1z), followed by converting to 1l, thus accelerating the equilibrium. The chromism is catalyzed by 0.25 mol% of PCC-2, and the reaction rate is improved by 80,400times. 1@PCC-2 can be further fabricated to a sol-gel that exhibits ion recognition properties. The resulting encapsulation and stabilization of an unconventional intermediate by a catalytic amount of the coordination cage provides fundamental insights into molecular isomerization and has potential use in chemical sensing.

关 键 词：porous coordination cage Zwitterion intermediate CAVITY Rhodamine B chromism 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]