Guest-induced topological transformation and near-infrared photothermal conversion featuring the Cp*Rh unit via coordination-driven self-assembly  

作　　者：Xin-Yu Wang Qiu-Shui Mu Xiang Gao Guo-Xin Jin 

机构地区：[1]Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,State Key Laboratory of Molecular Engineering of Polymers,Department of Chemistry,Fudan University,Shanghai 200438,China

出　　处：《Science China Chemistry》2025年第4期1345-1354,共10页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China(22031003,21720102004,and 22301040);the Shanghai Science Technology Committee(19DZ2270100).

摘　　要：Herein;we perform a topological transformation by guest induction;converting[2]catenane Rh-1 into the Rh-3 molecular figure-of-eight.The transformation involves the interaction of longerπ-acceptor half-sandwich RhⅢbimetallic building block B1[(Cp*Rh)2(TPPHZ)](OTf)4 and π-donor bipyridyl ligands 4;4'-bis((pyridin-4-ylthio)methyl)-1;1'-biphenyl with four molecules of pyrene under ambient temperature in high yields.Intriguingly;despite the involvement of a single pyrene molecule in modifying[2]catenane Rh-2 by transitioning B1 to B2;the underlying skeleton of Rh-2 remains unaltered.Furthermore;we explored the application of these substances before and after the reaction for near-infrared(NIR)photothermal conversion.Through meticulous structural analysis;the π-π stacking interactions play a pivotal role in stabilizing the abovementioned structures;enhancing the nonradiative transitions and initiating photothermal conversion in solution.Based on the results;the introduction of pyrene significantly intensified the π-π stacking interactions but diminished the electron density between the adjacent NDI units;leading to a decrease in the NIR photothermal conversion efficiency(from 58.29%to 51.60%).In this study;an innovative approach is introduced for fabricating valuable half-sandwich-structured NIR photothermal conversion materials;and this research has promising prospects for enhancing the field of materials science with potential candidates for future development.

关 键 词：topological transformation guest-induced self-assembly molecular figure-of-eight near-infrared photothermal conversion 

分 类 号：O641.3[理学—物理化学]