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Excimer Formation of Perylene Bisimide Dyes within Stacking-Restrained Folda-Dimers:Insight into Anomalous Temperature Responsive Dual Fluorescence

查看全文 作　　者：Congdi [1,2]Shang;Gang [2]Wang;Yu-Chen [3]Wei;Qingwei [2]Jiang;Ke [2]Liu;Meiling [2]Zhang;Yi-Yun [3]Chen;Xingmao [2]Chang;Fengyi [2]Liu;Shiwei [2]Yin;Pi-Tai [3]Chou;Yu [2]Fang 高影响力作者 机构地区：[1]College of Food Science and Engineering,Northwest A&F University,Shaanxi,Yangling 712100;[2]Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education,School of Chemistry and Chemical Engineering,Shaanxi Normal University,Shaanxi,Xi’an 710062;[3]Department of Chemistry,Taiwan University,Taipei 10617高影响力机构 出　　处：《CCS Chemistry》索引2022年第4卷第6期,共12页高影响力期刊 基　　金：the Natural Science Foundation of China(nos.21820102005,21527802,and 21673133);China 111 project(no.B14041);Program for Changjiang Scholars and Innovative Research Team in University(no.IRT-14R33). 摘　　要：We have fabricated a new perylene bisimide(PBI)folda-dimer(BPBI-CB-1)by tethering two PBI moieties to the ortho-carbon positions of a carborane unit.The synthesized compound adopted distinct configurations in different solvents with dual emissions as its characteristic.The two PBI moieties in the molecule appeared either in a weakly interacted,monomer-like state or brought into close π-π contact with each other,forming an interacted stacking state.The equilibrium between these two states was governed by the nature of solvents and testing temperature.Spectroscopic and theoretical studies concluded that dual emission bands originated from intramolecular monomer-like and stacking states,respectively.Remarkably,in a solvent like 1,2-dichloroethane(DCE),both emission intensities increased with rising temperatures.The positive temperature response of the monomer emission was ascribed to an increased amount of monomer-like population,owing to its endothermic energy state,while the excimer emission was rationalized by increased population of the bright exciton state,resulting in an increased emission yield that compensated the diminished population of the stacking state.To our knowledge,this is the first report on positive temperature-responsive dual emissions associated with the synergism of intramolecular intersubunit aggregation/dissociation and excimer transformation. 关 键 词：perylene bisimide folda-dimer intramolecular aggregation positive temperature effect carborane derivative
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