Effects of nonaromatic through-bond conjugation and through-space conjugation on the photoluminescence of nontraditional luminogens  

作　　者：Xiaomi Zhang Yunhao Bai Junwen Deng Peifeng Zhuang Huiliang Wang 

机构地区：[1]Beijing Key Laboratory of Energy Conversion and Storage Materials,College of Chemistry,Beijing Normal University,Beijing,China

出　　处：《Aggregate》2024年第3期348-361,共14页聚集体（英文）

基　　金：Program for Changjiang Scholars and Innovative Research Team(PCSIRT)in University;National Natural Science Foundation of China,Grant/Award Number:21574015。

摘　　要：Photoluminescence(PL)mechanisms of nontraditional luminogens(NTLs)have attracted great interest,and they are generally explained with intra/intermolecular through-space conjugation(TSC)of nonconventional chromophores.Here a new concept of nonaromatic through-bond conjugation(TBC)is proposed and it is proved that it plays an important role in the PL of NTLs.The PL behaviors of the three respective isomers of cyclohexanedione and gemdimethyl-1,3-cyclohexanedione were studied and correlated with their chemical and aggregate structures.These compounds show differentfluorescence emissions as well as dif-ferent concentration,excitation and solvent-dependent emissions.The compounds which undergo keto-enol tautomerism and hence with a conjugated ketone-enol structure(i.e.,nonaromatic TBC)show more red-shifted emissions.TBC effect reduces the energy gaps and facilitates the formation of stronger TSC in the aggre-gate state.The compounds in the ketone-enol form are also prone to occur excited state intra/intermolecular proton transfer(ESIPT).The cooperative effect of nonaro-matic TBC and TSC determines the PL behaviors of NTLs.This work provides a novel understanding of the PL mechanisms of NTLs and is of great importance for directing the design and synthesis of novel NTLs.

关 键 词：nontraditional luminogens cooperative effect through-bond conjugation through-space conjugation 

分 类 号：O62[理学—有机化学]