Multi-stimuli-responsive Zn(ii)-Schiff base complexes adjusted by rotatable aromatic rings

发光 位阻效应 配体(生物化学) 席夫碱 化学 结晶学 分子 亚甲基 荧光 晶体结构 光化学 立体化学 材料科学 受体 有机化学 物理 量子力学 生物化学 光电子学
作者
Han-Wen Zheng,Dong-Dong Yang,Qiong-Fang Liang,Xiang‐Jun Zheng
出处
期刊:Dalton Transactions [Royal Society of Chemistry]
卷期号:50 (45): 16803-16809 被引量:5
标识
DOI:10.1039/d1dt02476k
摘要

Multifunctional luminescent materials have attracted intensive interest. However, the mechanisms behind them are still to be explored. In this work, three Zn(II) complexes based on Schiff bases (HL1 and HL2) that contain rotatable aromatic rings were designed and prepared. They exhibited different mechanochromic luminescence (MCL) and acidochromism. The polymorphous ZnL12 and ZnL1a2 crystallize in different crystal systems with different conformations. The ligands in ZnL12 adopt a more twisted conformation than those in ZnL1a2. ZnL12 exhibits MCL with high contrast, while ZnL1a2 exhibits a negligible MCL property. This may be due to the looser packing of the complex induced by the more twisted conformation of the ligand HL1. ZnL12 could undergo crystal phase transformation into ZnL1a2 by grinding/fuming cycles. To increase the flexibility of the ligand, a methylene group was introduced to result in HL2, which can improve the mechanochromic luminescence effect of the Zn(II) complex with high color contrast. The ligands involved in coordination generally adopt a more twisted conformation than those free ligands due to the steric hindrance, resulting in more obvious MCL for complexes. By comparing the luminescence of ligands and their complexes under acid-base stimulation, it is found that the acidochromic properties could be attributed to the generation of ligands at the surface of complexes via the gaseous HCl-solid Zn(II) complex reaction. The high contrast mechanochromic and acidochromic luminescence properties would lead to promising potential applications of these complexes in smart fluorescent materials, and would also provide some ideas for the design of multi-stimuli responsive molecules.
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