Through‐Space CBr···π Halogen Interaction: Efficient Modulation of Reaction‐Based Photochromism and Photoluminescence at Crystalline States for Irradiation Time‐Dependent Anti‐Counterfeiting. (30th November 2020)

• Record Type: Journal Article
• Authors: Zhou, Zhibiao; Liu, Qing; Chen, Xian; Xu, Gaoqiang; Wang, Shuodong; Tu, Yujie; Zhang, Jia; Zheng, Xiaoyan; Xiang, Jiannan; Feng, Xing; Zhang, Yang; Xie, Sheng; Zeng, Zebing; Tang, Ben Zhong
• Is Part Of: Advanced functional materials. Volume 31:Number 10(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-11-30
• Subjects: aggregation‐induced emission -- anti‐counterfeiting -- halogen‐π interaction -- photo‐responsive solid‐state materials -- reaction‐based photochromism; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202009024
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: Reaction‐based photo‐responsive molecular systems have been used as a reliable platform for building intelligent materials, but often suffer from high inactivity in terms of conversion efficiency and reversibility when it comes to solid‐state applications. Herein, a class of Spiro‐conjugated diphenylindene (DPI) aggregation‐induced emission materials that exhibit solid‐state photocyclization‐based photochromism and photoluminescence, achieved by manipulating through‐space CBr···π halogen interactions is reported. In the crystalline state, the Spiro bridge enables a pair of perpendicularly configured CBr···π interactions that suppress photoluminescence while activating a highly reversible (>10 000 cycles) and efficient photochromism based on photocyclization. After breaking this intermolecular CBr···π interaction, for example, by grinding, the solid‐state photochromic properties are sensitively de‐activated. In addition, this spontaneously reversible photochromism behavior gives a controllable decolorization time (from a few seconds to a few minutes), depending on the light exposure conditions, while displaying a luminescence change. In a proof‐of‐principle study, these photo‐function features demonstrate an attractive potential for novel anti‐counterfeiting applications. This work reveals the efficient regulation of CBr···π halogen interactions for spatial molecular packing, molecular electronic transitions, and chemical transformations, paving the way for the development of solid‐state intelligent materials with good reversibility. Abstract : The Spiro hybridized diphenylethene derivatives feature a rarely robust crystalline‐state photochromism behavior with irradiation color‐dependent self‐decoloration, accomplished by the state‐dependent photoluminescence. This unique solid‐state photo‐activity is achieved by modulating the photocyclization activity through a pair of through‐space CBr···π halogen interactions. This work demonstrates a reliable strategy for the rational design of reaction‐based solid‐state materials with modulable multifunctionalities for potentially novel anti‐counterfeiting applications.