Zhang Yan-Yan, Chen Ze-Yao, Li Qian-Ge, Jin Xin-Xin, Cao Miao, Sun Rong, Wang Bing-Wu, Li Peng, Sui Qi
Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province, School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China.
Beijing National Laboratory for Molecular Science, Beijing Key Laboratory for Magnetoelectric Materials and Devices, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
Inorg Chem. 2024 Sep 2;63(35):16274-16283. doi: 10.1021/acs.inorgchem.4c02210. Epub 2024 Aug 18.
Different types of electron transfers (ETs) underlie the versatile use of various solid viologen-derived compounds, which is still insufficiently understood and difficult to control. Here, we demonstrate an effective strategy for modulating the key ET process in crystalline metalloviologen compounds (MVCs). By adjusting the coordinated transition metal ions bearing different electronic structures (e.g., , , ), three MVCs (i.e., , , and ) with highly consistent coordination environments have been synthesized successfully. Surprisingly, whether the photochromism (energy-induced ET mechanism) or the specific analyte recognition (molecule-induced ET mechanism), compound exhibits obvious photochromic behavior and differential dimethylamine detection. Combined detailed structural analysis with theoretical calculations, such unique ion-dependent properties, were correlated to the fine modulation of the electron density of the bipyridinium cores by metal ions. Additionally, thanks to the delicate recognition of dimethylamine vapor, a convenient test strip was prepared as a sensitive biogenic amine sensor for evaluating the real-time freshness of seafood.
不同类型的电子转移（ETs）是各种固体紫精衍生化合物广泛应用的基础，然而人们对其了解尚不充分且难以控制。在此，我们展示了一种调控结晶金属紫精化合物（MVCs）中关键ET过程的有效策略。通过调整具有不同电子结构的配位过渡金属离子（例如， ， ），成功合成了三种具有高度一致配位环境的MVCs（即 ， 和 ）。令人惊讶的是，无论是光致变色（能量诱导ET机制）还是特定分析物识别（分子诱导ET机制），化合物 都表现出明显的光致变色行为和对二甲胺的差异检测。结合详细的结构分析与理论计算，这种独特的离子依赖性性质与金属离子对联吡啶核心电子密度的精细调控相关。此外，由于对二甲胺蒸汽的灵敏识别，制备了一种便捷的测试条作为灵敏的生物胺传感器，用于评估海鲜的实时新鲜度。
