Unconventional Method for Fabricating Valence Tautomeric Materials: Integrating Redox Center within a Metal–Organic Framework

Due to the structural advantages displayed by Metal–Organic Frameworks (MOFs), integrating Valence Tautomerism (VT) systems within MOFs could be an effective strategy in order to break through the constraints of the traditional ones. Herein, we report the first successful integration of a VT system into a MOF termed VT-MOF-1. The structural characteristics of VT-MOF-1, such as dinuclear cobalt-catechol clusters and solvent-accessible pores, are both innovative and novel, potentially yielding new vitality within VT field. In addition, VT-MOF-1 exhibits specific behaviors responsive to temperature and different solvent molecules as n-butanol, tert-butanol, and isopropyl alcohol. The entropy values and configurations of the solvent molecules might be responsible for the tunable sensing behaviors.鉴于金属有机框架（Metal–Organic Frameworks，MOFs）所展现出的结构优势，将价态互变异构（Valence Tautomerism，VT）体系引入MOFs中，不失为突破传统体系局限的有效策略。本文首次成功将VT体系整合至名为VT-MOF-1的金属有机框架材料中。VT-MOF-1的结构特征（如双核儿茶酚合钴簇与溶剂可及孔道）兼具创新性与新颖性，有望为价态互变异构研究领域注入全新活力。此外，VT-MOF-1展现出对温度以及正丁醇、叔丁醇、异丙醇等不同溶剂分子的特异性响应行为。溶剂分子的熵值与构型，或是其可调谐传感性能的内在成因。