Packing Order Control in Conductive Metal–Organic Frameworks by Tuning Ligand Oxidation State
Abstract
Abstract Conductive metal–organic frameworks (c‐MOFs), composed of metal nodes and redox‐active ligands, have attracted growing interest due to the coexistence of porosity and charge transport. Notably, their electrical performance is closely related to the packing and ligand oxidation state within the framework, which has rarely been explored. Typical divalent metal nodes favor saturated intralayer square‐planar coordination to ligands in a single oxidation state, thereby predetermining the framework topology. Here, we report a packing and topology control strategy, achieved by tuning the ligand oxidation state and grounded in lanthanides (e.g., Gd) versatile coordination chemistry. Diffuse reflectance spectroscopy and single‐crystal transport measurements reveal that, at low temperature, coordination of Gd 3+ with 2,3,6,7,10,11‐hexahydroxytriphenylene (HHTP) in a lower mixed oxidation state (−4 and −5) yields a more ordered porous packing (Gd 1.5 HHTP) with superior electronic transport performance. In contrast, at elevated temperature, the ligand adopts a higher oxidation state (−3), and coordination with Gd 3+ yields a densely packed structure with local coordination disorder (GdHHTP), resulting in a markedly reduced electrical conductivity. This study demonstrates ligand‐oxidation‐state tuning provides an effective strategy for the precise control of structural order and charge transport in c‐MOFs, laying a theoretical foundation for the rational design of materials with tunable electronic properties.
Article Details
Authors (15)
Yunlong Fan
National Key Laboratory of Advanced Micro and Nano Manufacture Technology, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, School of Materials Science and Engineering
Bin Jiang
Zhenghan Zhang
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering
Haoyang Zhang
National Key Laboratory of Advanced Micro and Nano Manufacture Technology, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, School of Materials Science and Engineering
Luming Yang
Research Group ESR Spectroscopy
Tianyang Chen
School of Science and Engineering, The Chinese University of Hong Kong (Shenzhen), Longgang, Shenzhen, Guangdong 518172, China
Liu He
National Key Laboratory of Advanced Micro and Nano Manufacture Technology, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, School of Materials Science and Engineering
Yanjun Liu
Jinkun Guo
National Key Laboratory of Advanced Micro and Nano Manufacture Technology, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, School of Materials Science and Engineering
Tongyang Zhao
National Key Laboratory of Advanced Micro and Nano Manufacture Technology, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, School of Materials Science and Engineering
Ran Du
Cen Tang
CAS Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety National Center for Nanoscience and Technology Beijing China
Jian Li
Maojun Zheng
Key Laboratory of Artificial Structure and Quantum Control Ministry of Education School of Physics and Astronomy Shanghai Jiao Tong University Shanghai 200240 P.R. China
Jin‐Hu Dou
National Key Laboratory of Advanced Micro and Nano Manufacture Technology Key Laboratory of Polymer Chemistry and Physics of Ministry of Education School of Materials Science and Engineering Peking University Beijing 100871 P.R. China