Conjugated Nonplanar Copper-Catecholate Conductive Metal–Organic Frameworks via Contorted Hexabenzocoronene Ligands for Electrical Conduction
Guolong Xing, Jingjuan Liu, Yi Zhou, Shuai Fu, Jia‐Jia Zheng, Xi Su, Xingfa Gao, Osamu Terasaki, Mischa Bonn, Hai I. Wang, Long Chen
Abstract
Conductive metal–organic frameworks ( c -MOFs) with outstanding electrical conductivities and high charge carrier mobilities are promising candidates for electronics and optoelectronics. However, the poor solubility of planar ligands greatly hinders the synthesis and widespread applications of c -MOFs. Nonplanar ligands with excellent solubility in organic solvents are ideal alternatives to construct c -MOFs. Herein, contorted hexabenzocoronene ( c -HBC) derivatives with good solubility are adopted to synthesize c -MOFs. Three c -MOFs ( c -HBC-6O-Cu, c -HBC-8O-Cu, and c -HBC-12O-Cu) with substantially different geometries and packing modes have been synthesized using three multitopic catechol-based c -HBC ligands with different symmetries and coordination numbers, respectively. With more metal coordination centers and increased charge transport pathways, c -HBC-12O-Cu exhibits the highest intrinsic electrical conductivity of 3.31 S m –1 . Time-resolved terahertz spectroscopy reveals high charge carrier mobilities in c -HBC-based c -MOFs, ranging from 38 to 64 cm 2 V –1 s –1 . This work provides a systematic and modular approach to fine-tune the structure and enrich the c -MOF family with excellent charge transport properties using nonplanar and highly soluble ligands.