Two‐Dimensional Conjugated Metal–Organic Frameworks with a Ring‐in‐Ring Topology and High Electrical Conductance

• Published in: Angewandte Chemie Vol. 136; no. 26
• Main Authors: Yang, Mingyu, Zhang, Yi, Zhu, Renlong, Tan, Junjun, Liu, Jinxin, Zhang, Wei, Zhou, Meng, Meng, Zheng
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 21.06.2024
• Subjects: branched conjugation; Carrier mobility; Conductive 2D MOFs; Conjugation; Electrical conductivity; Electrical properties; Electrical resistivity; Heterogeneous double-pore; Ligands; Metal-organic frameworks; Terahertz Spectroscopy; Tessellation; Topology; X-ray diffraction
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202405333

Electrically conducting two‐dimensional (2D) metal–organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high‐performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M–DHHBTN (M=Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M–DHHBTN are elucidated through comprehensive analyses involving powder X‐ray diffraction, theoretical simulations, and high‐resolution transmission electron microscope. Optical‐pump terahertz‐probe spectroscopic measurements unveiled carrier mobility in DHHBTN‐based 2D MOFs spanning from 0.69 to 3.10 cm2 V−1 s−1. Among M–DHHBTN famility, Cu‐DHHBTN displayed high electrical conductivity reaching 0.21 S cm−1 at 298 K with thermal activation behavior. This work leverages the “branched conjugation” of the ligand to encode heteroporosity into highly conductive 2D MOFs, underscoring the significant potential of heterogeneous double‐pore structures for future applications. A new family of 2D conductive MOFs (named M–DHHBTN, M=Co, Ni, and Cu) with a unique ring‐in‐ring topology has been successfully constructed by using a highly branched and conjugated dodechydroxyhexabenzotrinaphthylene ligand, which offers the first example simultaneously achieving high electron conductivity and a heterogeneous dual‐pore structure in 2D MOFs.