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.

中文翻译：

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具有环中环拓扑和高电导率的二维共轭金属有机框架

导电二维（2D）金属有机框架（MOF）由于其卓越的结构可调性和出色的电性能而引起了人们的极大兴趣。然而，由于特定配体和孔结构的可用性有限，高性能材料的设计和合成面临着挑战。在这项研究中，我们采用了一种新型的高度支化的D3h对称平面共轭配体十二羟基六苯并三萘（DHHBTN）来制造一系列二维导电MOF，命名为M-DHHBTN（M = Co、Ni和Cu）。这个新的 MOF 系列提供两种不同类型的孔隙，将二维导电 MOF 的结构复杂性提升到了更高级的水平。通过粉末 X 射线衍射、理论模拟和高分辨率透射电子显微镜的综合分析，阐明了 M-DHHBTN 复杂的镶嵌图案。光泵太赫兹探针光谱测量揭示了基于 DHHBTN 的 2D MOF 中的载流子迁移率，范围从 0.69 到 3.10 cm2 V-1 s-1。在M-DHHBTN家族中，Cu-DHHBTN表现出高电导率，在298 K时达到0.21 S cm−1，并具有热活化行为。这项工作利用配体的“支化共轭”将异质孔隙编码到高导电性的二维 MOF 中，强调了异质双孔结构在未来应用中的巨大潜力。