Jianjun Zhang, Guojun Zhou, Hio-Ieng Un, Jianbo Song, Petko St Petkov, Rashid Iqbal, Shuai Fu, Xing Huang, Geping Zhang, Yang Lu, Darius Pohl, Renxiang Liu, Yubin Fu, Xiaodong Li, Wenjie Zhang, Bernd Rellinghaus, Alexey Alfonsov, Volodymyr Bon, Jie Ding, Stuart S P Parkin, Thomas Heine, Zhiyong Wang, Zhehao Huang, Henning Sirringhaus, Xinliang Feng, Renhao Dong
Electrically conductive two-dimensional (2D) conjugated metal-organic frameworks (c-MOFs) are emerging electronic materials with tunable topologies and metal nodes. However, the uniform reactivity of conventional high-symmetry ligands typically leads to homogeneous linking, limiting the programmable construction of diverse topologies and metal nodes from a single-type ligand. Here we report an anisotropic reticular chemistry strategy using the 1,2,5,6,9,10,12,13-octahydroxydibenzo-[fg,op]naphthacene ligand with diverse catechol reactivities to construct seven distinct c-MOF crystals. Site-selective coordination of 1,2,5,6,9,10,12,13-octahydroxydibenzo-[fg,op]naphthacene yields three topologically distinct copper-based c-MOFs, including 2D square-arranged (Cu-2D-sql), 2D honeycomb-arranged (Cu-2D-hcb) and one-dimensional linear (Cu-1D) structures. Cu-1D could further react with metal ions to produce four bimetallic CuM-2D-sql (M = Ni, Co, Zn or Mn) with defined bimetal node arrangements. Theoretical modelling and single-crystal electrical measurements reveal that this structural programming effectively modulates the charge transport behaviour. The anisotropic reticular chemistry strategy thus provides a route towards atomic-level control over the structures and electronic properties of conductive frameworks.