Synthesizing Cr-Based Two-Dimensional Conjugated Metal-Organic Framework Through On-Surface Substitution Reaction.

A single-layer Cr 3 (HITP) 2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) conjugated metal-organic framework (c-MOF) is synthesized under ultrahigh vacuum conditions by substituting Cr for Ni in Ni 3 (HITP) 2 template. As revealed by low-temperature scanning tunneling microscopy and scanning tunneling spectroscopy, while codeposition of Cr atoms and 2,3,6,7,10,11-hexaaminotriphenylene precursors produces irregular branches, crystalline Cr 3 (HITP) 2 frameworks are obtained by depositing Cr atoms to the Ni 3 (HITP) 2 templates. The density functional theory calculations reveal that the binding energy between Cr and HITP ligands is much higher than that for Ni, which hampers the growth of crystalline Cr 3 (HITP) 2 frameworks through direct coordination assembly but makes the substitution reaction energetically favorable. This work demonstrates a new strategy to prepare high-quality early-transition-metal-based c-MOFs under ultrahigh vacuum conditions.