2D Conjugated Metal–Organic Frameworks: Defined Synthesis and Tailor-Made Functions

作者：Jingjuan Liu, Guolong Xing, Long Chen · 发表于：Accounts of Chemical Research · 年份：2024 · DOI：10.1021/acs.accounts.3c00788 · 被引用次数：116 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications、Graphene research and applications

Conspectus 2D conjugated metal–organic frameworks (2D -MOFs) have emerged as a class of graphene-like materials with fully π-conjugated aromatic structures. Their unique structural characteristics provide abundant physiochemical features, including regular nanochannels, high electrical conductivity, and customizable band gaps. Recent intensive research has significantly advanced this field, yet the exploration of 2D c -MOFs with enhanced features is limited by the availability of organic linkages and topologies. Designing novel ligands is essential for the construction of new 2D c -MOFs with high crystallinity, excellent conductivity, and tailor-made functions. In this Account, we summarize our recent contributions in fine-tuning the topology of 2D c -MOFs through precise ligand design, thereby giving them fantastic structures and tailor-made functions. First, we propose the concept of replacing planar ligands by nonplanar ligands on conductive MOF skeletons. The incorporation of nonplanar ligands improves the solubility of large π-conjugated organic molecules without interfering with the interlayer π-stacking. Our investigation discovered that conjugate polycyclic aromatics-based ligands can be synthesized through in situ Scholl reactions by means of oxidative cyclodehydrogenation of a nonplanar precursor ligand during the solvothermal synthesis process. Hence, fully conjugated 2D c -MOFs can be directly synthesized from nonplanar organic ligands, simplifying and diversifyin...