Molecular Engineering of Metal-Organic Layers for Sustainable Tandem and Synergistic Photocatalysis.

Metal-organic layers (MOLs), a monolayered version of metal-organic frameworks (MOFs), have recently emerged as a novel two-dimensional molecular material platform to design multifunctional catalysts. MOLs inherit the intrinsic molecular tunability of MOFs and yet have more accessible and modifiable building blocks. Here we report molecular engineering of six MOLs via modulated solvothermal synthesis between HfCl 4 and three photosensitizing ligands followed by postsynthetic modification with two carboxylate-containing cobaloximes for tandem and synergistic photocatalysis. Morphological and structural characterization by transmission electron microscopy and atomic force microscopy and compositional analysis by inductively coupled plasma-mass spectrometry and nuclear magnetic resonance spectroscopy establish the MOLs as flat nanoplates with a periodic lattice structure of hexagonal symmetry. The MOLs efficiently catalyze tandem dehydrogenative coupling reactions and synergistic Heck-type coupling reactions. The most active MOL catalyst was used for the gram-scale synthesis of vesnarinone, a cardiotonic agent, in 80% yield with a turnover number of 400 and in eight consecutive reaction cycles without significant loss of activities.