Abstract
Summary The complexity of Ti chemistry in solution not only leads to the difficulty of isolating crystalline titanium metal-organic frameworks (Ti-MOFs) but also brings the challenge of controlled assembly of the crystal structure. We report here the first example of a controlled synthesis of a Ti-MOF structure through a linker-exchange strategy directly from a preformed Ti-O cluster. A Ti8O8 cluster precursor with terminal formate and acetate ligands (Ti8AF) was reacted with trimesic acid (BTC) under green and mild conditions, generating a microporous Ti-MOF (MIP-207) while preserving the connection and configuration of the Ti8O8 core. In addition, due to the ditopic meta-positional connection mode of the linker, the chemical environment and functionality of the structural voids could be easily tuned by substituting trimesate moieties with isophthalate-type linkers via concise one-pot reactions. This finally resulted in an adjustable performance in CO2 capture over N2.
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