Vapor-Phase Synthesis of Metal-Organic Frameworks from Homoleptic Metal Carbonyl Synthons

Incorporating low-valent metals as nodes in metal-organic frameworks (MOFs) is orthogonal to the commonly accepted strategy to robust and porous structures. The electronic structures of low-valent metals are chemically unique and have driven the successes of organometallic chemistry. The translation of these properties into MOFs is largely impeded by the lack of generalizable synthetic approaches. Homoleptic metal carbonyls are bona fide zero-valent and volatile synthons, which, by partial chemical substitution may tether ditopic ligands into MOF architectures. We herein demonstrate the formation of CO2 adsorbing MOFs from the direct gas-phase substitution of CO by ditopic 4,4′-bipyridine at Mo and W centers. This approach allows facile gas phase coating of these MOFs onto substrates such as indium tin oxide. We envisage this strategy could be generalized to a multitude of mono- and polynuclear metal carbonyls, thereby paralleling the diversity of conventional MOFs.