Vapor-phase synthesis of low-valent metal-organic frameworks from metal carbonyl synthons

Carl Emil Andersen, James Neill McPherson, Mónica Giménez-Marqués, Jingguo Li, Mariusz Kubus, Sho Ito, Christian R. Göb, Sascha Ott, René Wugt Larsen, Guillermo Mínguez Espallargas, Kasper S. Pedersen*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review


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. Metal carbonyls are bona fide low-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 vapor-phase substitution of CO by ditopic 4,4′-bipyridine at Mo(0) and W(0) centers, which allows facile coating of low-valent MOFs onto substrates such as indium tin oxide. We envisage this strategy could be generalized to a multitude of mono- and polynuclear metal carbonyls, paralleling the diversity of conventional MOFs.

Original languageEnglish
JournalJournal of Materials Chemistry C
Issue number34
Pages (from-to)11460-11465
Publication statusPublished - 2023


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