SCHEDULED MAINTENANCE
Vapor-phase synthesis of low-valent metal–organic frameworks from metal carbonyl synthons†
a
James Neill
McPherson,
a
Mónica
Giménez-Marqués,
b
Jingguo
Li,
c
Sho
Ito,
d
Christian R.
Göb,
e
Sascha
Ott,
c
René Wugt
Larsen,
a
Guillermo
Mínguez Espallargas
b
and
Kasper S.
Pedersen
*a
Abstract
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.
- This article is part of the themed collections: Fundamentals and Applications of Functional Framework Materials, Journal of Materials Chemistry C HOT Papers and #MyFirstJMCC
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