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Linker Rectifiers for Covalent Attachment of Transition‐Metal Catalysts to Metal‐Oxide Surfaces
Author(s) -
Ding Wendu,
Negre Christian F. A.,
Palma Julio L.,
Durrell Alec C.,
Allen Laura J.,
Young Karin J.,
Milot Rebecca L.,
Schmuttenmaer Charles A.,
Brudvig Gary W.,
Crabtree Robert H.,
Batista Victor S.
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201400063
Subject(s) - electron transfer , covalent bond , chemistry , catalysis , amide , electron paramagnetic resonance , molecule , transition metal , photochemistry , oxide , metal , organic chemistry , nuclear magnetic resonance , physics
Linkers that favor rectification of interfacial electron transfer are likely to be required for efficient photo‐driven catalysis of multi‐electron reactions at electrode surfaces. Design principles are discussed, together with the synthesis and characterization of a specific pair of molecular linkers, related by inversion of the direction of an amide bond in the heart of the molecule. The linkers have a terpyridyl group that can covalently bind Mn as in a well‐known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO 2 surfaces. The appropriate choice of the sense of the amide linkage yields directionality of interfacial electron transfer, essential to enhance electron injection and slow back‐electron transfer. Support comes from electron paramagnetic resonance and terahertz spectroscopic measurements, as well as computational modeling characterizing the asymmetry of electron transfer properties.