Resolving orbital pathways for intermolecular electron transfer
| Autor: | Gerald J. Meyer, Michael D. Turlington, Curtis P. Berlinguette, Cameron W. Kellett, Wesley B. Swords |
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| Rok vydání: | 2018 |
| Předmět: |
Science
General Physics and Astronomy chemistry.chemical_element 02 engineering and technology 010402 general chemistry 01 natural sciences Article General Biochemistry Genetics and Molecular Biology Homologous series chemistry.chemical_compound Electron transfer Atomic orbital Physics::Chemical Physics lcsh:Science Multidisciplinary Intermolecular force Resolution (electron density) General Chemistry 021001 nanoscience & nanotechnology Acceptor 0104 chemical sciences Ruthenium Condensed Matter::Soft Condensed Matter chemistry Chemical physics Covalent bond lcsh:Q 0210 nano-technology |
| Zdroj: | Nature Communications Nature Communications, Vol 9, Iss 1, Pp 1-10 (2018) |
| ISSN: | 2041-1723 |
| Popis: | Over 60 years have passed since Taube deduced an orbital-mediated electron transfer mechanism between distinct metal complexes. This concept of an orbital pathway has been thoroughly explored for donor–acceptor pairs bridged by covalently bonded chemical residues, but an analogous pathway has not yet been conclusively demonstrated for formally outer-sphere systems that lack an intervening bridge. In our present study, we experimentally resolve at an atomic level the orbital interactions necessary for electron transfer through an explicit intermolecular bond. This finding was achieved using a homologous series of surface-immobilized ruthenium catalysts that bear different terminal substituents poised for reaction with redox active species in solution. This arrangement enabled the discovery that intermolecular chalcogen⋯iodide interactions can mediate electron transfer only when these interactions bring the donor and acceptor orbitals into direct contact. This result offers the most direct observation to date of an intermolecular orbital pathway for electron transfer. It is known that intermolecular interactions impact electron transfer rates, but the mechanisms involved are challenging to define experimentally. Here, the authors have developed a platform that enables atomic orbital resolution of electron transfer through an explicit intermolecular interaction. |
| Databáze: | OpenAIRE |
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