Diosmium compounds containing bis(imidazole)- p -quinone bridging ligands
The doubly deprotonated bridging ligand L derived from 2,6-bis(2-pyridyl)-1,5-dihydro-1',4'-benzoquinono[2',3'- :5',6'- ']diimidazole H L forms coordination compounds with two bis(2,2'-bipyridine)osmium(II) complex fragments in ([1](ClO ) ) and configurations...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry Vol. 51; no. 10; p. 4058 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
England
08.03.2022
|
| ISSN: | 1477-9234, 1477-9234 |
| Online Access: | Get more information |
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| Summary: | The doubly deprotonated bridging ligand L
derived from 2,6-bis(2-pyridyl)-1,5-dihydro-1',4'-benzoquinono[2',3'-
:5',6'-
']diimidazole H
L
forms coordination compounds with two bis(2,2'-bipyridine)osmium(II) complex fragments in
([1](ClO
)
) and
configurations ([2](ClO
)
) of {(μ-L
)[Os(bpy)
]
}(ClO
)
, as evident from crystal structure analyses. Exchange of the metal-coordinating 2-pyridyl functions in the bridge through non-coordinating 4-tolyl substituents (L
→ L
) leads to [3](ClO
)
which involves chelation of the [Os(bpy)
]
groups through imidazole-N and carbonyl-O atoms of the central
-quinone function. In addition to identification, the compounds were subjected to electrochemical (CV, DPV) and spectroelectrochemical (UV-vis-NIR, EPR) analyses of electron transfer, the results being supported by results from TD-DFT calculations. Essential differences between [1
]/[2
] and [3
] systems were found regarding variable but mostly metal centred oxidation, the two processes separated much more for [3
]. The first reduction is bpy ([1
], [2
]) or quinone ligand centred ([3
]). Electronic structures and electron transfer behaviour are thus highly sensitive to differences of configuration and coordination. |
|---|---|
| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1477-9234 1477-9234 |
| DOI: | 10.1039/d2dt00184e |