Fluoro-bridged dimanganese(III) porphyrin dimer: Effect of intermacrocyclic interactions in modulating metal spin state
| Autor: | Sankar Prasad Rath, Sayantani Banerjee, Debangsu Sil, Sudip Ghosh |
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| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | Journal of Porphyrins and Phthalocyanines. 25:522-532 |
| ISSN: | 1099-1409 1088-4246 |
| DOI: | 10.1142/s1088424621500401 |
| Popis: | The synthesis, structure, and spectroscopic properties of a remarkably deformed dimanganese(III)-[Formula: see text]-fluoro porphyrin dimer in connection to its diiron(III) [Formula: see text]-fluoro and [Formula: see text]-hydroxo counterparts is reported. It is the most recent addition to the continued effort in understanding the effect of intermacrocyclic interaction on the molecular structure and properties of di-heme proteins. The dimanganese(III)-[Formula: see text]-fluoro porphyrin dimer, similar to its [Formula: see text]-hydroxo analogs, stabilizes two equivalent high-spin ([Formula: see text]= 2) manganese(III) centers. This is in contrast to the diiron(III) analogs where the [Formula: see text]-hydroxo complex stabilizes two inequivalent iron(III) centers with two different spin states of iron in the same molecule while the [Formula: see text]-fluoro complex stabilizes two equivalent metal centers with intermediate spin ([Formula: see text]= 3/2) state. The present results further establish the extreme interdependence of the energetically accessible spin states of the metal and the extent of porphyrin core deformation. It is very likely that nature utilizes the same powerful tool to modulate large change in the electronic structure and properties of the heme center needed for its function. |
| Databáze: | OpenAIRE |
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