Silver(III)⋅⋅⋅Silver(III) Interactions that Stabilize the syn Form in a Porphyrin Dimer Upon Oxidation

Singh, Akhil Kumar ; Khan, Firoz Shah Tuglak ; Rath, Sankar Prasad (2017) Silver(III)⋅⋅⋅Silver(III) Interactions that Stabilize the syn Form in a Porphyrin Dimer Upon Oxidation Angewandte Chemie International Edition, 56 (30). pp. 8849-8854. ISSN 1433-7851

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Official URL: http://doi.org/10.1002/anie.201705108

Related URL: http://dx.doi.org/10.1002/anie.201705108

Abstract

The interaction between two AgII porphyrins, connected covalently through a highly flexible ethane bridge, in a metalloporphyrin dimer has been investigated upon stepwise oxidation. X-ray structure determination of one and two-electron oxidized complexes has clearly revealed only metal-centered oxidation that results in short Ag−N (porphyrin) distance with large distortion in the porphyrin macrocycle. The 2e-oxidized complex exhibits significant metallophilic interaction in the form of a close AgIII⋅⋅⋅AgIII contact that brings two porphyrin rings more cofacial with syn-conformation, which would otherwise stabilize in an anti-form. The interaction also leads to an intense emission peak at 546 nm at 77 K in the photoluminescence study.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons, Inc.
ID Code:120837
Deposited On:06 Jul 2021 06:22
Last Modified:06 Jul 2021 06:22

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