Intermacrocyclic Interactions upon Stepwise Oxidations in a Monometallic Porphyrin Dimer: Ring versus Metal-Center Oxidations and Effect of Counter Anions.
Chemistry
; 26(63): 14405-14418, 2020 Nov 11.
Article
em En
| MEDLINE
| ID: mdl-32567719
ABSTRACT
The effect of intermacrocyclic interactions was studied by controlled and stepwise oxidations of a monometallic silver(II) porphyrin dimer that contains a highly flexible ethane bridge. Monometallic dimers are unique systems and behave differently from their dimetallic analogues on the basis of their available sites for storing oxidizing equivalents. UV-visible spectrometry, 1 Hâ
NMR spectroscopy, XPS and single crystal X-ray diffraction studies clearly suggest the removal of the first electron from the metal center. The removal of the second electron occurred from the ring center to form a π-cation radical and, thereby, form a very unique mixed-valent species. However, unlike in all other ethane-bridged metalloporphyrin dimers reported earlier, the 2e-oxidized species showed quite unusual structures depending on the nature of counter ions. Ions, such as SbF6 , SbCl6 and PF6 , are engaged in strong interactions with the porphyrin π-cation radical and causes substantial structural changes, including large deformation of the ring. The solid-state structure remains intact in solution as well. The observations are further supported by DFT calculations.
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Base de dados:
MEDLINE
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2020
Tipo de documento:
Article
País de afiliação:
Índia