Symmetry-Broken Intermolecular Charge Separation of Cationic Radicals.
Angew Chem Int Ed Engl
; 62(15): e202301348, 2023 Apr 03.
Article
em En
| MEDLINE
| ID: mdl-36792536
ABSTRACT
A quadrupolar compound Pyr-BA with two pyrrole-type nitrogen atoms doped externally was prepared in this work. In high contrast with other π ionic radicals, its cationic radical Pyr-BAâ
+ undergoes unusual symmetry-broken charge separation (SB-CS), generating the mixed valence complex of Pyr-BA+1-q â
â
â
Pyr-BA+1+q , where q is the degree of charge transfer. Variable-temperature (VT) single-crystal analysis, absorption and EPR experiments all confirmed that aggregation and lower temperature would help to facilitate this SB-CS process. Gibbs energy calculations and gauge-including magnetically induced current simulation both validate that, for Pyr-BAâ
+ , SB-CS behavior is more favorable than the conventional dimerization mode. To the best of our knowledge, this is the first study that shows solid single-crystal evidence for spontaneous SB-CS between identical ionic radicals. Such a unique phenomenon is of great significance both in terms of fundamental aspects and uncharted material science.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
China