Dual-radical-based molecular anisotropy and synergy effect of semi-conductivity and valence tautomerization in a photoswitchable coordination polymer.
Natl Sci Rev
; 10(6): nwad047, 2023 Jun.
Article
em En
| MEDLINE
| ID: mdl-37476568
ABSTRACT
Organic radicals are widely used as linkers or ligands to synthesize molecular magnetic materials. However, studies regarding the molecular anisotropies of radical-based magnetic materials and their multifunctionalities are rare. Herein, a photoisomerizable diarylethene ligand was used to form {[CoIII(3,5-DTSQ·-)(3,5-DTCat2-)]2(6F-DAE-py2)}·3CH3CN·H2O (o-1·3CH3CN·H2O, 6F-DAE-py2 = 1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene), a valence-tautomeric (VT) coordination polymer. We directly observed dual radicals for a single crystal using high-field/-frequency (â¼13.3 T and â¼360 GHz) electron paramagnetic resonance (EPR) spectroscopy along the c-axis, which was further confirmed by angle-dependent Q-band EPR spectroscopy. Moreover, a conductive anomaly close to the VT transition temperature was observed only when probes were attached at the ab plane of the single crystal, indicative of synergy between valence tautomerism and conductivity. Structural anisotropy studies and density functional theory (DFT) calculations revealed that this synergy is due to electron transfer associated with valence tautomerism. This study presents the first example of dual-radical-based molecular anisotropy and charge-transfer-induced conductive anisotropy in a photoswitchable coordination polymer.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Natl Sci Rev
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
China