Issue 24, 2023

A tetrathiafulvalene salt of the nitrite (NO2) anion: investigations of the spin-Peierls phase

Abstract

Electrocrystallization of ortho-dimethyltetrathiafulvalene (o-DMTTF) in the presence of a nitrite (NO2) anion affords a 2 : 1 phase, namely (o-DMTTF)2NO2, the first example of an isolated cation radical salt with NO2. The o-DMTTF molecule organizes into strongly dimerized stacks that adopt a rare chessboard organization, associated with a strongly 1D structure. As a consequence of dimerization, the salt exhibits a semiconducting behavior (σRT = 5 S cm−1, Eact = 0.1 eV). The bent NO2 anion is disordered on the inversion center but does not exhibit any anion-ordering transition. Combined SQUID magnetometry and electron paramagnetic resonance (EPR) experiments demonstrate the appearance of a spin-Peierls transition with TSP = 70 K. The temperature dependence of the spin gap and associated dimerization parameter δ across the spin-Peierls transition have been determined. The low-temperature narrow EPR line observed below TSP is attributable to intrinsic magnetic defects localized on the o-DMTTF molecules themselves. The broadening of the EPR line at higher magnetic fields is associated with the disordered NO2 anions surrounding these magnetic defects, contributing to the inhomogeneity of their g factor.

Graphical abstract: A tetrathiafulvalene salt of the nitrite (NO2−) anion: investigations of the spin-Peierls phase

Supplementary files

Article information

Article type
Paper
Submitted
20 Dec 2022
Accepted
23 Jan 2023
First published
24 Jan 2023
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. C, 2023,11, 8170-8177

A tetrathiafulvalene salt of the nitrite (NO2) anion: investigations of the spin-Peierls phase

L. Soriano, M. Orio, O. Pilone, O. Jeannin, E. Reinheimer, N. Quéméré, P. Auban-Senzier, M. Fourmigué and S. Bertaina, J. Mater. Chem. C, 2023, 11, 8170 DOI: 10.1039/D2TC05431K

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