Issue 42, 2015

Spin frustration in antiperovskite systems: (TTF˙+ or TSF˙+)3[(Mo6X14)2−Y]

Abstract

Two novel antiperovskite charge-transfer (CT) solids composed of a tetraselenafulvalene radical cation (TSF˙+), a dianionic molybdenum cluster unit [Mo6X14]2−, and a halogen anion (Y) (X, Y = Cl, Br) were prepared by electrocrystallization. Their crystal structures and magnetic properties with regard to spin frustration are discussed together with those of isostructural tetrathiafulvalene (TTF) CT solids previously reported. Both TSF and TTF salts have an apex sharing distorted octahedral spin lattice with a rhombohedral R[3 with combining macron] space group. The calculated overlap integrals based on the crystal structures and insulating nature of the TSF salts indicate that they are Mott insulators. Their spin susceptibilities obeyed the Curie–Weiss law and exhibited an antiferromagnetic ordering at lower temperatures for the TSF salts (Néel temperature, TN = 3.0 K for X = Y = Cl and 5.5 K for X = Y = Br) than the TTF salts. The Curie–Weiss temperatures (|ΘCW| ∼ 1.6–6.3 K) for the TSF salts are lower than those of the TTF salts. For the TSF salts, spin-flop behavior was detected at 3.2 T for X = Y = Cl and 1.5 T for X = Y = Br at 1.9 K. Due to both the distortion of the octahedral geometry of the spin lattice and the anisotropic molecular orientation, the geometrical spin frustrations in TSF and TTF systems are weakened.

Graphical abstract: Spin frustration in antiperovskite systems: (TTF˙+ or TSF˙+)3[(Mo6X14)2−Y−]

Supplementary files

Article information

Article type
Paper
Submitted
09 Jul 2015
Accepted
24 Sep 2015
First published
24 Sep 2015

J. Mater. Chem. C, 2015,3, 11046-11054

Author version available

Spin frustration in antiperovskite systems: (TTF˙+ or TSF˙+)3[(Mo6X14)2−Y]

T. Hiramatsu, Y. Yoshida, G. Saito, A. Otsuka, H. Yamochi, Y. Shimizu, Y. Hattori, Y. Nakamura, H. Kishida, H. Ito, K. Kirakci, S. Cordier and C. Perrin, J. Mater. Chem. C, 2015, 3, 11046 DOI: 10.1039/C5TC02075A

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