Charge transfer phase transition with reversed thermal hysteresis loop in the mixed-valence Fe9[W(CN)8]6·xMeOH cluster†,10.1039/C3CC48029A

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Charge transfer phase transition with reversed thermal hysteresis loop in the mixed-valence Fe9[W(CN)8]6·xMeOH cluster†

Szymon Chorazy,Robert Podgajny,Wojciech Nogaś,Wojciech Nitek,Marcin Kozieł,Michał Rams,Ewa Juszyńska-Gałązka,Jan Żukrowski,Czesław Kapusta,Koji Nakabayashi,Takashi Fujimoto,Shin-ichi Ohkoshi,Barbara Sieklucka

Chemical Communications Pub Date : 01/10/2014 00:00:00 , DOI:10.1039/C3CC48029A

Abstract

A bimetallic pentadecanuclear cyanido-bridged {Fe₉[W(CN)₈]₆ (MeOH)₂₄}·xMeOH cluster of an Fe^II/III–W^IV/V mixed valence nature, reveals a reversible single-crystal-to-single-crystal transformation, concomitant with metal-to-metal charge transfer between Fe and W ions. The dominance of ^HSFe^II–NC–W^V units at a high temperature, and ^HSFe^III–NC–W^IV units at a low temperature, leads to an unprecedented reversed thermal hysteresis loop in magnetic measurements.