Thermo- and electro-switchable Cs⊂{Fe₄–Fe₄} cubic cage: spin-transition and electrochromism

Abstract

A mixed valence Cs{Fe4-Fe4} cyanido-cube was synthesized and structurally characterized. The molecule, which is robust in solution, shows a remarkable electronic versatility. Electrochromic properties associated with nine different electronic states...

Building responsive materials by assembling {Fe4Co4} switchable molecular cubes

“…[38, 40,52] Moreover, FeCo distances corresponding to the edges of the cubic units are particularly visible with the intense peak located at 4.95 Å, while those arising from the cube face diagonal observed at around 7 Å, are barely detectable within the two samples. Finally, at higher r, the PDF fades as expected for short-range ordering.…”

Thermally Induced Reversible Metal-to-Metal Charge Transfer in Mixed-Valence {Fe III 4 Fe II 4 } Cubes

“…33 Later, Glatz decorated a partly reduced cube with the Cs@{Fe II,LS 4 -Fe III,HS 3 Fe II,HS } core, in which the only high-spin Fe(II) center exhibited SCO behaviour. 34 Different from the normally observed charge-transfer induced spin transition (CTIST) in the heterometallic Fe/Co compounds, 35,36 the CT and spin transition (ST) processes may proceed more separately in the Fe-Fe system, whereas more efforts are needed to figure out how it works. [41][42][43]…”

Mixed-valence {FeII2FeIII4} hexanuclear complexes with thermally induced Fe(iii) spin-crossover behavior

“…Recent comprehensive academic studies have shown that some of the excellent tricyanidoferrate(III) anions ([(Tp R )Fe(CN) 3 ] − , Tp R = poly(pyrazol-1-yl)borate) have been used in the construction of SCO materials because their ligand fields and redox potentials can be methodically tuned to a wide range using different substitution groups on the pyrazole ring. 56,57 Based on this type of unit, a series of [(Tp R )Fe(CN) 3 ] − -based complexes have been constructed, such as {Fe III 2 Fe II } trinuclears, 57 {Fe III 2 Fe II 2 } squares, 40,56 {Fe III 4 Fe II 4 } cubic cages, 58,59 and {Fe III 2 Fe II } n one-dimensional (1D) chains. 60,61 Most of the complexes with spin-crossover properties usually change their spin only at the Fe II site.…”