From ferromagnets to high-spin molecules: the role of the organic ligands

Talal Mallah1, Arnaud Marvilliers1, Éric Rivière1
1Laboratoire de Chimie Inorganique UMR CNRS 8613, Université Paris-Sud, 91405 Orsay, France

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Tài liệu tham khảo

10.1080/00018739700101558

10.1002/anie.199619471

10.1021/ic980109w

10.1021/ja00049a078

Ginsberg A. P., 1971, Inorg, Chim. Acta Rev., 5, 45

10.1039/a802351d

10.1002/anie.198508341

10.1039/c39950000061

Morpugo G. O., 1980, Crystal structure and spectroscopic properties of a polynuclear complex between [bis(2-aminoethyl)amine]copper(II) and hexacyanoferrate(III), J. Chem. Soc. Dalton Trans., 111

Scuiller A., 1996, A rationale route to high spin molecules via hexacyanometallates: a new µ-cyano CrIIIMnII 6 heptanuclear complex with a low-lying S = 27/2 ground state, New J. Chem., 20, 1

10.1021/ic970160k

P. Day (The Royal Institution London UK ). Has Professor Mallah made a cluster

containing a central ferrocyanide ion with six surrounding high-spin Fe(III)? Such

a species would mimic the local structure of Prussian blue for which we proposed

a mechanism to explain the ferromagnetic exchange between Fe(III) involving the

intervalence charge-transfer configuration many years ago (Mayoh & Day 1976).

T. Mallah. We have made a pentanuclear cluster containing a central ferrocyanide

with four surrounding high-spin Fe(III) chelated by a pentadentate ligand containing

two phenolato groups. The magnetic properties clearly show a ferromagnetic interac

tion between the high-spin Fe(III) ions through the diamagnetic low-spin Fe(II) as

observed in Prussian blue. A mechanism involving the intervalence charge transfer

configuration proposed by Mayoh & Day (1976) explains the ferromagnetic exchange

interaction. Unfortunately we were not able to observe the intervalence optical band

in our compound because of the presence of an intense band centred at 580 nm due

to the charge transfer between the phenolato groups and Fe(III).