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Hexacyanometalate Molecular Chemistry: Heptanuclear Heterobimetallic Complexes; Control of the Ground Spin State
Author(s) -
Marvaud Valérie,
Decroix Caroline,
Scuiller Ariane,
GuyardDuhayon Carine,
Vaissermann Jacqueline,
Gonnet Florence,
Verdaguer Michel
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200390192
Subject(s) - antiferromagnetism , ground state , crystallography , chemistry , ferromagnetism , singlet state , metal , denticity , magnetic susceptibility , spin states , crystal structure , condensed matter physics , inorganic chemistry , excited state , physics , atomic physics , organic chemistry
Following a bottom‐up approach to nanomaterials, we present a rational synthetic route from hexacyanometalates [M(CN) 6 ] 3− (M=Cr III , Co III ) cores to well‐defined heptanuclear complexes. By changing the nature of the metallic cations and using a localised orbital model it is possible to control and to tune the ground state spin value. Thus, with M=Cr III , d 3 , S =3/2, three heptanuclear species were built and characterised by mass spectrometry in solution, by single‐crystal X‐ray diffraction and by powder magnetic susceptibility measurements, [Cr III (CNM′L n ) 6 ] 9+ (M′=Cu II , Ni II , Mn II , L n =polydentate ligand), showing spin ground states S G =9/2 [Cu II ], with ferromagnetic interactions J Cr,Cu =+45 cm −1 , S G =15/2 [Ni II ] and J Cr,Ni =+17.3 cm −1 , S G =27/2 [Mn II ], with an antiferromagnetic interaction J Cr,Mn =−9 cm −1 , (interaction Hamiltonian ℋ=− J Cr,M [ S Cr Σ i S M ( i )], i =1–6). With M=Co III , d 6 , S =0, the heptanuclear analogues [Co III (CN−M′L n ) 6 ] 9+ (M′=Cu II , Ni II , Mn II ) were similarly synthesised and studied. They present a singlet ground state and allow us to evaluate the weak antiferromagnetic coupling constant between two next‐nearest neighbours M′CoM′.