Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 15, Issue 47, Pages 13150-13160Publisher
WILEY-BLACKWELL
DOI: 10.1002/chem.200901938
Keywords
EPR spectroscopy; heterometallic rings; magnetic properties; spin frustration
Categories
Funding
- EPSRC (UK)
- Network of Excellence MAGMANet
- University of Manchester
- Royal Society
Ask authors/readers for more resources
The synthesis and structural characterization of three heterometallic rings templated about imidazolium cations is reported. The compounds are [2,4-DiMe-ImidH][(Cr7NiF8)-F-II(O(2)CtBu)(16)] 1 (2,4-DiMe-ImidH = the cation of 2,4-dimethylimidazole), [ImidH](2)[Cr6Ni2II-F-8(O(2)CCtBu)(16)] 2 (ImidH = the cation of imidazole), and [1-Bz-ImidH](2) [(Cr7Ni2F9)-F-II(O(2)CtBu)(18)] 3 (1-Bz-Imid H = the cation of 1-benzylimidazole). The structures show the formation of octagonal arrays of metals for 1 and 2 and a nonagon of metal centers for 3. In all cases the edges of the polygon are bridged by a single fluoride and two pivalate ligands, and the position of the divalent metal centers cannot be distinguished by X-ray diffraction. Magnetic studies combined with EPR spectroscopy allow the characterization of the magnetic states of the compounds. In each case the exchange is antiferromagnetic with a magnetic exchange parameter J approximate to -5.8 cm(-1), and it is not possible to differentiate the exchange between two Cr-III centers (J(CrCr)) from the exchange between a Cr-III and a Ni-II center (J(CrNi)). For 2 there is evidence for the presence of at least two, possibly four, linkage isomers of the heterometallic ring, caused by the presence of two divalent metal centers in the ring. The EPR spectroscopy of 3 suggests an S=1/2 ground state of the ring and that it is likely that only one linkage isomer is present.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available