TY - JOUR
T1 - EPR spectroscopy of a family of Cr(III) 7M(II) (M = Cd, Zn, Mn, Ni) "wheels": studies of isostructural compounds with different spin ground states
AU - Piligkos, Stergios
AU - Weihe, Høgni
AU - Bill, Eckhard
AU - Neese, Frank
AU - El Mkami, Hassane
AU - Smith, Graham M
AU - Collison, David
AU - Rajaraman, Gopalan
AU - Timco, Grigore A
AU - Winpenny, Richard E P
AU - McInnes, Eric J L
N1 - Keywords: Algorithms; Cadmium; Chromium; Crystallography, X-Ray; Electron Spin Resonance Spectroscopy; Manganese; Models, Chemical; Molecular Conformation; Molecular Structure; Nickel; Zinc
PY - 2009
Y1 - 2009
N2 - Spinning wheels: The presented highly resolved multifrequency continuous wave EPR spectra (e.g., see figure) of the heterooctametalic "wheels" Cr(7)M provide rare examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excited spin states is observed.We present highly resolved multifrequency (X-, K-, Q- and W-band) continous wave EPR spectra of the heterooctametalic "wheels", [(CH(3))(2)NH(2)][Cr(III) (7)M(II)F(8)((CH(3))(3)CCOO)(16)], hereafter Cr(7)M, where M=Cd, Zn, Mn, and Ni. These experimental spectra provide rare examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excited spin states is observed. We interpret the EPR spectra by use of restricted size effective subspaces obtained by the rigorous solution of spin-Hamiltonians of dimension up to 10(5) by use of the Davidson algorithm. We show that transferability of spin-Hamiltonian parameters across complexes of the Cr(7)M family is possible and that the spin-Hamiltonian parameters of Cr(7)M do not have sharply defined values, but are rather distributed around a mean value.
AB - Spinning wheels: The presented highly resolved multifrequency continuous wave EPR spectra (e.g., see figure) of the heterooctametalic "wheels" Cr(7)M provide rare examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excited spin states is observed.We present highly resolved multifrequency (X-, K-, Q- and W-band) continous wave EPR spectra of the heterooctametalic "wheels", [(CH(3))(2)NH(2)][Cr(III) (7)M(II)F(8)((CH(3))(3)CCOO)(16)], hereafter Cr(7)M, where M=Cd, Zn, Mn, and Ni. These experimental spectra provide rare examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excited spin states is observed. We interpret the EPR spectra by use of restricted size effective subspaces obtained by the rigorous solution of spin-Hamiltonians of dimension up to 10(5) by use of the Davidson algorithm. We show that transferability of spin-Hamiltonian parameters across complexes of the Cr(7)M family is possible and that the spin-Hamiltonian parameters of Cr(7)M do not have sharply defined values, but are rather distributed around a mean value.
U2 - 10.1002/chem.200801895
DO - 10.1002/chem.200801895
M3 - Journal article
C2 - 19199301
SN - 0947-6539
VL - 15
SP - 3152
EP - 3167
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
IS - 13
ER -