TY - JOUR
T1 - Structures and XPS studies of several 3d-4f cyano-bridged LnIII-FeIII/CoIII heterometallic complexes
AU - Akitsu, Takashiro
AU - Einaga, Yasuaki
N1 - Funding Information:
This work was supported by a Grant-in-Aid for the 21st Century COE program ‘KEIO Life Conjugate Chemistry’ form the Ministry of Education, Culture, Sports, Science, and Technology, Research Foundation for Opto-Science and Technology, and Japan and Mizuho Foundation for the Promotion of Science.
PY - 2006/9/11
Y1 - 2006/9/11
N2 - Characterization and crystal structure determination of 3d-4f cyano-bridged bimetallic assemblies, Ln(DMF)4(H2O)3Co(CN)6 · H2O (DMF = N,N′-dimethylformamide, Ln = Tb, Dy, Ho and Er) have been newly carried out. We have observed their isostructural features and gradual decreasing cell constants and corresponding changes of local bond distances and angles around the cyano-bridges in accord with the ionic radii changes due to lanthanoid contraction. In order to elucidate the reasons that only Nd-Fe and Nd-Co complexes can exhibit photo-induced magnetic functions, we have also investigated the electronic properties for several analogous 3d-4f complexes, Ln(DMF)4(H2O)3M(CN)6 · H2O (Ln = Ce, Nd, Sm, Gd, Tb, Dy, Ho and Er; M = Co and Fe), by means of X-ray photoelectron spectroscopy (XPS). We found that the characteristic bent features of Nd-N-C bond angles and the slight shift of binding energies of Ln 4d3/2 peaks in the 3d-4f systems being closed to mixed-valence states might be the reasons for the novel functions.
AB - Characterization and crystal structure determination of 3d-4f cyano-bridged bimetallic assemblies, Ln(DMF)4(H2O)3Co(CN)6 · H2O (DMF = N,N′-dimethylformamide, Ln = Tb, Dy, Ho and Er) have been newly carried out. We have observed their isostructural features and gradual decreasing cell constants and corresponding changes of local bond distances and angles around the cyano-bridges in accord with the ionic radii changes due to lanthanoid contraction. In order to elucidate the reasons that only Nd-Fe and Nd-Co complexes can exhibit photo-induced magnetic functions, we have also investigated the electronic properties for several analogous 3d-4f complexes, Ln(DMF)4(H2O)3M(CN)6 · H2O (Ln = Ce, Nd, Sm, Gd, Tb, Dy, Ho and Er; M = Co and Fe), by means of X-ray photoelectron spectroscopy (XPS). We found that the characteristic bent features of Nd-N-C bond angles and the slight shift of binding energies of Ln 4d3/2 peaks in the 3d-4f systems being closed to mixed-valence states might be the reasons for the novel functions.
KW - 3d-4f Complexes
KW - Crystal structures
KW - Cyanide-bridged
KW - Heterometallates
KW - XPS
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U2 - 10.1016/j.poly.2006.03.026
DO - 10.1016/j.poly.2006.03.026
M3 - Article
AN - SCOPUS:33747494204
SN - 0277-5387
VL - 25
SP - 2655
EP - 2662
JO - Polyhedron
JF - Polyhedron
IS - 13
ER -