ic100158g_si_001.cif (22.21 kB)

Magnetic Properties versus Network Dimensionality of Cerium(III) Octacyanotungstate(V) Compounds

Download (22.21 kB)
posted on 03.05.2010 by Marcin Kozieł, Robert Pełka, Michał Rams, Wojciech Nitek, Barbara Sieklucka
The reaction of cerium(III) nitrate, sodium octacyanotungstate(V), and 2,2′-bipyrimidine (bpm) under various conditions leads to the formation of three new compounds: ionic [Ce2(bpm)(dmf)6(H2O)8][W(CN)8]2·3H2O (1; dmf = N,N-dimethylformamide), tetranuclear molecules [Ce2(bpm)(dmso)8(H2O)4][W(CN)8]2·4H2O (2; dmso = dimethyl sulfoxide), and a two-dimensional inorganic−organic hybrid coordination polymer {[Ce2(bpm)(dmf)8(H2O)2][W(CN)8]2}n·2nH2O (3), all of which contain the subunit [Ce2(μ-bpm)] within the structure. These systems were characterized by single-crystal X-ray diffractometry, FTIR spectroscopy, and thermogravimetric analysis. Magnetic susceptibility measurements for 13 were performed on polycrystalline samples of the compounds. Magnetic behavior was interpreted in terms of the ligand-field splitting parameters and the exchange interaction between lanthanide centers and a d-electron spin carrier. The results confirmed the ferromagnetic cyano-mediated {Ce−NC−W} interaction JCeW = 1.7 (2) and 1.4(3) cm−1 (3) compared to the antiferromagnetic {Ce−bpm−Ce} interaction JCeCe = −1.1 cm−1 (1 and 2).