Reaction of the deprotonated N-thiophosphorylated thioureas RNHC(S)NHP(S)(OiPr)(2) (R = Ph, HL(I); 2-MeC(6)H(4)-, HL(II); 2,6-Me(2)C(6)H(3)-, HL(III); 2,4,6-Me(3)C(6)H(2)-, HL(IV); Me-, HL(V)) with Ni(II) leads to complexes of the formula [NiL(I-V)(2)]. The molecular structures of the thioureas HL(II-V) and the complexes [NiL(II-V)(2)] in the solid were elucidated by single-crystal X-ray diffraction analysis. In the complexes, the metal is found to be in a square planar trans-N(2)S(2) ([NiL(II-IV)(2)]) environment formed by the C=S sulfur atoms and the P-N nitrogen atoms, or in a square planar trans-S(2)S'(2) ([NiL(V)(2)]) environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands. DFT calculations confirmed that the [Ni(L(II-IV)-N,S)(2)] isomers are more stable (by 16-21 kcal mol(-1)) than the corresponding [Ni(L(II-IV)-S,S')(2)] conformers. The main reason for higher stability of the 1,3-N,S vs. 1,5-S,S' isomers is the formation of intramolecular N-H···S=P hydrogen bonds. In solution the complexes [Ni(L(II-V)-N,S)(2)] have an exclusive 1,3-N,S coordination, while the compound [Ni(L(I)-N,S)(2)] exhibits two isomers in the (1)H and (31)P NMR spectra. The major species is assigned to the 1,3-N,S coordinated isomer, while the minor (∼25%) signals are due to the 1,5-S,S' isomer. UV-Vis spectroscopic results are in line with this. The electrochemical measurements reveal reversible one-electron reduction and irreversible oxidations, both assigned to ligand-centred processes.

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Large single crystals of the garnet imanite, Ca(3)Ti(2)Si(3)O(12), were synthesized by a floating zone technique. Near-infrared to visible spectroscopy presents an optical gap of 1.65 eV at 4 K, proving the insulating character of this garnet compound. Electron paramagnetic resonance data indicate that the d(1) electron of Ti(3+) exhibits an orbital contribution to the spin moment (g = 1.859(1)). An antiferromagnetic state is observed below T(N) = 7 K, confirmed by magnetic susceptibility and specific heat data. X-ray diffraction investigations on powders and single crystals of imanite reveal that the crystal structure agrees well with expectations: the cubic symmetry Ia3d describes all obtained single crystal and powder diffraction data.