Abstract:We have prepared some 3d-4f cyanide-bridged Ln(DMF) 4

In order to understand novel structural features of crystal packing of [CuL 2 ][Ni(CN) 4 ]•2H 2 O (L = (1R,2R)-1,2diaminocyclohexane), we have investigated temperature effect, metal-size effect, and isotope effect and their temperature dependence (100-300 K) with synchrotron powder X-ray diffraction (XRD) for ( 1) [CuL 2 ][M(CN) 4 ]•2H 2 O (M=Pd, Pt), (2) [CuL' 2 ][M(CN) 4 ] (M=Ni, Pd, and Pt; L' = N-ethylethylenediamine), and (3) [CuL'' 2 ][M(CN) 6 ]•nH 2 O (L'' =(1S,2S)-1,2dimethylcyclohexanediamine. M=Cr, Co, and Fe; isotopes of H 2 O are 1 H(H), 2 H(D), and 18 O(O), respectively). The effect of the factors of ( 1) (temperature difference of 200 K) is comparable to metal size for the system of (1). Combinatorial preparation of (2) gave rise to the most stable Pd(II) complexes predominantly. Isotope effect of water molecules resulted in little structural changes of lattice for (3).

Abstract:We have investigated temperature dependence of crystal structure of a chiral cyanide-bridged bimetallicCell parameters and most of bond distances decreased on cooling for 1. However, only a long Cu-N bond of semi-coordination increases on cooling, which is the first example of negative thermal elongation of specific bond distances.

We have prepared four H/D isotope forms of Nd(DMF)4(H2O)3Fe(CN)6·H2O (DMF = N,N-dimethylformamide) by using D2O or DMF-d1. Temperature dependence of magnetization exhibits H/D isotope effects resulting from intermolecular hydrogen bonds. Temperature dependence of Fe 2p3/2 and 2p1/2 XAS and 57Fe Mössbauer spectra suggested that the influence of coordination environment could be distiguished from the influence of crystal lattice based on preliminary crystallographic results.