The two-dimensional coordination polymer spin-crossover compound Fe(pyridine) 2 [Ni(CN) 4 ] (1) and its isotope substituted analogues Fe(pyridine-D 5 ) 2 [Ni(CN) 4 ] (2) and Fe(pyridine-15 N) 2 [Ni(CN) 4 ] (3) have been synthesised and the isotope effect on the thermal spin-crossover behaviour has been studied using magnetic susceptibility, 57 Fe Mo ¨ssbauer, Raman and calorimetric techniques. All these methods confirmed that upon isotope substitution-contrary to previous observations-the spin transition temperature shifted downwards from 202 to 194 K. The theoretical analysis of spectroscopic data has revealed that this shift was a result of a subtle balance between different vibrational and electronic factors.
A newly prepared metal complex Fe(4,4'-bipyridine)Ni(CN) 4¨n H 2 O, which was estimated to have a structure similar to the Hofmann-type clathrate host, changed its color from orange to deep orange and yellow on exposure to ethanol and acetone vapor, respectively, and the respective samples showed thermally induced two-step and one-step spin transitions.
The title compound, poly[diamminehexa-"-cyano-dicopper(I)copper(II)mercury(II)], [Cu 3 Hg(CN) 6 (NH 3 ) 2 ] n , has a novel threefold-interpenetrating structure of three-dimensional frameworks. This three-dimensional framework consists of two-dimensional network Cu 3 (CN) 4 (NH 3 ) 2 complexes and rod-like Hg(CN) 2 complexes. The two-dimensional network complex contains trigonal±planar Cu I (site symmetry m) and octahedral Cu II (site symmetry 2/m) in a 2:1 ratio. Two types of cyanide group form bridges between three coordination sites of Cu I and two equatorial sites of Cu II to form a twodimensional structure with large hexagonal windows. One type of CN À group is disordered across a center of inversion, while the other resides on the mirror plane. Two NH 3 molecules (site symmetry 2) are located in the hexagonal windows and coordinate to the remaining equatorial sites of Cu II . Both N atoms of the rod-like Hg(CN) 2 group (Hg site symmetry 2/m and CN À site symmetry m) coordinate to the axial sites of Cu II . This linkage completes the threedimensional framework and penetrates two hexagonal windows of two two-dimensional network complexes to form the threefold-interpenetrating structure.
The title compound, [MnNi(CN)4(C5H5N)2], has a layered structure of a two-dimensional network complex Mn(py)2Ni(CN)4, in which linkages of cyanide between the equatorial coordination sites of octahedral MnII ions (site symmetry 2/m) and those of square planar NiII ions (site symmetry 2/m) form a square mesh network. Pyridine ligands (located on mirror planes) coordinate to the axial sites of the MnII ions from both sides of the network.
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