A supramolecular spin crossover Fe(III) complex and its Cr(III) isomer: stabilization of water-chloride cluster within supramolecular host

作者：Saha Rajat; Biswas Susobhan; Steele Ian M; Dey Kamalendu^*; Mostafa Golam

来源：Dalton Transactions, 2011, 40(13): 3166-3175.

DOI：10.1039/c0dt01256d

The metal complexes, [M(Hdammthiol)(2)]Cl center dot 3H(2)O [M = Cr(III) (1), Fe(III) (2)] [where H(2)dammthiol is the thiol form of the ligand, diacetylmonoxime morpholine N-thiohydrazone] were synthesized by metal template reactions of diacetylemonoxime with morpholine N-thiohydrazide in the presence of CrCl3 center dot 6H(2)O and FeCl3 center dot 6H(2)O. Both the complexes (1 and 2) were characterized by single crystal X-ray crystallography, spectroscopic (IR and UV-vis), Mossbauer and TGA analyses. The single crystal X-ray studies of both complexes show that the supramolecular hosts, constructed by the discrete mononuclear complexes, form supramolecular channels along the c-axis which are filled up by water-chloride clusters. In both complexes, the 1D water-chloride chain with chair-like architecture within the supramolecular hosts presents novelty. The magnetic measurement study of Fe(III) complex shows a spin crossover from S = 1/2 at 2.5 K to S = 5/2 at 300 K. At very low temperature, the presence of strong cooperative hydrogen bonding interactions stabilizes the S = 1/2 state.

• 出版日期2011-4