“[Ni(L)(MeCN)]2+ complex cation as a template for the assembly of extended I3–·I5– and I5–·I7– polyiodide networks {L = 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane}. Synthesis and structures of “[Ni(L)(MeCN)]I8 and “[Ni(L)(MeCN)]I12

ARAGONI, MARIA CARLA;ARCA, MASSIMILIANO;F. DEMARTIN;F. A. DEVILLANOVA;A. GARAU;ISAIA, FRANCESCO;LIPPOLIS, VITO;S. RIZZATO;G. VERANI

2004-01-01

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Abstract

The compounds [Ni(L)(MeCN)]I8 (1) and [Ni(L)(MeCN)]I12 (2) have been obtained from the reactions of the complexes [Ni(L)(L')][BF4](2+n) {L = 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane; L' = MeCN, Cl–, Br–, I–; n = charge of L'} with an excess of I2 (molar ratios of 6, 10 and 20 have been used), in the presence of the stoichiometric amount of I– (as Bu4nNI) necessary to balance the charge of the complex cation [Ni(L)(L')](2+n)+. An X-ray diffraction analysis shows that, independently on the nature of L', both 1 and 2 contain the complex cation [Ni(L)(MeCN)]2+, which is therefore capable of templating two different polyiodide networks based on interacting I3–/I5– and I5–/I7 units, respectively. The solid state FT-Raman spectra of 1 and 2 are discussed based on their structural features.