[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

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 of 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.