[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-phenantrolinophane}. 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)(L0)][BF4]ð2þnÞ {L¼2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane; L0 ¼MeCN, Cl, Br, I; n¼charge of L0} 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 Bun4 NI) necessary to balance the charge of the complex cation [Ni(L)(L0)]ð2þnÞþ. An X-ray diffraction analysis shows that, independently of the nature of L0, both 1 and 2 contain the complex cation [Ni(L)(MeCN)]2þ, which is therefore capable of templating two different polyiodide networks based on interacting I 3 /I 5 and I 5 /I7 units, respectively. The solid state FT-Raman spectra of 1 and 2 are discussed based on their structural features.