The subtle effect of methyl substituent in C2-symmetric template on the formation of halocluster hybrids

•Through dication templated self-assembly six novel haloclusters were synthesized.•Compounds 2, 4 and 6 consisted of composite chains with metal–metal interaction.•While compounds 1, 3 and 5 comprise 0–1 dimensional anion framework.•The subtle template effect between dbm and ddb were compared.

Six novel haloclusters, namely {[dmb]2[Cu4I8]}·2DMF (1), {[ddb][Cu4I6]}n (2), {[dmb][Ag2I4]}n (3), {[ddb][Ag4I6]}n (4), {[dmb]2[Ag2Br6]} (5) and {[ddb][Ag4Br6]}n (6), were encountered in our investigation of the subtle template effect of methyl substituent on the formation of hybrids. The dications we chosen as C2-symmetric template is α,α′-di(3-methylimidozole-1-yl)benzene dichloride (abbreviated into dmb) or α,α′-di(2,3-dimethylimidozole-1-yl)benzene dichloride (abbreviated into ddb). The X-ray crystallography shows the more methyl substituents that exist in template, the more inorganic/organic interactions form in the hybrid net oriented by ddb. It is the H-bonds and electrostatic interactions between the organic counteractions and inorganic moieties that do the contribution to the crystal packing. These compounds have been further characterized by IR spectroscopy, UV–Vis spectra and thermostability properties.

Graphical abstractSix novel dication-directed haloclusters comprising of 0–1D supramolecular anion frameworks together with the subtle template effect of methyl group were reported.Figure optionsDownload full-size imageDownload as PowerPoint slide