Self-assembly of five new organic-inorganic hybrids based on two new flexible tricationic templates

Five new haloclusters, namely, {[Tbmpm](MeOH)[Cu3Br6]} (1), {[Tbmpm][Cu-2(SCN)(5)]}(n) (2), {[Tbmpm][Ag4Br7]}(n) (3), {[Tbmpm](0.5)[Ag2Br2.2(SCN)(0.7)]}(n) (4) and {[Tbpm][Cu-2(SCN)(5)]}(n) (5) [Tbmpm center dot 3Br = 1,3,5-tri(4-methylpyridiniummethyl)-2,4,6-trimethylbenzene tribromide and Tbpm center dot 3Br = 1,3,5-tri(4-methylpyridiniummethyl) benzene tribromide] were synthesized by the cation-templated self-assembly with Cu/AgX (X = Br, I, SCN) in N, N-dimethyl formamide (DMF) and MeOH system. The X-ray crystallography analysis showed that these compounds were all composed of discrete organic cations and halocluster anions. Compound 1 has a trinuclear structure, compound 2 exhibits an anion complex composed of 1D chain and mononuclear structure, compounds 3 and 4 present similar 1D silver cluster. More interesting, compound 5 possesses a rare 2D polypseudorotaxane structure. The H-bonds and electrostatic interactions between the organic counteractions and inorganic moieties also do the contribution to the crystal packing. These compounds were further characterized by IR spectra, UVVis, PXRD, and thermal gravimetric analysis (TGA). Their luminescent properties were also investigated in the solid state. (C) 2014 Elsevier B.V. All rights reserved.