New organically templated thiocyanatocadmates and chlorocuprate(II): synthesis and structural characterization

With various organic base molecules as the countercations, five new thiocyanatocadmates [H2(tmen)][Cd(SCN)4] (tmen = N,N,N',N'-tetramethylethylenediamine) 1, [H2(tmba)][Cd2(SCN)6] (tmba = N,N,N',N'-tetramethyl-1,4-butanediamine) 2, [H2(teen)][Cd2(SCN)6] (teen = N,N,N',N'-tetra-ethylethylenediamine) 3, [H(amp)][Cd(SCN)2(CH3COO)] (amp = 2-amino-6-methylpyridine) 4 and [H(abp)]4[Cd(SCN)4]SO4·H2O (abp = 2-amino-6-bromopyridine) 5, and one new chlorocuprate(II) [H2(cha)][CuCl4] (cha = 1,4-cyclohexanediamine) 6 were obtained from a series of simple room-temperature self-assemblies at pH = 2 or 6.5. X-ray single-crystal diffraction analysis reveals that (i) templated by [(CH3)2NH(CH2)2NH(CH3)2](2+) (H2(tmen)(2+)), the anion [Cd(SCN)4](2-) in 1 shows a 1-D linear single-chain structure, whereas templated by [(CH3)2NH(CH2)4NH(CH3)2](2+) (H2(tmba)(2+)), the anion [Cd2(SCN)6](2-) in 2 shows a 1-D linear double-chain structure. The number of C atoms between the two N atoms in the templating agent controls the width of the anionic chain through the N(amino)-H···N(SCN) interactions; (ii) templated by [(C2H5)2NH(CH2)2NH(C2H5)2](2+) (H2(teen)(2+)), the anion [Cd2(SCN)6](2-) in 3 exhibits a 3-D open-framework structure, which is based on zigzag anionic chains. A direct change of the substituent group from -CH3 to -C2H5 alters indirectly the shape of the anionic chain from a linear shape to a zigzag shape; (iii) 4 shows a 3-D supramolecular network structure, which is built up from the 1-D zigzag anionic structures by the H(amp)(+) molecules via N-H···O interactions. The formation of the zigzag chain derives from the chelation of the CH3COO(-) groups to the Cd(2+) centers; (iv) 5 is indeed a double salt of [H(abp)]2[Cd(SCN)4] and [H(abp)]2SO4. SO4(2-) and H(abp)(+) form a supramolecular aggregation. Surrounded by the aggregations, the anion [Cd(SCN)4](2-) only shows a dinuclear structure; and (v) templated by H2(cha)(2+), the anion [CuCl4](2-) in 6 displays a 2-D perovskite layer structure. The photoluminescence analysis indicates that upon excitation (λ(ex) = 335 nm for 4, λ(ex) = 395 nm for 5), and emit light (λ(em) = 365 nm for 4, λ(em) = 470 nm for 5), which can be seen clearly under the UV lamp.