Five hybrid thiocyanate networks oriented by polyvalent cationic templates: Synthesis, structure and properties

•Compound 1 exhibits a 3D polypseudorotaxane network.•Compounds 2, 3 display 2D sandwich architecture.•Compounds 4 and 5 present 2D polypseudorotaxane layer.•SCN− can present all five coordinating modes.

The N-1-methylimidazole-substituted multication-templated self-assembly of CuSCN/AgSCN leads to five novel complex salts: {(tbi)[Cu3(SCN)6]}n (1), {(tbmi)[Cu2(SCN)5]}n (2), {(tebi)[Cu(SCN)2]4}n (3), {(tebi)[Cu(SCN)2]4}n (4) and {(tbmi)2[Ag5(SCN)11]}n (5) [tbi3+ = 1,3,5-tri[3′(1′-methyl)imidazoliummethyl]benzene, tbmi3+ = 1,3,5-tri[3′-(1′-methyl)imidazoliummethyl]-2,4,6-trimethylbenzene and tebi4+ = 1,2,4,5-tetra[3′-(1′-methyl)imidazoliummethyl]benzene]. Single-crystal X-ray diffraction shows that 2, 3 and 5 display a 2D sandwich structure, 4 presents a 2D polypseudorotaxane network, whereas, 1 exhibits a 3D polypseudorotaxane architecture. It is worth noting that SCN− can present five coordinating modes. All these results confirm the versatile template effect and correct choice of multications. In addition, elemental analysis, IR and UV–Vis spectra, powder X-ray diffraction patterns, thermogravimetric analyses of these complexes have been investigated.

Graphical abstractInspired by the lack of supramolecular hybrids induced by the multivalent interactions, we conducted five integrations of trication or tetracation with thiocyanates via strict templated self-assembly. These compounds 1, 4, and 5 represent the first type of 2–3D polypseudorotaxane nets.Figure optionsDownload full-size imageDownload as PowerPoint slide