Hybrid Supramolecules for Azolium-Linked Cyclophane Immobilization and Conformation Study: Synthesis,...

In this paper, one imidazole macrocyclic divalent cation with a flexible configuration was chosen with the aim of the immobilization of its conformation. Six novel organic-inorganic hybrid supramolecules {([syn/anti-did](CdI₄)(C₂H₃N)} (1), {([syn/anti-did](HgI₄)(C₂H₃N)} (2), {([syn/syn-did](Pb₂I₈)(PbI₅)} (3), {([syn/syn-did](Bi₂I₈)(BiI₅)} (4), {([syn/syn-did](Ag₄Br₆)} (5), and {([syn/anti-did](Ag₂I₄)} (6) [did²⁺ = (1²z, 5²z)-1¹H, 5¹H-1, 5(1, 3)-diimidazol-3-iuma-3, 7(1, 2)-dibenzenacyclooctaphane-1³, 5³-diium] have been synthesized through the self-assembly reaction of did²⁺ with different metals under solvothermal reaction. These compounds have been unambiguously confirmed by powder X-ray diffraction, IR, thermogravimetric and X-ray single-crystal diffraction. Crystallographic analysis shows that the anions of compounds 1 and 2 are isostructural with mononuclear anion structure, the anions of compounds 3, 4, and 6 are of binuclear structure, and compound 5 anion is a one-dimensional anionic chain structure. Imidazole cyclophanes of organic cations may exist in a syn/syn-conformation in 3-5 or syn/anti conformation in 1, 2, 6, but tilting angles in compounds 1-6 were different. This article described the photocatalytic degradation of organic dye in waste water and the optical band gap of compounds 1-6. The calculated semiconductor band gap of compounds 1-6 is smaller than that of TiO₂, so compounds 1-6 have semiconductor properties. Compound 1 has the smallest band gap value, and the photocatalytic performance is the best.