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](CdI)(CHN)} (), {([syn/anti-did](HgI)(CHN)} (), {([syn/syn-did](PbI)(PbI)} (), {([syn/syn-did](BiI)(BiI)} (), {([syn/syn-did](AgBr)} (), and {([syn/anti-did](AgI)} () [did = (1z, 5z)-1H, 5H-1, 5(1, 3)-diimidazol-3-iuma-3, 7(1, 2)-dibenzenacyclooctaphane-1, 5-diium] have been synthesized through the self-assembly reaction of did 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 and are isostructural with mononuclear anion structure, the anions of compounds , , and are of binuclear structure, and compound anion is a one-dimensional anionic chain structure. Imidazole cyclophanes of organic cations may exist in a syn/syn-conformation in - or syn/anti conformation in , , , but tilting angles in compounds - were different. This article described the photocatalytic degradation of organic dye in waste water and the optical band gap of compounds -. The calculated semiconductor band gap of compounds - is smaller than that of TiO, so compounds - have semiconductor properties. Compound has the smallest band gap value, and the photocatalytic performance is the best.