Reactivity of Polyiodide Toward 1,6-Bis(pyridinium)hexane (bphx): Syntheses and Structures of Two Organic-Inorganic Hybrid Clusters [(bphx)₃·(Pb₃I₈Br₄)] and [(bphx)₂·(Cu₄I₈)]

Abstract

In this article, the solution-phase reaction of metal iodides with bphx yields two novel organic-inorganic hybrid clusteric halides: [(bphx) 3 (Pb 3 I 8 Br 4 )] and [(bphx) 2 (Cu 4 I 8 )] (bphx = 1, 6-bis(pyridinium)hexane dication), which are characterized by X-ray crystallography and IR spectroscopy. The title trinuclear compound 1 crystallizes in Orthorhombic, space group Pccn with a = 29.077(10)Å, b = 12.030(4)Å, c = 19.749(7)Å. Tetranuclear oligomer 2 crystallizes in Monoclinic, space group P2(1)/c with a = 10.1630(5)Å, b = 15.2477(7)Å, c = 15.3222(7)Å. Both compounds exhibit unusual supramolecular organization wherein bphx dications reside in the channels as an efficient template. The complex 2 gives a fluorescence center at 567 nm under excitation at 450 nm, which is considered to mainly arise from the [Cu 4 I 8 ] 4− unit.