Synthesis, structural studies and computational evaluation of cyclophanes incorporating imidazole-2-selones

Abstract

We report new cyclophanes containing imidazole-2-selone groups linked by xylylene rings. A set of imidazole-2-selone cyclophanes is synthesized by reaction corresponding to imidazolium cyclophanes with selenium in the presence of K₂CO₃. The structural behavior of the new imidazole-2-selone cyclophanes was determined by ¹H and ¹³C NMR spectra and X-ray diffraction studies. Cyclophanes incorporating o-xylylene or mesitylene-m-cyclophane linked by selone groups were mutually syn in both the solid state and solution, and the cyclophanes showed a conformation similar to the cone conformation of calix[4]arenes. Cyclophanes incorporating p-xylylene or m-xylylene linked by selone groups showed two conformations in the solution: one mutually syn and the other mutually anti. There was no interconversion for both conformations observed on the NMR timescale. In the solid state, three conformations were detected for the p-xylylene-linked cyclophane: one is mutually syn and the other two are mutually anti and partial cone conformations. In the m-xylylene-linked case, only anti-conformation was characterized in the solid state. A density functional analysis was conducted to interpret the stability of the studied compounds and shed light on their origin. The energy preference analysis is in consistent agreement with the observed geometries and their co-existence.