Synthesis, Crystal Structure, Physical Properties, and Application of a Series of Functional Dibenzo[d,f][1,3]dioxepine Derivatives

Abstract

The twisted aromatics, functional dibenzo[d,f][1,3]dioxepine derivatives were synthesized in high yields from reactions of 5,5′-dibromo-2,2′-biphenol with corresponding ketal or ketone compounds under acid catalysis. The structures of these compounds were characterized by ¹H NMR, elemental analysis, UV-Vis absorption spectrum and X-ray diffraction analysis. The conformation of O—C—O bridged biphenyl derivatives with varied substitute groups on 6,6′-position was studied by X-ray crystallography and force-field simulation. The result of calculations by UNIVERSAL 1.02 force field in Cerius² package(4.6) indicates that dibenzo[d,f][1,3]dioxepine derivatives show twisted conformations and the twisted angle between the phenyl rings is about 40°, which is accordant with the result from crystal structure determination, though the obtained angles in the crystal of dibenzo[d,f][1,3]dioxepine derivatives with the varied substitute groups on 6,6′-position are shown to be slightly shifted to 40° owing to intermolecular interactions in crystal stacking. DSC studies exhibit that the substitute groups on 6,6′-position can induce a large variation of endothermic peaks ranging from 80 to 135 °C. The conjugated polymers based on dibenzo[d,f][1,3]dioxepine derivatives, which have ultraviolet emitting with a quantum efficiency of 10%, were obtained by Yamamoto coupling.