Crystal structure and photoreactivity of a halogen-bonded cocrystal based upon 1,2-diiodoperchlorobenzene and 1,2-bis(pyridin-4-yl)ethylene

Abstract

The formation of a photoreactive cocrystal based upon 1,2-diiodoperchlorobenzene (1,2-C6I2Cl4 ) and trans-1,2-bis(pyridin-4-yl)ethylene (BPE) has been achieved. The resulting cocrystal, 2(1,2-C6I2Cl4 )·(BPE) or C6Cl4I2·0.5C12H10N2, comprises planar sheets of the components held together by the combination of I...N halogen bonds and halogen–halogen contacts. Notably, the 1,2-C6I2Cl4 molecules π-stack in a homogeneous and face-to-face orientation that results in an infinite column of the halogen-bond donor. As a consequence of this stacking arrangement and I...N halogen bonds, molecules of BPE also stack in this type of pattern. In particular, neighbouring ethylene groups in BPE are found to be parallel and within the accepted distance for a photoreaction. Upon exposure to ultraviolet light, the cocrystal undergoes a solid-state [2 + 2] cycloaddition reaction that produces rctt-tetrakis(pyridin-4-yl)cyclobutane (TPCB) with an overall yield of 89%. A solvent-free approach utilizing dry vortex grinding of the components also resulted in a photoreactive material with a similar yield.