Synthesis, Characterization, and Solid-State Structure of [8]Cycloparaphenylenes with Inherent Chirality.

Abstract

We report here the synthesis of two [8]cycloparaphenylenes ([8]CPP) derivatives, 1 and 2, bearing a monosubstituted benzene moiety. The presence of the substituent implies a planar chirality for the monosubstituted [8]CPP 1 and 2, whose configuration is here described by applying the chirality descriptors pR and pS. Experimental evidence of this planar chirality has been obtained through 1H VT NMR studies and by addition of Pirkle's reagent. This was confirmed by the X-ray crystal structure of 2, which represents an interesting example of solid-state structure of a monosubstituted [8]CPP derivative. Derivative 2 crystallizes in two monoclinic crystal forms (α and β), which show a herringbone motif. The [8]CPP ring of the α form encapsulates two dichloromethane molecules, held through C-H···π interactions, while in the β form, open channels are partially filled by highly disordered solvent molecules.