Synthesis and Polymerization of an --Substituted Tetraalkoxy [2.2]Paracyclophane-1,9-diene.

This contribution describes the synthesis of an unsymmetrical substituted tetraalkoxy[2.2]paracyclophane-1,9-diene comprised of an -substituted and a -substituted dioctyloxybenzene. ()-4,5,12,15-tetraoctyloxy-[2.2]paracyclophane-1,9-diene (()-pCpd) and ()-4,5,13,16-tetraoctyloxy-[2.2]paracyclophane-1,9-diene (()-pCpd) are formed as planar chiral enantiomers. Unlike other tetraalkoxy-substituted pCpds that form as diastereomers, both the ()-pCpd and the ()-pCpd can be polymerized via ring-opening metathesis polymerization (ROMP) using Grubbs' third generation initiator (G3) as it is achiral. Living ROMP afford copolymers featuring alternating ,-poly(-phenylenevinylene)s (PPV)s. The polymers' unique, blue-shifted optical properties are due to the alkoxy-substitution in the polymer's backbone and the resulting materials could be photoisomerized to the all- polymer. This strategy affords tetraalkoxy-pCpd monomers in high yields for the polymerization of soluble PPVs with low or narrow dispersities.