Iptycene-Containing Poly(aryleneethynylene)s

The syntheses of two novel iptycene monomers, 1,4-diiodotriptycene (5) and 2,3-diiodo-4,9-dihydro-4,9-benzonaphtho[2,3,c]thiophene (10), are described herein. These monomers were subsequently copolymerized with a number of diethynylphenyl monomers via a Sonogashira−Hagihara coupling to afford both regiodefined polymers and random terpolymers. Terpolymers derived from coupling 5 and 2,5-dihexadecyloxy1,1,4-diiodobenzene with a diethynylpentiptycene exhibit emission spectra that are only slightly perturbed from solution to the solid state, suggesting that polymer association is effectively inhibited in condensed phases. An “all-iptycene” polymer (13) derived from the copolymerization of 10 with a diethynylpentiptycene monomer is also notable in that it owes its solubility to a combination of its nonlinearity and the presence of rigid iptycene groups rather than to flexible side chains.