Synthesis of strained macrocyclic biaryls for enthalpy-driven ring-opening polymerization

Colquhoun, H.M., Zhu, Z.X., Dudman, C.C., O'Mahoney, C.A., Williams, D.J. and Drew, M.G.B. (2005) Synthesis of strained macrocyclic biaryls for enthalpy-driven ring-opening polymerization. Macromolecules, 38 (25). pp. 10413-10420. ISSN 0024-9297 doi: 10.1021/ma0517796

Abstract/Summary

Polymerizable macrocyclic biarylene-ether-ketones and biarylene-ether-sulfones are accessible from linear, bis(chloro)-terminated oligomers via nickel-catalyzed, intramolecular coupling under pseudo-high-dilution conditions. Single-crystal X-ray analyses of the resulting cyclo-oligomers reveal extremely distorted and highly strained geometries, with 4,4 '-biphenylene units showing deviations of up to 70 degrees from linearity.