Synthesis and Characterization of Repeating Sequence Copolymers of Fluorene and Methylene Monomers

A series of well-defined multiblock (mb) copolymers consisting of alternating 9,9-dihexylfluorene and methylene segments has been prepared. Poly(9,9-dihexylfluorene-mb-methylene)s (PFMs) with repeat units of F_xM_y (x = 1−4, y = 10, 18 and x = 5−8, y = 18) were assembled by tandem metal-catalyzed acyclic diene metathesis (ADMET) polymerization/hydrogenation from α,ω-olefin bearing precursors. The polymers exhibited weight-average molecular weights ranging from M_w = 10 to 57 kDa. The PFMs exhibit photophysical properties, absorbance, and emission consistent with the length of the fluorene sequence. Glass and melting transition temperatures also increase with fluorene segment length.