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-<i>mb</i>-methylene)s (PFMs) with repeat units of F<i><sub>x</sub></i>M<i><sub>y</sub></i> (<i>x</i> = 1−4, <i>y</i> = 10, 18 and <i>x</i> = 5−8, <i>y</i> = 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 <i>M</i><sub>w</sub> = 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.