<i>cis</i>-/<i>trans</i>-Specific Synthesis of Functionalized Bottlebrush Ring Opening Metathesis Polymerization Polymers Containing Terthiophene and Pyrene That Exhibit Unique Thermal and Emission Properties

<i>Z</i>-Specific (99% <i>cis</i>) and <i>E</i>-specific (90% <i>trans</i>) syntheses of functionalized bottlebrush polymers (BBPs) by living ring opening metathesis polymerization (ROMP) of <i>exo</i>-<i>N</i>-substituted norbornene-2,3-dicarboximides (NDIs) containing terthiophene (3T) and pyrene (Pyr) moieties connected to a long methylene spacer (<i>n</i>-dodecyl) have been demonstrated by the (arylimido)-vanadium(V)-alkylidene catalysts in toluene at 50 °C. Thermal properties in the resultant BBPs measured by DSC thermograms are affected by the <i>cis</i>/<i>trans</i> selectivity; the resultant <i>cis</i>-BBPs containing 3T possessed a melting temperature at 111.2 °C, whereas the corresponding <i>trans</i>-BBPs are amorphous. The differences in <i>cis</i>-/<i>trans</i>-BBPs (containing 3T, Pyr) toward the emission properties have also been demonstrated due to a different degree in the inter/intra-polymer interaction through the functionality.