<i>cis</i>-/<i>trans</i>-SpecificSynthesis of Functionalized Bottlebrush Ring Opening Metathesis PolymerizationPolymers Containing Terthiophene and Pyrene That Exhibit Unique Thermaland 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.

Publication Details

Journal
Figshare
Published
2025-03-05
DOI
https://doi.org/10.1021/acsmacrolett.4c00845.s001
Primary Topic
X-ray Diffraction in Crystallography
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article
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article

cis-/trans-SpecificSynthesis of Functionalized Bottlebrush Ring Opening Metathesis PolymerizationPolymers Containing Terthiophene and Pyrene That Exhibit Unique Thermaland Emission Properties

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X-ray Diffraction in Crystallography
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cis-/trans-SpecificSynthesis of Functionalized Bottlebrush Ring Opening Metathesis PolymerizationPolymers Containing Terthiophene and Pyrene That Exhibit Unique Thermaland Emission Properties

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Abstract

<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.

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X-ray Diffraction in Crystallography
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<i>cis</i>-/<i>trans</i>-SpecificSynthesis of Functionalized Bottlebrush Ring Opening Metathesis PolymerizationPolymers Containing Terthiophene and Pyrene That Exhibit Unique Thermaland Emission Properties · Figshare (2025) | TGRS Research Map | TGRS