Abstract
Conjugated polymers with cyclic structures are interesting because their symmetry leads to unique electronic properties. Recent advances in Vernier templating now allow large shape-persistent fully conjugated porphyrin nanorings to be synthesized, exhibiting unique electronic properties. We examine the impact of different conformations on exciton delocalization and emission depolarization in a range of different porphyrin nanoring topologies with comparable spatial extent. Low photoluminescence anisotropy values are found to occur within the first few hundred femtoseconds after pulsed excitation, suggesting ultrafast delocalization of excitons across the nanoring structures. Molecular dynamics simulations show that further polarization memory loss is caused by out-of-plane distortions associated with twisting and bending of the templated nanoring topologies.
Highlights
Conjugated polymers have been studied extensively because of their semiconducting and optical properties, which offer great potential for a diverse range of applications[1] such as organic light-emitting diodes,[2,3] field-effect transistors,[4,5] and polymer solar cells.[6,7] Recently, macrocycles have attracted increasing attention as quasi-infinite π-conjugated systems exhibiting unique electronic and optical behavior.[8]
A promising approach to synthesis of nanosized fully πconjugated macrocycles based on porphyrin units has been developed using template-directed self-assembly.[15,16]
We examine to what extent out-of-plane distortions of a particular nanoring topology affect the polarization memory of the transition dipole moment and whether such effects can be predicted by molecular mechanics simulations
Summary
Conjugated polymers have been studied extensively because of their semiconducting and optical properties, which offer great potential for a diverse range of applications[1] such as organic light-emitting diodes,[2,3] field-effect transistors,[4,5] and polymer solar cells.[6,7] Recently, macrocycles have attracted increasing attention as quasi-infinite π-conjugated systems exhibiting unique electronic and optical behavior.[8]. We examine to what extent out-of-plane distortions of a particular nanoring topology affect the polarization memory of the transition dipole moment and whether such effects can be predicted by molecular mechanics simulations.
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