Spherical Assemblies from π-Conjugated Alternating Copolymers: Toward Optoelectronic Colloidal Crystals

JACS

Taeko Adachi †, Liang Tong †, Junpei Kuwabara †‡, Takaki Kanbara †‡, Akinori Saeki §, Shu Seki §, and Yohei Yamamoto *†‡

 http://pubs.acs.org/doi/abs/10.1021/ja3106626

The authors demonstrated that polymers such as polyfluorene and polythiophene having a single monomer component hardly formed defined and discrete objects but only gave ill-defined aggregates. In contrast, alternating copolymers typically having both fluorene and thiophene components in their repeating unit self-assembled into well-shaped spheres with diameters ranging from several hundreds of nanometers to several micrometers. Such clear differences in terms of the assembling geometries derive from the rigidity and crystallinity of the polymers, where the copolymers possess large steric hindrance on their backbone that reduces planarity of the polymers and inhibits anisotropic crystal growth, leading to the formation of structurally isotropic spheres. Changing the assembling parameters can systematically control diameter and deviation of the spheres. Furthermore, photocarrier lifetimes of the spheres were markedly enhanced by more than 3 orders of magnitude.