Controlling the Morphological Features, Aspect Ratio and Emission Patterns of Supramolecular Copolymers by Restricted Dimensional Growth

Abstract One of the bottlenecks associated with supramolecular polymerization of functional π‐systems is the spontaneous assembly of monomers leading to one‐ or two‐dimensional (1D or 2D) polymers without control over chain length and optical properties. In the case of supramolecular copolymerization of monomers that are structurally too diverse, preferential self‐sorting occurs unless they are closely interacting donor‐acceptor pairs. Herein, it is established that the spontaneous 1D polymerization of a phenyleneethynylene ( PE ) derivative and the 2D polymerization of a Bodipy derivative ( BODIPY ) can be controlled by copolymerizing them in different ratios, leading to unusual spindle‐shaped structures with controlled aspect ratio, as evident by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM) studies. For example, when the content of BODIPY is 50 % in the BODIPY ‐ PE mixture, the 1D polymerization of PE is significantly restricted to form elongated spindle‐like structures having an aspect ratio of 4–6. The addition of 75 % of BODIPY to PE resulted in circular spindles having an aspect ratio of 1–2.5, thereby completely restricting the 1D polymerization of PE monomers. Moreover, the resultant supramolecular copolymers exhibited morphology and aspect ratio dependent emission features as observed by the time‐resolved emission studies.