Crystallization-Driven Controlled Two-Dimensional (2D) Assemblies from Chromophore-Appended Poly(L-lactide)s: Highly Efficient Energy Transfer on a 2D Surface.

A rational approach towards precision two-dimensional (2D) assemblies by crystallization-driven self-assembly (CDSA) of poly(L-lactides) (PLLAs), end-capped with dipolar dyes like merocyanine (MC) or naphthalene monoimide (NMI) and hydrophobic pyrene (PY) or benzene (Bn) is described. PLLA chains crystallize into diamond-shaped platelets in isopropanol, which forces the terminal dyes to assemble into a 2D array on the platelet surface by either dipolar interactions or π-stacking and exhibit tunable emission. Dipolar dyes play a critical role in imparting colloidal stability and structural uniformity to the 2D crystals, which is partly compromised for hydrophobic ones. Co-crystallization between NMI- and PY-labeled PLLAs yields similar diamond-shaped co-platelets with highly efficient (≈80 %) Förster Resonance Energy Transfer on the 2D surface. Further, the "living" CDSA method confers enlarged, segmented block co-platelets using one of the homopolymers as "seed" and the other as "unimer".