Shape-tunable two-dimensional assemblies from chromophore-conjugated crystallizable poly(L-lactides) with...

This work reports temperature-dependent shape-changeable two-dimensional (2D) nanostructures by crystallization-driven self-assembly (CDSA) from a chromophore-conjugated poly(L-lactide) (PLLA) homopolymer (PTZ-P1) that contained a polar dye, phenothiazine (PTZ), at the chain-end of the crystallizable PLLA. The CDSA of PTZ-P1 in a polar solvent, isopropanol (iPrOH), by an uncontrolled heating-cooling process, majorly generates lozenge-shaped 2D platelets via chain-folding-mediated crystallization of the PLLA core, leading to the display of the phenothiazines on the 2D surface that confers colloidal stability and orange-emitting luminescent properties to the crystal lamellae. Isothermal crystallization at 60 °C causes a morphological change in PTZ-P1 platelets from lozenge to truncated-lozenge to perfect hexagon under different annealing times, while no shape change was noticed in the structurally similar PTZ-P2 polymer with a longer PLLA chain under similar conditions. This study unveils the complex link between the 2D platelet morphologies and degree of polymerization (DP) of PLLA and the corona-forming dye character. Further, the co-assembly potential of PTZ-P1 with hydrophobic pyrene-terminated PLLAs of varying chain lengths (PY-P1, PY-P2, and PY-P3) was examined, as these two dyes could form a Förster Resonance Energy Transfer (FRET) pair on the 2D surface. The impact of the length of the crystallizable PLLA on the photophysical properties of the surface-occupied chromophores revealed crucial insights into interchromophoric interactions on the platelet surface. A reduction in the propensity for π-stacking with increasing chain-folding in longer PLLAs is manifested in the chain-length-dependent FRET efficiencies and excimer emission lifetimes within the resultant monolayered 2D assemblies. The unconventional "butterfly-shaped" molecular architecture of the tested phenothiazine, combined with its varied functional features and polar character, adds a distinctive dimension to the underdeveloped field of CDSA of chromophore-conjugated poly(L-lactides), opening future avenues for the development of advanced nanostructured biodegradable 2D materials with programmable morphology and optical functions.