Efficient Energy Funneling in Spatially Tailored Segmented Conjugated Block Copolymer Nanofiber-Quantum Dot or Rod Conjugates.

Hybrid systems composed of conjugated polymers and inorganic semiconductor nanocrystals such as quantum dots (QDs) and nanorods (QRs) represent highly desirable multifunctional materials for applications from energy harvesting to light emission and sensing. Herein, we describe energy transfer studies between low-dispersity segmented conjugated polymer micellar nanofibers integrated with quantum dots that are spatially confined to discrete regions in the hybrid assembly via noncovalent interactions. The nanofibers were prepared from diblock copolymers with a crystallizable poly(di-n-hexylfluorene) (PDHF) core-forming block and different corona-forming blocks using the seeded-growth "living" crystallization-driven self-assembly method. The highly ordered crystalline PDHF core in the fibers functions as a donor and permits long-range exciton transport (>200 nm). Energy can therefore be funneled through the fiber core to QDs and QRs that function as acceptor materials and which are noncovalently bound to spatially defined coronal regions of poly(2-vinylpyridine) (P2VP) or quaternized polyfluorene (QPF). Using steady-state and time-resolved spectroscopy, we demonstrate that efficient energy transfer (over 70%) occurs from the crystalline PDHF donor core to the acceptor CdSe QRs attached at the fiber termini. The emission of the PDHF donor in the hybrid conjugate was extensively quenched (by 84%), and a subsequent 4-fold enhancement of the QR emission in solution was observed. These results indicate that the conjugates prepared in this work show promise for potential applications in fields such as light-emitting diodes, photovoltaics, chemical sensors, and photocatalysis.