A Versatile Strategy toward Donor-Acceptor Nanofibers with Tunable Length/Composition and Enhanced Photocatalytic Activity.

Living crystallization-driven self-assembly (CDSA) has emerged as an efficient strategy to generate nanofibers of π-conjugated polymers (CPNFs) in a controlled fashion. However, reports of donor-acceptor (D-A) heterojunction CPNFs are extremely rare. The preparation of these materials remains a challenge due to the lack of rational design guidelines for the D-A π-conjugated units. Herein, we report a versatile CDSA strategy based upon carefully designed D-A--oligomers in which electron-deficient benzothiadiazole (BT) or dibenzo[,]thiophene 5,5-dioxide (FSO) units are attached to the two ends of an oligo(-phenylene ethynylene) heptamer [BT-OPE-BT, FSO-OPE-FSO]. This arrangement with the electron-deficient groups at the two ends of the oligomer enhances the stacking interaction of the A-D-A π-conjugated structure. In contrast, D-A-D structures with a single BT in the middle of a string of OPE units disrupt the packing. We employed oligomers with a terminal alkyne to synthesize diblock copolymers BT-OPE-BT--P2VP and BT-OPE-BT--PNIPAM (P2VP = poly(2-vinylpyridine), PNIPAM = poly(-isopropylacrylamide)) and FSO-OPE-FSO--P2VP and FSO-OPE-FSO--PNIPAM. CDSA experiments with these copolymers in ethanol were able to generate CPNFs of controlled length by both self-seeding and seeded growth as well as block comicelles with precisely tunable length and composition. Furthermore, the D-A CPNFs with a BT-OPE-BT-based core demonstrate photocatalytic activity for the photooxidation of sulfide to sulfoxide and benzylamine to -benzylidenebenzylamine. Given the scope of the oligomer compositions examined and the range of structures formed, we believe that the living CDSA strategy with D-A-based co-oligomers opens future opportunities for the creation of D-A CPNFs with programmable architectures as well as diverse functionalities and applications.