文献类型：期刊文献

英文题名：A Versatile Strategy toward Donor-Acceptor Nanofibers with Tunable Length/Composition and Enhanced Photocatalytic Activity

作者：Huang, Fengfeng[1];Ma, Junyu[1];Nie, Jiucheng[1];Xu, Binbin[2];Huang, Xiaoyu[1];Lu, Guolin[1];Winnik, Mitchell A.[3,4];Feng, Chun[1,2]

机构：[1]Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Fluorine & Nitrogen Chem & Adv Mat, Shanghai 200032, Peoples R China;[2]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Shanghai 200237, Peoples R China;[3]Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada;[4]Univ Toronto, Dept Chem Engn & Appl Chem, Toronto, ON M5S 3E2, Canada

年份：2024

卷号：146

期号：36

起止页码：25137

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20243616977845);WOS:【SCI-EXPANDED(收录号:WOS:001308478000001)，CCR-EXPANDED(收录号:WOS:001308478000001)】；

基金：The authors are thankful for financial support from National Natural Science Foundation of China (52122314, U22A20131, 52173014, and 52361165657), Strategic Priority Research Program of Chinese Academy of Sciences (XDB0590000), and Shanghai Scientific and Technological Innovation Project (21520780100, 22JC1401000, and 22ZR1475400). M.A.W. thanks NSERC Canada for its financial support. The authors thank Dr. Kun Cui for his assistance with TEM measurements.

语种：英文

外文关键词：Alkylation - Conjugated polymers - Cracking (chemical) - Elastomers - Hydrogen bonds - Oligomers - Photocatalytic activity - Photolysis - Photooxidation - Polycyclic aromatic hydrocarbons - Polyphenylene vinylene - Self assembly - Thiophene

摘要：Living crystallization-driven self-assembly (CDSA) has emerged as an efficient strategy to generate nanofibers of pi-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 pi-conjugated units. Herein, we report a versatile CDSA strategy based upon carefully designed D-A-co-oligomers in which electron-deficient benzothiadiazole (BT) or dibenzo[b,d]thiophene 5,5-dioxide (FSO) units are attached to the two ends of an oligo(p-phenylene ethynylene) heptamer [BT-OPE7-BT, FSO-OPE7-FSO]. This arrangement with the electron-deficient groups at the two ends of the oligomer enhances the stacking interaction of the A-D-A pi-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-OPE7-BT-b-P2VP and BT-OPE7-BT-b-PNIPAM (P2VP = poly(2-vinylpyridine), PNIPAM = poly(N-isopropylacrylamide)) and FSO-OPE7-FSO-b-P2VP and FSO-OPE7-FSO-b-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-OPE7-BT-based core demonstrate photocatalytic activity for the photooxidation of sulfide to sulfoxide and benzylamine to N-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.