文献类型：期刊文献

英文题名：Crystallization-Driven Self-Assembly toward Uniform Nanofibers Containing a Donor-Acceptor Core with Near-Infrared Absorption/Emission, Photodynamic, and Photothermal Activities: A Small Variation on the Structure of Donor-Acceptor Segment Matters

作者：Ma, Junyu[1];Huang, Fengfeng[1];Zhang, Sen[1];Ye, Jing[2];Huang, Xiaoyu[1];Lu, Guolin[1];Feng, Chun[1,3]

机构：[1]Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Synthet Self Assembly Chem Organ Funct Mol, Shanghai 200032, Peoples R China;[2]Shanghai Inst Technol, Sch Chem & Environm Engn, Shanghai 201418, Peoples R China;[3]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Shanghai 200237, Peoples R China

年份：2023

卷号：56

期号：21

起止页码：8529

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20234815112522);WOS:【SCI-EXPANDED(收录号:WOS:001096764700001)】；

基金：The authors are thankful for the financial support from the National Science Foundation for Distinguished Young Scholars (51825304), the National Natural Science Foundation of China (52122314 and U22A20131), the project of Bureau of International Cooperation, CAS (121731KYSB20200006), the Shanghai Scientific and Technological Innovation Project (21520780100, 21ZR1481700, 22JC1401000, and 22ZR1475400), the Innovation Program of Shanghai Municipal Education Commission (2019-01-07-00-05-E00012), and the East China University of Science and Technology (SLD13223004). The authors thank Dr. Kun Cui for his assistance in TEM measurements, Dr. Xiulong Mao (Luminary Studio) for the simulation of the trimeric packing mode, and the beamline BL16B1 at SSRF for providing the beam time.

语种：英文

外文关键词：Aromatic compounds - Block copolymers - Conjugated polymers - Fibers - Infrared devices - Light absorption - Oligomers - Polymerization - Self assembly

摘要：Although living crystallization-driven self-assembly (CDSA) has emerged as a facile approach to generate uniform pi-conjugated-polymer-based fiber-like micelles, the extension of living CDSA to prepare uniform donor-acceptor (D-A) fiber-like micelles of controlled length with attractive near-infrared (NIR) absorption/emission, photodynamic (PD), and photothermal (PT) properties is virtually unexplored. Herein, three block copolymers composed of the same corona-forming P2VP(44) (P2VP = poly(2-vinylpyridine), the subscript is the degree of polymerization) but different D-A pi-conjugated core-forming co-oligomers of OPE4-DPP-OPE4 (OPE4 = oligo(p-phenylene ethynylene), DPP = diketopyrrolopyrrole) are designed and synthesized to probe the steric and electronic effect of co-oligomers of OPE4-DPP-OPE4 on their CDSA behaviors and photophysical properties. One co-oligomer contains a DPP with two 2-ethylhexyl side chains flanked by two thiophene-OPE4 segments (b-T-OPE4-DPP-OPE4). The variation of the second one is the replacement of 2-ethylhexyl side chains with linear octyls (l-T-OPE4-DPP-OPE4). The last one is composed of a DPP with two linear octyl side chains flanked by two phenylene-OPE4 segments (l-P-OPE4-DPP-OPE4). Uniform fiber-like micelles can be generated by a self-seeding approach for b-T-OPE4-DPP-OPE4-b-P2VP(44) and l-P-OPE4-DPP-OPE4-b-P2VP(44), whereas polydisperse fiber-like micelles only can be obtained for l-T-OPE4-DPP-OPE4-b-P2VP(44) likely due to the multiple packing modes of l-T-OPE4-DPP-OPE4. Intriguingly, the aging of micelles of l-T-OPE4-DPP-OPE4-b-P2VP(44) can promote the conversion of the packing mode of l-T-OPE4-DPP-OPE4 units to their most thermodynamically stable packing mode, and thus, self-seeding of aged seed micelles of l-T-OPE4-DPP-OPE4-b-P2VP(44) gave uniform fiber-like micelles of controlled length. More interestingly, micellar solution of b-T-OPE4-DPP-OPE4-b-P2VP(44) exhibits NIR absorption/emission, PT, and PD activities upon the light irradiation at 660 nm. Although micellar solution of l-T-OPE4-DPP-OPE4-b-P2VP(44) also shows NIR absorption/emission and PT activity, its PD activity is much lower relative to that of b-T-OPE4-DPPa-OPE4-b-P2VP(44). The micellar solution of l-P-OPE4-DPP-OPE4-b-P2VP(44) exhibits neither NIR absorption/emission nor PT/PD activities upon the light irradiation at 660 nm. All these results showed that a small variation of structure of OPE4-DPP-OPE4 can lead to distinct CDSA behaviors and absorption/emission/PD/PT properties.