Effect of Phosphotungstic Acid on Self-seeding of Oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine)※
Received date: 2021-12-13
Online published: 2022-01-07
Supported by
National Natural Science Foundation of China(51825304); National Natural Science Foundation of China(52122341); National Natural Science Foundation of China(51873229); National Natural Science Foundation of China(51961145103); Youth Innovation Promotion Association of CAS(Y2020062)
Self-seeding route of living crystallization-driven self-assembly with merits of easily-handling and excellent compatibility with various block copolymers (BCPs) has been considered as one of the most important strategies to generate uniform nanofibers of controlled length and composition. Polyoxometalates with unique structure and shape are usually endowed with attractive electric/magnetic/optical properties. Herein, the influence of phosphotungstic acid (H3O40PW12) on the self-seeding of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV5-b-P2VP42, the subscripts represent the number of repeat unit of each block) was systematically examined aiming to get more insight on the effect of polyoxometalates on living crystallization-driven self-assembly. Uniform fiber-like micelles of OPV5-b-P2VP42 are formed with addition of different molar ratios of phosphotungstic acid to pyridyls of P2VP, αacid/v, from 0 to 0.20. The percentage of surviving seed micelles decreased exponentially with increasing annealing temperature regardless of αacid/v from 0 to 0.10, demonstrating the typical characteristics of self-seeding behaviors. The most striking finding of this work is that the resistance of seed micelles toward the dissolution upon annealing is enhanced significantly with the increasing of αacid/v, leading to the formation of shorter fiber-like micelles with a higher αacid/v. For example, fiber-like micelles with average length of 1325, 232, 137 and 73 nm were formed with αacid/v of 0, 0.01, 0.05 and 0.10, respectively, upon the heating of seed micelles of OPV5-b-P2VP42 with average length of 22 nm at 60 ℃ for 45 min, followed by cooling/aging at 30 ℃ for 24 h. It is likely that the coordination, instead of hydrogen bonding interaction, between phosphotungstic acid and pyridyls, contributes to the enhancement of resistance of seed micelles toward the dissolution. The tight and multi-dentate coordination between phosphotungstic acid and pyridyls of P2VP chains would make the P2VP chain crosslink. The crosslinking would weaken the repulsion within P2VP chains and increase the energy for the dissolution of micelles. This work not only provides more information to deepen our understanding on the influence of nature of corona chains on living crystallization-driven self-assembly (CDSA), especially self-seeding process, but also presents a new platform to generate uniform hybrid polyoxometalate/polymer nanofibers of controlled length.
Zhiqin Wang , Bo Xiang , Xiaoyu Huang , Guolin Lu . Effect of Phosphotungstic Acid on Self-seeding of Oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine)※[J]. Acta Chimica Sinica, 2022 , 80(3) : 297 -302 . DOI: 10.6023/A21120557
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