Supramolecular Copolymerization by Sequence Reorganization of a Supramolecular Homopolymer. Issue 24 (24th May 2018)

• Record Type: Journal Article
• Authors: Nadamoto, Kouhei; Maruyama, Kei; Fujii, Naoka; Ikeda, Toshiaki; Kihara, Shin‐ichi; Haino, Takeharu
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 24(2018)
• Page Start: 7028
• Page End: 7033
• Publication Date: 2018-05-24
• Subjects: host–guest complexes -- molecular recognition -- porphyrins -- sequence-regulated copolymers -- supramolecular polymers; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201800980
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The homopolymeric sequence formed by the head‐to‐head association of tetrakisporphyrin1 is completely dissociated by the competitive association of the ditopic guestG2, resulting in the supramolecular copolymer poly‐1 ⋅G2 with an alternatingly repeating host–guest sequence. The 1:1 stoichiometry of1 andG2 is confirmed by a Job plot using UV/Vis titration and diffusion‐ordered NMR spectroscopy (DOSY). The solution viscometry for poly‐1 and poly‐1 ⋅G2 suggests that the supramolecular chain of poly‐1 behaves like a rod, whereas the supramolecular copolymer chain of poly‐1 ⋅G2 behaves like a swelled fat chain, which is entangled in the semi‐dilute regime. Atomic force microscopy shows that the supramolecular polymer poly‐1 ⋅G2 is highly oriented through the interdigitation of the long alkyl chains. Abstract : Supramolecular sequence reorganization : A supramolecular homopolymer is structurally reorganized into the supramolecular copolymer with an alternatingly repeating host–guest sequence via the competitive association of the ditopic guest. The structural reorganization results in regulation of the main‐chain properties in solution.