Living Supramolecular Polymerization
Kazunori Sugiyasu
Molecular Design & Function Group, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
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Supramolecular polymers are a new type of polymer in which monomeric units are brought together by reversible and highly directional non-covalent bonds, such as hydrogen bonding, coordination bonding, and p-p stacking. Therefore, supramolecular polymers are endowed with intriguing functionalities and properties that originate from the dynamic behavior of the non-covalent bonds. However, the “dynamic” reversible polymerization process in turn implies that controlling the length of supramolecular polymers is entropically unlikely. As such, in contrast to conventional polymer chemistry, an important challenge in realizing living polymerization technique has still remained in the supramolecular polymer chemistry1.
In this presentation, I would like to show the first example of living supramolecular polymerization reported by us recently2. Our supramolecular polymerization was very unique in that the polymerization pathway was coupled with a competing aggregation pathway3. This pathway complexity dictated the spontaneous supramolecular polymerization to be kinetically controlled, and the addition of “seeds” of the supramolecular polymer initiated the supramolecular polymerization. We have investigated this polymerization process in a similar way to analyze the living polymerization: (1) the polymerization kinetics was the first order to the concentration of the seeds, (2) polymerization can be repeated many times, and (3) polydispersity indices (PDI) of the obtained polymers were around 1.1. All these results demonstrated that we succeeded for the first time in realizing living supramolecular polymerization.
Scheme 1. Pathway complexity of supramolecular polymerization2.
References
1. (a) de Greef, T. F. A.; Smulders, M. M. J.; Wolffs, M. ; Schenning, A. P. H. J.; Sijbesma, R. P.; Meijer, E. W. Chem. Rev. 2009, 109, 5687; (b) van der Zwaag, D.; de Greef, T. F. A.; Meijer, E. W. Angew. Chem. Int. Ed. 2015, 54, 8334; (c) Ogi, S.; Stepanenko, V.; Sugiyasu, K.; Takeuchi, M.; Würthner, F. J. Am. Chem. Soc. 2015, 137, 3300; (d) Kang, J.; Miyajima, D.; Mori, T.; Inoue, Y.; Aida, T. Science 2015, 347, 646.
2. Ogi, S.; Sugiyasu, K.; Manna, S.; Samitsu, S.; Takeuchi, M. Nat. Chem. 2014, 6, 188.
3. Ogi, S.; Fukui, T.; Melinda, L. J.; Takeuchi, M.; Sugiyasu, K. Angew. Chem. Int. Ed. 2014, 53, 14363.
CURRICULUM VITAE – Dr. Kazunori Sugiyasu
PERSONAL
Date & Place of Birth October 04, 1977, Japan
Work Address National Institute for Materials Science,
1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
Telephone +81-29-859-2110
Fax +81-29-859-2101
EDUCATION
B.Sc. Kyushu University, 2000
M. Sc. Kyushu University, 2002
Ph. D. Kyushu University (Prof. Seiji Shinkai), 2005
PROFESSIONAL CAREER
PostDoc Fellow MIT (Prof. Tim Swager), 2005-2007
PostDoc Fellow National Institute for Materials Science, 2007
Senior Resercher National Institute for Materials Science, 2008-present
RESEARCH INTERESTS
(1) Conjugated Polymers
(2) Supramolecular Polymers
SELECTIVE PUBLICATIONS
1. C. Pan, C. Zhao, M. Takeuchi, K. Sugiyasu “Conjugated oligomers and polymers sheathed with designer sidechains” Chem. Asian J., 2015, 10, 1820-1835. (Focus Review)
2. S. Ogi, T. Fukui, M. L. Jue, M. Takeuchi, K. Sugiyasu “Kinetic control over pathway complexity in supramolecular polymerization through modulating the energy landscape by rational molecular design” Angew. Chem. Int. Ed., 2014, 53, 14363-14367.
3. S. Ogi, K. Sugiyasu, S. Manna, S. Samitsu, M. Takeuchi “Living supramolecular polymerization realized through a biomimetic approach” Nature Chem., 2014, 6, 188-195.
4. C. Pan, K. Sugiyasu, J. Aimi, A. Sato, M. Takeuchi “Picket-fence polythiophene and its diblock copolymers that afford microphase separation comprising a stacked and an isolated polythiophene ensemble” Angew. Chem. Int. Ed., 2014, 53, 8870-8875.
5. M. Kiguchi, T. Ohto, S. Fujii, K. Sugiyasu, S. Nakajima, M. Takeuchi, H. Nakamura “Single molecular resistive switch obtained via sliding multiple anchoring points and varying effective wire length” J. Am. Chem. Soc., 2014, 136, 7327-7332.
6. C. Pan, K. Sugiyasu, Y. Wakayama, A. Sato, M. Takeuchi, K. Sugiyasu “Thermoplastic fluorescent conjugated polymers: benefits of preventing p-p stacking” Angew. Chem. Int. Ed., 2013, 52, 10775-10779.
7. K. Sugiyasu, Y. Honsho, R. M. Harrison, A. Sato, T. Yasuda, S. Seki, M. Takeuchi “A self-threading polythiophene: defect-free insulated molecular wires endowed with long effective conjugation length” J. Am. Chem. Soc., 2010, 132, 14754-14756.