Subject Number : S-16-NM-0008
Support Type : 機器利用
Proposal Title (English) : Supramolecular living polymerization （Pathway Complexity in Kinetically Controlled Supramolecuar Polymerization）
Username (English) : Sung Ho Jung
Affiliation (English) :JSPS

1. Summary
Self-assembly has become a key technology for fabrication of ordered functional structures with useful properties for various application fields1. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process2, their unique pathway complexity is connected with design of supramolecular structure. We confirm that we can modulate pathway complexity in supramolecular polymerization through rational molecular design.

2. Experimental
1H NMR and 13C NMR spectra were measured on a JEOL ECS-400 spectrometer with tetramethylsilane (0 ppm for 1H) or residual CHCl3 (77 ppm for 13C) as an internal standard.
Platform staffs provided supports such as instructions and trouble shootings of NMR measurement.

3. Results and Discussion

Scheme 1. Molecular structures of 1S and 1O.

The unique self-assembly behavior of porphyrin derivative of 1O is already reported from our group3. We introduced methyl sulfide group instead of methyl ether in molecular structure for constructing new pathway complexity from molecular design. We synthesized the molecular structure of 1S, which was successfully characterized by 1H and 13C NMR analysis.

Figure 1. (a) 1H NMR and (b) 13C NMR of 1S.

4. References
[1] D. Go, X. Zhang, V. Stpaneko, F. Wurthner, Nat. Commun. 2015, 6, 7009.
[2] P. Korevaar, S. George, A. Markvoort, M. Smulders, P. Hilbers, A. Schenning, T. Greef, E. Meijer, Nature
2012, 481, 492.
[3] S. Ogi, K. Sugiyasu, S. Manna, S. Samitsu, M. Takeuchi, Nature Chemistry 2012, 481, 492. Nature Chemistry, 2014, 6, 188.

5. Publication/Presentation
(1) M. Endo, T. Fukui, S. Jung, S. Yagai, M. Takeuchi, K. Sugiyasu, “Photo-regulated living supramolecular polymerization established by combining energy landscapes of photoisomerization and nucleation-elongation processes” J. Am. Chem. Soc. 138, (2016) 11347-11353.