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Perfluorophenyl-Directed Giant Porphyrin J-Aggregates |
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| Authors: | Dr Mitsuhiko Morisue Ikuya Ueno Kunihiko Muraoka Dr Shun Omagari Dr Takayuki Nakanishi Prof Yasuchika Hasegawa Dr Takaaki Hikima Prof Sono Sasaki |
| Institution: | 1. Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585 Japan;2. Graduate School of Engineering, Hokkaido University, North 13 West 8, Kita-ku, Sapporo, 060-8628 Japan
Present address: School of Materials and Chemical Technology, Tokyo Institute of Technology, Ookayama 2–12-1-S8, Meguro-ku, Tokyo, 152-8552 Japan;3. Graduate School of Engineering, Hokkaido University, North 13 West 8, Kita-ku, Sapporo, 060-8628 Japan Present address: Department of Materials Science and Technology, Tokyo University of Science, 6-3-1 Niijuku, Katsushika-ku, Tokyo, 125-8585 Japan;4. Graduate School of Engineering, Hokkaido University, North 13 West 8, Kita-ku, Sapporo, 060-8628 Japan;5. RIKEN SPring-8 Center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5148 Japan;6. Faculty of Fiber Science and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585 Japan |
| Abstract: | Quadrupolar interactions of porphyrin bearing two pentafluorophenylethynyl terminals ( 1 ) drove the formation of a successive one-dimensional staircase structure, i.e., J-aggregates, to yield millimeter-length needles with a single-crystalline character in methylcyclohexane solution. In contrast, π-stacked interactions of porphyrin bearing two nonfluorinated phenyl terminals ( 2 ) formed no aggregates in solution. A spin-cast film of 1 also showed bathochromic shift of the Soret and Q bands, indicating the formation of J-aggregates. The molecular arrangement of the J-aggregates was revealed by microbeam glazing-incidence wide-angle X-ray diffraction (GIWAXD), and was in good agreement with the optimized structure generated by density functional theory (DFT) calculations. |
| Keywords: | aggregation J-aggregates porphyrinoids quadrupolar interaction supramolecular chemistry |