Thermosalience in Macrocycle-Based Soft Crystals via Anisotropic Deformation of Disilanyl Architecture
- Kenichiro OmotoKenichiro OmotoDepartment of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanDivision of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama-cho, Ikoma 630-0192, JapanMore by Kenichiro Omoto,
- Toyotaka NakaeToyotaka NakaeDepartment of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Toyotaka Nakae,
- Masaki NishioMasaki NishioDepartment of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Masaki Nishio,
- Yoshinori Yamanoi*Yoshinori Yamanoi*[email protected]Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Yoshinori Yamanoi,
- Hidetaka KasaiHidetaka KasaiDivision of Physics, Faculty of Pure and Applied Sciences, Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, JapanMore by Hidetaka Kasai,
- Eiji NishiboriEiji NishiboriDivision of Physics, Faculty of Pure and Applied Sciences, Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, JapanMore by Eiji Nishibori,
- Takaki MashimoTakaki MashimoDivision of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, JapanMore by Takaki Mashimo,
- Tomohiro SekiTomohiro SekiDivision of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, JapanMore by Tomohiro Seki,
- Hajime ItoHajime ItoDivision of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, JapanInstitute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido 060-8628, JapanMore by Hajime Ito,
- Kazuki NakamuraKazuki NakamuraDepartment of Image and Materials Science, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, JapanMore by Kazuki Nakamura,
- Norihisa KobayashiNorihisa KobayashiDepartment of Image and Materials Science, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, JapanMore by Norihisa Kobayashi,
- Naofumi NakayamaNaofumi NakayamaCONFLEX Corporation, 3-23-17 Takanawa, Minato-ku, Tokyo 108-0074, JapanMore by Naofumi Nakayama,
- Hitoshi GotoHitoshi GotoDepartment of Computer Science and Engineering, Toyohashi University of Technology, 1-1 Tempaku-cho, Toyohashi, Aichi 441-8580, JapanMore by Hitoshi Goto, and
- Hiroshi Nishihara*Hiroshi Nishihara*[email protected]Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Hiroshi Nishihara
Abstract
We describe here the preparation of soft crystals using disilanyl macrocycle C4 possessing four p-phenylenes circularly connected by four flexible disilane bonds. Single crystals of C4 exhibited a reversible thermal single-crystal-to-single-crystal (SCSC) phase transition behavior between two crystal phases accompanied by remarkable mechanical motion (thermosalient effect), as revealed by thermal analyses and X-ray diffraction measurements. Detailed structural analyses implied that flexibility of the parallelogram disilanyl architecture and molecular packing mode via weak intermolecular interactions facilitated a concerted structural transformation (parallel crank motion) of macrocycles in the crystal, thus resulting in the SCSC phase transition accompanied by anisotropic shrinking/elongation of the cells to induce the thermosalient effect. This work explores a new area of organosilicon chemistry and presents the potential utility of disilanyl macrocycles as soft crystals.
Cited By
This article is cited by 2 publications.
- Bibhuti Bhusan Rath, Gianpiero Gallo, Robert E. Dinnebier, Jagadese J. Vittal. Reversible Thermosalience in a One-Dimensional Coordination Polymer Preceded by Anisotropic Thermal Expansion and the Shape Memory Effect. Journal of the American Chemical Society 2021, 143 (4) , 2088-2096. https://doi.org/10.1021/jacs.0c12363
- Bibhuti Bhusan Rath, Jagadese J. Vittal. Single-Crystal-to-Single-Crystal [2 + 2] Photocycloaddition Reaction in a Photosalient One-Dimensional Coordination Polymer of Pb(II). Journal of the American Chemical Society 2020, 142 (47) , 20117-20123. https://doi.org/10.1021/jacs.0c09577