Liquid/Liquid Interfacial Synthesis of a Click Nanosheet

Amalia Rapakousiou; Ryota Sakamoto; Ryo Shiotsuki; Ryota Matsuoka; Ukyo Nakajima; Tigmansu Pal; Rintaro Shimada; Amran Hossain; Hiroyasu Masunaga; Satoshi Horike; Yasutaka Kitagawa; Sono Sasaki; Kenichi Kato; Takeaki Ozawa; Didier Astruc; Hiroshi Nishihara

doi:10.1002/chem.201700201

Liquid/Liquid Interfacial Synthesis of a Click Nanosheet

Chemistry. 2017 Jun 22;23(35):8443-8449. doi: 10.1002/chem.201700201. Epub 2017 May 26.

Authors

Amalia Rapakousiou^{1

2}, Ryota Sakamoto^{1

3}, Ryo Shiotsuki¹, Ryota Matsuoka¹, Ukyo Nakajima¹, Tigmansu Pal¹, Rintaro Shimada¹, Amran Hossain⁴, Hiroyasu Masunaga⁵, Satoshi Horike⁶, Yasutaka Kitagawa⁷, Sono Sasaki^{8

9}, Kenichi Kato⁹, Takeaki Ozawa¹, Didier Astruc¹⁰, Hiroshi Nishihara¹

Affiliations

¹ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
² IMDEA Nanociencia Ciudad Universitaria de Cantoblanco, C/Faraday 9, 28049, Madrid, Spain.
³ JST-PRESTO, 4-1-8, Honcho, Kawaguchi, Saitama, 332-0012, Japan.
⁴ Venture Laboratory, Kyoto Institute of Technology, Matsugasaki Hashigami cho 1, Sakyo-ku, Kyoto, 606-8585, Japan.
⁵ Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198, Japan.
⁶ Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
⁷ Division of Chemical Engineering, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3, Machikaneyama, Toyonaka, Osaka, 560-8531, Japan.
⁸ Faculty of Fiber Science and Engineering, Kyoto Institute of Technology, Matsugasaki Hashikami-cho 1, Sakyo-ku, Kyoto, 606-8585, Japan.
⁹ RIKEN SPring-8 Center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5148, Japan.
¹⁰ ISM, UMR CNRS No. 5255, University of Bordeaux, 33405, Talence Cedex, France.

PMID: 28419580
DOI: 10.1002/chem.201700201

Abstract

A liquid/liquid interfacial synthesis is employed, for the first time, to synthesize a covalent two-dimensional polymer nanosheet. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) between a three-way terminal alkyne and azide at a water/dichloromethane interface generates a 1,2,3-triazole-linked nanosheet. The resultant nanosheet, with a flat and smooth texture, has a maximum domain size of 20 μm and minimum thickness of 5.3 nm. The starting monomers in the organic phase and the copper catalyst in the aqueous phase can only meet at the liquid/liquid interface as a two-dimensional reaction space; this allows them to form the two-dimensional polymer. The robust triazole linkage generated by irreversible covalent-bond formation allows the nanosheet to resist hydrolysis under both acidic and alkaline conditions, and to endure pyrolysis up to more than 300 °C. The coordination ability of the triazolyl group enables the nanosheet to act as a reservoir for metal ions, with an affinity order of Pd²⁺ >Au³⁺ >Cu²⁺ .

Keywords: cycloaddition; interfaces; polymers; synthesis design; transition metals.