Solvent-Vapor-Induced Reversible Single-Crystal-to-Single-Crystal Transformation of a Triphosphaazatriangulene-Based Metal-Organic Framework

Soichiro Nakatsuka; Yusuke Watanabe; Yoshinobu Kamakura; Satoshi Horike; Daisuke Tanaka; Takuji Hatakeyama

doi:10.1002/anie.201912195

Solvent-Vapor-Induced Reversible Single-Crystal-to-Single-Crystal Transformation of a Triphosphaazatriangulene-Based Metal-Organic Framework

Angew Chem Int Ed Engl. 2020 Jan 20;59(4):1435-1439. doi: 10.1002/anie.201912195. Epub 2019 Dec 27.

Authors

Soichiro Nakatsuka¹, Yusuke Watanabe¹, Yoshinobu Kamakura¹, Satoshi Horike², Daisuke Tanaka¹, Takuji Hatakeyama¹

Affiliations

¹ Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan.
² Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto, 606-8501, Japan.

PMID: 31773880
DOI: 10.1002/anie.201912195

Abstract

A triphosphaazatriangulene (H₃ L) was synthesized through an intramolecular triple phospha-Friedel-Crafts reaction. The H₃ L triangulene contains three phosphinate groups and an extended π-conjugated framework, which enables the stimuli-responsive reversible transformation of [Cu(HL)(DMSO)⋅(MeOH)]_n , a 3D-MOF that exhibits reversible sorption characteristics, into (H₃ L⋅0.5 [Cu₂ (OH)₄ ⋅6 H₂ O] ⋅4 H₂ O), a 1D-columnar assembled proton-conducting material. The hydrophilic nature of the latter resulted in a proton conductivity of 5.5×10^-3 S cm^-1 at 95 % relative humidity and 60 °C.

Keywords: metal-organic frameworks; phospha-Friedel-Crafts reaction; phosphorus; polycycles; proton transport.