A Multi-Redox Responsive Cyanometalate-Based Metallogel

Kiyotaka Mitsumoto; Jamie M Cameron; Rong-Jia Wei; Hiroyuki Nishikawa; Takuya Shiga; Masayuki Nihei; Graham N Newton; Hiroki Oshio

doi:10.1002/chem.201605542

A Multi-Redox Responsive Cyanometalate-Based Metallogel

Chemistry. 2017 Jan 31;23(7):1502-1506. doi: 10.1002/chem.201605542. Epub 2017 Jan 6.

Authors

Kiyotaka Mitsumoto¹, Jamie M Cameron¹, Rong-Jia Wei¹, Hiroyuki Nishikawa², Takuya Shiga¹, Masayuki Nihei¹, Graham N Newton^{1

3}, Hiroki Oshio¹

Affiliations

¹ Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan.
² Department of Chemistry, Faculty of Science, Ibaraki University, 2-1-1 Bunkyo, Mito, Ibaraki, 310-8371, Japan.
³ School of Chemistry, University of Nottingham, University Park Nottingham, Nottingham, NG7 2RD, UK.

PMID: 27917549
DOI: 10.1002/chem.201605542

Abstract

A TTF-based (TTF=tetrathiafulvalene) tridentate ligand (α-(4'-methyl-4,5-di-n-dodecylthylthiotetrathiafulvalene-5'-ylthio)- α'-[2,2,2-tris(1-pyrazolyl)ethoxy]-p-xylene) (L) with long-chain alkyl moieties was prepared in order to obtain a new multi-redox active gelator based on a mixed-metal octanuclear complex [Fe^III₄ Ni^II₄ (CN)₁₂ (tp)₄ (L)₄ ](BF₄ )₄ (1). The magnetism, electrochemistry, and gelation behavior of 1 were studied and 1,2-dichlorobenzene solutions of 1 are shown to display thermoreversible gelation behavior at room temperature. Furthermore, the gel phase of 1 was shown to undergo room-temperature gel-to-sol transformations induced by both the oxidation and reduction of the gelator complex by F₄ TCNQ or [Fe^II (Cp*)₂ ], respectively.

Keywords: cyanometalate; redox active; sol-gel; stimuli-responsive materials; supramolecular chemistry.