Photogeneration of Microporous Amorphous Coordination Polymers from Organometallic Ionic Liquids

Abstract

Ruthenium-containing organometallic ionic liquids with the B(CN) anion were developed that generate microporous amorphous coordination polymers upon UV irradiation. UV light irradiation of [Ru(C H )(C H R)][B(CN) ] (R=butyl, ethyl, octyl) quantitatively generated a yellow powder of a coordination polymer with the formula [Ru(C H ){B(CN) }] . In this reaction, the arene ligand is eliminated by UV irradiation and coordination polymer is formed by coordination of the cyano groups of the anion to the Ru ion. The photogenerated solids exhibited nitrogen absorption properties due to their microporous structure. This paper proposes a method to fabricate functional coordination polymers by photoirradiation of liquids.

Post-Synthetic Modification of Ionic Liquids Using Ligand-Exchange and Redox Coordination Chemistry

“…This work shows that conventional UV-vis spectroscopy enables deep insight into IL nanostructure that otherwise would be difficult to detect. UV-vis spectra have been used in isolated instances to confirm the presence of metal ions extracted into ionic liquids 84 and to understand conversion of metal-containing ionic liquids into coordination polymers, 85,86 whereas this work applies ligand-field analysis to confirm compositional purity and distinguish between mononuclear and polynuclear complexes. Although the solid-like nature of the VCl4 --based ILs suggested the presence of strong intermolecular interactions, UV-vis allowed specific hypotheses about the nanostructure composition to be tested through comparison to TD-DFT simulated spectra.…”

Metal-Containing Poly(ionic liquid) Exhibiting Photogeneration of Coordination Network: Reversible Control of Viscoelasticity and Ionic Conductivity

“…[2][3][4][5][6][7][8][9] To develop materials that undergo structural transformation by external stimuli, we have synthesized ILs containing photoreactive ruthenium (Ru) sandwich complexes. [10][11][12][13] For example, we reported previously that IL 1 (Figure 1) transforms into an amorphous coordination polymer (CP) 2 upon UV photoirradiation. 10 In this reaction, photodissociation of the arene ligand followed by coordination of the cyano group to the Ru center forms the network structure.…”

Thermal properties, crystal structures, and phase diagrams of ionic plastic crystals and ionic liquids containing a chiral cationic sandwich complex

“…ILs have attracted considerable interest for their application as solvents and in electrochemistry owing to their characteristic properties such as nonvolatility, nonflammability, and high ionic conductivity. 11 Recently, we developed a variety of IPCs [12][13][14][15][16] and ILs [17][18][19][20][21] containing cationic sandwich complexes. The plastic phase is ascribed to the globular shape of the sandwich complexes.…”

“…The plastic phase is ascribed to the globular shape of the sandwich complexes. 22,23 The use of organometallic complexes for IPCs or ILs leads to various functions such as magnetic properties, [15][16][17][18] electrical properties, 19 and photochemical reactivities, 20,21 which are not exhibited by onium salts. To elucidate the boundary between IPCs and ILs, we previously investigated the phase behavior of sandwich complex salts, which is shown in Fig.…”