90004938

open access

Accepted Manuscript

Multifunctional Ionic Liquids from Rhodium(I) Isocyanide Complexes: Thermochromic, Fluorescence, and Chemochromic Properties Based on Rh-Rh Interaction and Oxidative Addition

English (英語)

Chemistry-A European Journal

24(23)

6239-6247

Wiley-VCH Verlag

2018-04-20

2019-05-01

Square-planar rhodium(I) isocyanide complexes exhibit unique chemical reactivities such as the formation of Rh−Rh bonds and oxidative addition. This paper details the syntheses and properties of multifunctional ionic liquids containing Rh(I) isocyanide complexes [Rh(nBuNC)4]X (X = Tf2N (= N(SO2CF3)2−), Nf2N (= N(SO2C4F9)2−), FSA (= N(SO2F)2−), CF3BF3−). Salts with Tf2N and Nf2N were liquids, whereas those with FSA and CF3BF3 were solids at room temperature. The salts exhibited thermochromism in the liquid state, changing from orange at high temperatures to blue‐purple at lower temperatures. This is based on the equilibrium between monomer, dimer, and other oligomers associated with Rh−Rh bond formation. The salts also exhibited fluorescence. Exposure of the Tf2N salt to methyl iodide vapor produced ionic liquid mixtures [Rh(nBuNC)4]x[Rh(nBuNC)4IMe](1−x)[Tf2N], concomitant with a color change from purple to red, orange, and yellow, extending the thermochromic color range. The reaction of the Tf2N salt and iodine produced mononuclear and polynuclear iodine adducts. Thus, these liquids exhibit thermochromism, fluorescence, vapochromism, chemical reactivities, and characteristic properties of ionic liquids.

thermal properties

学術雑誌論文

© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This is the peer reviewed version of the following article: [Chemistry-A European Journal,24(23):6239-6247], which has been published in final form at http://dx.doi.org/10.1002/chem.201800333. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-Archiving.