Solvatochromism and Theoretical Studies of Dicyanobis(phenylpyridine)iridium(III) Complex Using Density Functional Theory

Noorshida Mohd Ali(1*), Anthony J. H. M. Meijer(2), Michael D. Ward(3), Norlinda Daud(4), Norhayati Hashim(5), Illyas Md Isa(6)

(1) Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900, Tanjong Malim, Perak, Malaysia
(2) Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, United Kingdom
(3) Department of Chemistry, University of Warwick, Coventry, CV4 7AL, United Kingdom
(4) Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900, Tanjong Malim, Perak, Malaysia
(5) Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900, Tanjong Malim, Perak, Malaysia
(6) Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900, Tanjong Malim, Perak, Malaysia
(*) Corresponding Author


Luminescent cyanometallate [Ir(ppy)2(CN)2] (ppy = C6H5C5H4N) has recently gained attention due to its desired photophysical properties. Our research group reported that the [Ir(ppy)2(CN)2] has shown a negative solvatochromism like [Ru(bipy)(CN)4]2–, resulting in a blue-shift of the UV-Vis absorption bands in the water. Therefore, to gain insight into the specific solvent-solute interaction governed by the hydrogen bond in the solvation hydration shell, density functional theory (DFT) calculations were performed on the singlet ground state of the [Ir(ppy)2(CN)2] and its solvent environment in the water at B3LYP level theory. It was demonstrated, seven water molecules provided a good description of the relevant spectra: IR and UV-Vis. The calculation reproduced the positions and intensities of the observed n(CºN) bands at 2069 and 2089 cm–1. The calculated MLCT transition wavelength was 366 nm vs. a measured value of 358 nm, differing by 8 nm. The study revealed the water molecules interacted with cyanide ligands through CN⋯H-OH type hydrogen bonds and water-water interactions (HO-H⋯OH2 type hydrogen bonds) were involved in the solvation hydration shell around the [Ir(ppy)2(CN)2].


iridium(III) anionic complex; DFT calculation; solvation hydration shell; cyanide ligand


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