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Molecular Design of pH-Sensitive Ru(II)–Polypyridyl Luminophores

Romanova, Julia, Sadik, Yousif, Prabhath, M. R. Ranga, Carey, J. David and Jarowski, Peter D. (2019) Molecular Design of pH-Sensitive Ru(II)–Polypyridyl Luminophores The Journal of Physical Chemistry A, 123 (23). pp. 4921-4928.

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Abstract

Three new [Ru(bpy)2X]+ complex ions, where bpy represents bipyridyl ligand and X denotes pyridyl diazolate or pyrazinyl diazolate coordination site, have been computationally designed and synthesized as pH-sensitive molecules. The choice of pyridyl and pyrazinyl moieties allows for the nitrogen content to vary, whereas the influence of the protonation site is quantified by using 1,2-diazolate and 1,3-diazolate derivatives. The absorption and emission properties of the deprotonated and protonated complex ions were characterized by UV–vis and photoluminescence spectroscopy as well as by time-dependent density functional theory. Protonation causes (1) a strong blue shift in the lowest energy 3MLCT → S0 emission wavelengths, (2) a substantial increase in the emission intensity, and (3) a change in the character of the corresponding 3MLCT emitting states. The blue shift in the emission wavelength becomes less pronounced when the nitrogen content in the X-ligand increases and when going from 1,2- to 1,3-diazolate derivatives. The contrast in the emission intensity of the protonated/deprotonated forms is the highest for the complex ion, containing a 2-pyridyl derivative of the 1,2-diazolate. The complex ions are suggested as potential pH-responsive materials based on change in the color and intensity of the emitted radiation. The broad impact of the research demonstrates that the modification of the nitrogen content and position within the protonable ligands is an effective approach for modulation of the pH-optosensing properties of Ru–polypyridyl complexes.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Electronic Engineering
Authors :
NameEmailORCID
Romanova, Julia
Sadik, Yousify.sadik@surrey.ac.uk
Prabhath, M. R. Ranga
Carey, J. Daviddavid.carey@surrey.ac.uk
Jarowski, Peter D.
Date : 13 June 2019
Funders : Leverhulme Trust
DOI : 10.1021/acs.jpca.9b03019
Copyright Disclaimer : © 2019 American Chemical Society
Depositing User : Clive Harris
Date Deposited : 20 Jun 2019 12:46
Last Modified : 20 Jun 2019 12:48
URI: http://epubs.surrey.ac.uk/id/eprint/852056

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