Prev. Article Next Article Table of Contents

Article

Ground- and Excited-State Electronic Structure of an Emissive Pyrazine-Bridged Ruthenium(II) Dinuclear Complex

Supporting Info

Wesley R. Browne,^† Noel M. O'Boyle,^† William Henry,^† Adrian L. Guckian,^† Sabine Horn,^† Thomas Fett,^† Christine M. O'Connor,^‡ Marco Duati,^§ Luisa De Cola,^§ Colin G. Coates, Kate L. Ronayne, John J. McGarvey, and Johannes G. Vos*^†

Contribution from the National Centre for Sensor Research, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland, School of Chemistry, Dublin Institute of Technology, Kevin Street, Dublin 8, Ireland, HIMS, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands, and School of Chemistry, Queen's University Belfast, Belfast BT9 5AG, Northern Ireland

J. Am. Chem. Soc., 2005, 127 (4), pp 1229–1241

DOI: 10.1021/ja046034e

Publication Date (Web): January 8, 2005

†

Dublin City University.

Present address: Organic and Molecular Inorganic Chemistry, Rijksuniversiteit Groningen, Nijenborgh 4, Groningen, The Netherlands.

‡

Dublin Institute of Technology.

Universiteit van Amsterdam.

Queen's University Belfast.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, Johannes.vos@dcu.ie

Abstract

The synthesis, characterization, and electrochemical, photophysical, and photochemical properties of the binuclear compounds [(Ru(H₈-bpy)₂)₂((Metr)₂Pz)](PF₆)₂ (1) and [(Ru(D₈-bpy)₂)₂((Metr)₂Pz)](PF₆)₂ (2), where bpy is 2,2‘-bipyridine and H₂(Metr)₂Pz is the planar ligand 2,5-bis(5‘-methyl-4‘H-[1,2,4]triaz-3‘-yl)pyrazine, are reported. Electrochemical and spectro-electrochemical investigations indicate that the ground-state interaction between each metal center is predominantly electrostatic and in the mixed-valence form only a low level of ground-state delocalization is present. Resonance Raman, transient, and time-resolved spectroscopies enable a detailed assignment to be made of the excited-state photophysical properties of the complexes. Deuteriation is employed to both facilitate spectroscopic characterization and investigate the nature of the lowest excited states.