Ground- and Excited-state Chemistry of [bis(2,2'-bipyridine)(2-(2-pyridyl)pyrazine) Ruthenium(II)]

Ground- and Excited-state Chemistry of [bis(2,2'-bipyridine)(2-(2-pyridyl)pyrazine) Ruthenium(II)]
Author: Elena Ferloni
Publisher:
Total Pages: 732
Release: 2012
Genre:
ISBN: 9781267728272

Download Ground- and Excited-state Chemistry of [bis(2,2'-bipyridine)(2-(2-pyridyl)pyrazine) Ruthenium(II)] Book in PDF, Epub and Kindle

Ruthenium(II) diimines have been extensively studied for their notable photo physical properties. Of particular interest are compounds with ligands with peripheral base sites, where the metal-to-ligand charge transfer shifts electron density onto the ligand yielding an emissive state of increased in basicity. One well known example of such complexes, (bis(2,2'-bipyridine) (2-3-bis(2-pyridyl) pyrazine) ruthenium(II), [Ru(bpy)2dpp] 2+, has been studied extensively, yet questions remained regarding the sequence of protonation steps at the two peripheral dpp nitrogens in the ground and excited states and the magnitude of the photo-induced change in acid-base properties at each site. In order to reach a deeper understanding of the kinetic and thermodynamic steps involved in its protonation and coordination, a similar complex was synthesized and studied, (bis(2,2'-bipyridine) (2-(2-pyridyl) pyrazine) ruthenium(II), [(bpy)2Ru(pypz)]2+. The alternative ligand is identical in almost every respect to dpp except for the absence of the free pyridyl ring and the fact that it has only one possible protonation site instead of two. The pypz ligand, thus, represents an ideal candidate to elucidate how the pyrazinyl nitrogen on the coordinated dpp would behave if the additional pyridyl ring on dpp was not present. The differences and similarities in the properties of [(bpy)2Ru(pypz)]2+ and [Ru(bpy)2dpp]2+ in the same environment are highlighted here, describing the peculiar behavior of the acid-base sites of each complex upon excitation and their role in protonation reactions and coordination reactions to d10 metals, namely zinc.

Synthesis and Spectroscopic Characterisation of Bis(bis(Bipyridine)ruthenium(II))-3,3',4,4'-Tetraiminobiphenyl and Its Redox Products

Synthesis and Spectroscopic Characterisation of Bis(bis(Bipyridine)ruthenium(II))-3,3',4,4'-Tetraiminobiphenyl and Its Redox Products
Author: P. R. Auburn
Publisher:
Total Pages: 20
Release: 1990
Genre:
ISBN:

Download Synthesis and Spectroscopic Characterisation of Bis(bis(Bipyridine)ruthenium(II))-3,3',4,4'-Tetraiminobiphenyl and Its Redox Products Book in PDF, Epub and Kindle

Tetraiminobiphenyl forms a redox series of binuclear complexes obtained by coordinating the Ru(bpy)2 (bpy = 2, 2 - bipyridine) fragment at each end of the molecule. The ligand is capable of existing in six redox states, and three of these, including a mixed valence species, are characterised as their bis(Ru(bpy)2) complexes. Electrochemical, electron spin resonance and optical data are presented. These are discussed in terms of localisation and delocalisation of the ruthenium to ligand charge transfer states as a function of redox level. The mixed valence species displays an intervalence (ligand to ligand) charge transfer band, and the degree of electronic coupling is shown to be relatively large. There is some evidence that the biphenyl twist angle changes with oxidation state suggesting that these complexes might be useful building blocks for molecular wires and switches. Keywords: Biphenyl, Ruthenium, Redox, Bipyridine. (JES).