Issue 41, 2008
From the journal:

Dalton Transactions

Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core†

Isabelle M. Dixon,a   Emilie Lebon,a   Gilles Loustau,a   Pierre Sutra,a   Laure Vendier,a   Alain Igau*a  and  Alberto Jurisb  

* Corresponding authors

a Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205 route de Narbonne, 31077 Toulouse Cedex 4, France
E-mail: alain.igau@lcc-toulouse.fr
Fax: +33 561 553 003
Tel: +33 561 333 159

b Dipartimento di Chimica “G. Ciamician”, Università di Bologna, via Selmi 2, 40126 Bologna, Italy
E-mail: alberto.juris@unibo.it
Fax: +39 512 099 456
Tel: +39 512 099 481

Abstract

The synthesis of new ruthenium(II) terpyridine bipyridine complexes bearing a phosphorus(III) ligand is presented. The steric and electronic properties of the phosphorus ligand were varied using aminophosphines, alkyl and aryl phosphites and the bulky tri(isopropyl)phosphine. All complexes were characterized by multi-nuclear NMR spectroscopy, mass spectrometry and X-ray diffraction analysis. The electronic properties of the complexes were probed by cyclic voltammetry, absorption and luminescence spectroscopy. The complexes do not show luminescence at room temperature, whereas at 77 K in an alcoholic matrix, emission is observed in the range 600–650 nm with lifetimes of 3.5–5.5 μs, originating from 3MLCT states. The MLCT transition spans over 65 nm, which corresponds to a variation of 0.4 eV in the HOMO–LUMO gap. The oxidation potential of the ruthenium varies over a broad range of 290 mV, from +1.32 V vs. SCE with L = PiPr3 to +1.61 V vs. SCE with L = P(OPh)3. This range is unprecedented upon the variation of a single monodentate ligand coordinated by the same heteroatom in the same oxidation and charge states. This work underlines the specific capacity of phosphorus in bringing up a large variety of electronic properties by changing its substituents.

Graphical abstract: Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core

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Article information

DOI
https://doi.org/10.1039/B806325G
Article type
Paper
Submitted
18 Apr 2008
Accepted
01 Jul 2008
First published
02 Sep 2008

Dalton Trans., 2008, 5627-5635

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Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core

I. M. Dixon, E. Lebon, G. Loustau, P. Sutra, L. Vendier, A. Igau and A. Juris, Dalton Trans., 2008, 5627 DOI: 10.1039/B806325G

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