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Issue 41, 2008
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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

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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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Publication details

The article was received on 18 Apr 2008, accepted on 01 Jul 2008 and first published on 02 Sep 2008


Article type: Paper
DOI: 10.1039/B806325G
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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