Ferrocenyl-Functionalised Terpyridines and Their Transition-Metal Complexes: Syntheses, Structures and Spectroscopic and Electrochemical Properties

Terpyridine ligands of the type Fc′‐X‐tpy′ (Fc′=ferrocenyl or octamethylferrocenyl, X=rigid spacer, tpy′=4′‐substituted 2,2′:6′,2″‐terpyridine) were prepared, crystallographically characterised and used for the synthesis of di‐ and trinuclear bis(terpyridine) complexes of RuII, FeII and ZnII. Donor–...

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Published in:Chemistry : a European journal 2003-06, Vol.9 (12), p.2819-2833
Main Authors: Siemeling, Ulrich, Vor der Brüggen, Jens, Vorfeld, Udo, Neumann, Beate, Stammler, Anja, Stammler, Hans-Georg, Brockhinke, Andreas, Plessow, Regina, Zanello, Piero, Laschi, Franco, Fabrizi de Biani, Fabrizia, Fontani, Marco, Steenken, Steen, Stapper, Marion, Gurzadyan, Gagik
Format: Article
Language:English
Subjects:
electrochemistry
heterometallic complexes
ligand design
luminescence
time- resolved spectroscopy
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Summary:Terpyridine ligands of the type Fc′‐X‐tpy′ (Fc′=ferrocenyl or octamethylferrocenyl, X=rigid spacer, tpy′=4′‐substituted 2,2′:6′,2″‐terpyridine) were prepared, crystallographically characterised and used for the synthesis of di‐ and trinuclear bis(terpyridine) complexes of RuII, FeII and ZnII. Donor–sensitiser dyads and triads based on RuII were thoroughly investigated by (spectro)electrochemistry, UV/Vis, transient absorption and luminescence spectroscopy, and an energy level scheme was derived on the basis of the data collected. Intramolecular quenching of the photoexcited RuII complexes by the redox‐active Fc′ groups can occur reductively and by energy transfer. Both the redox potential of the donor Fc′ and the nature of the spacer X have a decisive influence on excited‐state lifetimes and emission properties of the complexes. Some of the compounds show room‐temperature luminescence, which is unprecedented for ferrocenyl‐functionalised compounds of this kind. Redox‐functionalised terpyridines have been utilised for the construction of geometrically well‐defined donor–sensitiser dyads and triads (see picture). This unique molecular system allows the independent and systematic variation of molecular parameters relevant to electron and energy transfer, that is, the redox potential of the donor unit and the length of the rigid π spacer.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.200204412