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Supramolecular Chemistry Volume 19, 2007 - Issue 1-2
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Original Articles

Surface-Active Mononuclear and Dinuclear Ru(II) Complexes based on Thio-substituted Terpyridines Bearing Cyclodextrin Recognition Units

Maria José J. Pereira Silva School of Chemistry, University of Birmingham, Edgbaston, B15 2TT, UK
,
Paolo Bertoncello Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK
,
Nikolaos N. Daskalakis Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK
,
Neil Spencer School of Chemistry, University of Birmingham, Edgbaston, B15 2TT, UK
,
Benson M. Kariuki School of Chemistry, University of Birmingham, Edgbaston, B15 2TT, UK
,
Patrick R. Unwin Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK
&
Z. Pikramenou School of Chemistry, University of Birmingham, Edgbaston, B15 2TT, UKCorrespondence[email protected]
 show all
Pages 115-127 | Received 15 Jun 2006, Accepted 29 Aug 2006, Published online: 02 Apr 2007
 
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Abstract

Ruthenium(II) surface active complexes based on a tpySH ligand have been prepared and characterised, (1) [Ru(tpyada)(tpySH)](PF6)2, (2) [Ru(biptpy)(tpySH)](PF6)2 and (3) [Ru(pm-β-CD(ttp))(tpySH)](PF6)2. The complexes bear a surface active thiol group and a recognition unit which is either a β-cyclodextrin or a hydrophobic tail (adamantyl- or biphenyl) in order to utilise cyclodextrin recognition for the formation of supramolecular wires using bottom up approaches. Monolayers of [Ru(tpyada)(tpySH)](PF6)2 on ITO surfaces are studied by electrochemical techniques. Detailed NMR analysis of tpySH reveals the presence of two tautomers, an “NH” and an “SH” form. The X-ray crystal structure of the oxidised form of the ligand tpySStpy is reported. A new ligand tpySCH2Stpy is prepared and its dinuclear Ru(II) complexes are reported, (4) [(ttp)Ru(tpyS CH2Stpy)Ru(ttp)]+2, (5) [(biptpy)Ru(tpySCH2Stpy)Ru(bitpy)]+2, (6) [(pm-β-CD(ttp))Ru(tpySCH2 Stpy)Ru(pm-β-CD(ttp))]+2. The complexes show characteristic red 3MLCT luminescence which is much stronger than their analogous mononuclear counterparts.

Acknowledgements

Financial support from the Marie Curie Research Training Network grant “UNI-NANOCUPS” (MRTN-CT-2003-504233) is appreciated. P.B greatly acknowledges support via a Marie Curie Intra-European Fellowship (MEIF-CT-2005-515356) under the 6th European Community Framework Programme. We also wish to acknowledge COST-D31 action and the Aventis Foundation for support (MJJPS).

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