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Fluorescent Chemosensors for Heavy Metal Ions Based on Bis(terpyridyl) Ruthenium(II) Complexes Containing Aza-Oxa and Polyaza Macrocycles

✍ Scribed by Miguel E. Padilla-Tosta; José Manuel Lloris; Ramón Martínez-Máñez; M. Dolores Marcos; Miguel A. Miranda; Teresa Pardo; Felix Sancenón; Juan Soto


Publisher
John Wiley and Sons
Year
2001
Tongue
English
Weight
370 KB
Volume
2001
Category
Article
ISSN
1434-1948

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✦ Synopsis


Reactions of 4Ј-[4-(bromomethyl)phenyl]-2,2Ј:6Ј,2ЈЈ-terpyridine with 4,10-diaza-15-crown-5 and 1-aza-12-crown-4 in dichloromethane yielded the ligands L 1 and L 3 , respectively. Reaction of an excess of 4Ј-[4-(bromomethyl)phenyl]-2,2Ј:6Ј,2ЈЈ-terpyridine with 4,10-diaza-15-crown-5 yielded L 2 , while treatment of the same terpyridine ligand with 1,4,7,10,13-pentaazacyclopentadecane afforded L 4 . Reactions of L 1 , L 3 , and L 4 with Ru(mtpy)Cl 3 (mtpy = 4Ј-methyl-2,2Ј:6Ј,2ЈЈ-terpyridine) in methanol yielded the metallo receptors [Ru(L 1 )(mtpy)][PF 6 ] 2 , [Ru(L 3 )(mtpy)][PF 6 ] 2 , and [Ru(L 4 )(mtpy)][PF 6 ] 2 after precipitation with ammonium hexafluorophosphate and column chromatography. On treating L 3 with RuCl 3 , the homoleptic ruthenium complex [Ru(L 3 ) 2 ][PF 6 ] 2 was obtained. The synthesized metallo receptors contain oxa-aza crown or polyazacycloalkane moieties as recognition sites and [Ru(tpy) 2 ] 2+ cores as the signal-generating centre. The electronic spectra of the complexes are as expected for an Ru(tpy) 2 2+ chromophore, with the main Ru[d(π)] Ǟ tpy(π*) MLCT transition at ca. 484 nm and intense