ISSN:
1434-1948
Schlagwort(e):
Terpyridine
;
Copper sensing
;
Cyclam
;
Fluorescence
;
Solution studies
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
A synthetic strategy has been devised for the preparation of new compounds in which terpyridyl fragments are linked to 1,4,8,11-tetraazacyclotetradecane (cyclam). Reaction of excess cyclam with 4′-[(4-bromomethyl)phenyl]-2,2′:2″,6′-terpyridine afforded the ligand 1-[4′-p-tolyl-(2,2′:6′,2″-terpyridyl)]-1,4,8,11-tetraazacyclotetradecane (L1) in which the tetraaza macrocycle was covalently attached to one benzyl-terpyridyl fragment. Under similar conditions reaction of cyclam with excess 4′-[(4-bromomethyl)phenyl]-2,2′:2″,6′-terpyridine gave the tetra substituted cyclam derivative 1,4,8,11-[4′-p-tolyl-(2,2′:6′,2″-terpyridyl)]-1,4,8,11-tetraazacyclotetradecane (L2). The multidentate ligand L2 was crystallographically characterised by single-crystal X-ray diffraction techniques. Reaction of L1 with [Ru(mtpy)Cl3] gave the heteroleptic ruthenium(II) complex [Ru(L1)(mtpy)][PF6]2 (mtpy = 4′-methyl-2,2′:6′2″-terpyridine). The fluorescent intensity of the metallo-receptor [Ru(L1)(mtpy)][PF6]2 was quenched selectively in the presence of copper(II) in an aqueous environment. To gain insight into the nature of this interaction, potentiometric titrations on [Ru(L1)(mtpy)]2+ in the presence of Cu2+ were carried out. The quenching of the emission intensity was associated with the presence of the copper {Cu[Ru(L1)(mtpy)]}4+ complex in solution. The receptor 1-[4′-methyl-(2,2′:6′,2″-terpyridyl)]-1,4,8,11-tetraazacyclotetradecane (L3), in which the cyclam fragment is separated from the terpyriyl by a methylene group, has also been synthesised by reaction of 4′-bromomethyl-2,2′:2″,6′-terpyridine and cyclam. With L3 as starting material, the ruthenium complex [Ru(L3)(mtpy)]2+ was prepared in order to evaluate the effect that the nature of the spacer has on the quenching of the fluorescence upon addition of Cu2+.
Zusätzliches Material:
5 Ill.
Materialart:
Digitale Medien
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