Enantiopure lanthanide complexes incorporating a tetraazatriphenylene sensitiser and three naphthyl groups: exciton coupling, intramolecular energy transfer, efficient singlet oxygen formation and perturbation by DNA binding.
In cationic nine-coordinate chiral terbium and europium complexes incorporating exciton-coupled naphthyl groups and a tetraazatriphenylene sensitising chromophore, efficient intramolecular energy transfer occurs leading to population of the naphthyl triplet state. With the terbium complex, the absolute quantum yield of singlet oxygen formation is 51% (lambda(exc) 355 nm), and for the Eu complex the intensity of metal-based emission increases by up to 350% on binding to poly(dGdC) or calf-thymus DNA, and was greater for the delta-isomer.
Bobba
Gabriella
G
Department of Chemistry, University of Durham, South Road, Durham, UK DH1 3LE.
Bretonnière
Yann
Y
Frias
Juan-Carlos
JC
Parker
David
D
D000818:Animals; D002417:Cattle; D002942:Circular Dichroism; D004247:DNA / Q000378:metabolism*; D015342:DNA Probes / Q000737:chemistry; D004735:Energy Transfer; D005063:Europium / Q000737:chemistry / Q000378:metabolism; D005682:Gadolinium / Q000737:chemistry / Q000378:metabolism; D007700:Kinetics; D028581:Lanthanoid Series Elements / Q000737:chemistry* / Q000378:metabolism; D008163:Luminescent Measurements; D009281:Naphthalenes / Q000737:chemistry* / Q000378:metabolism; D010618:Phenanthrolines / Q000737:chemistry* / Q000378:metabolism; D011131:Polyribonucleotides / Q000737:chemistry / Q000378:metabolism; D011789:Quantum Theory; D026082:Singlet Oxygen / Q000737:chemistry*; D013053:Spectrophotometry / Q000379:methods; D013237:Stereoisomerism; D013725:Terbium / Q000737:chemistry / Q000378:metabolism
D015342:DNA Probes; D028581:Lanthanoid Series Elements; D009281:Naphthalenes; D010618:Phenanthrolines; D011131:Polyribonucleotides; D013725:Terbium; D026082:Singlet Oxygen; D005063:Europium; D004247:DNA; C427203:calf thymus DNA; D005682:Gadolinium