Fullerene bridged metallocyclodextrin donor-acceptor complexes: optical spectroscopy and photophysics.
Two pyridine substituted beta-cyclodextrins have been synthesized and coordinated to the photoactive metal centres, [Ru(II)(bpy)2] and [Re(I)(CO)3bpy], where bpy is 2,2'-bipyridyl. The photophysical and electrochemical properties of these model complexes have been examined and compared with dinuclear complexes formed when C60 was included between two cyclodextrin cavities of the metallocyclodextrin units. On inclusion of C60, significant quenching of the emission of the luminophores is observed. Concentration and laser power dependence confirm that this quenching is intramolecular. The quenching process is interpreted in terms of a photoinduced electron transfer between the photosensitizer and C60 centre on the basis of spectroscopic and electrochemical evidence. Rate constants of 1.3 +/- 0.1 x 10(8) and 7.0 +/- 0.4 x 10(7) s(-1) have been determined for the Ru and Re based complexes, respectively. Significantly, these large rate constants indicate that that there is substantial electronic communication across the cyclodextrin at least for excited state processes.
National Centre for Sensor Research, School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland.
Andrea
A
McNally
Robert J
RJ
Forster
Noel R
NR
Russell
Tia E
TE
Keyes
D015082:2,2'-Dipyridyl / Q000737:chemistry; D004563:Electrochemistry; D037741:Fullerenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010777:Photochemistry; D012211:Rhenium / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013055:Spectrophotometry, Infrared / Q000379:methods; D013059:Spectrum Analysis, Raman / Q000379:methods; D013997:Time Factors; D047392:beta-Cyclodextrins / Q000737:chemistry*
D037741:Fullerenes; D009942:Organometallic Compounds; D047392:beta-Cyclodextrins; D015082:2,2'-Dipyridyl; D012211:Rhenium; D012428:Ruthenium; C069837:fullerene C60