Photoinduced electron-transfer within osmium(II) and ruthenium(II) bis-terpyridine donor acceptor dyads.
The synthesis and photophysical characterization of two different series of electron donor-acceptor dyads containing Ru(II) and Os(II) bis-terpyridines (M(tpy)(2)(2+)) were prepared and studied in order to compare the oft-studied Ru(tpy)(2)(2+) chromophore with the less studied Os(tpy)(2)(2+) chromophore. The first series of dyads incorporates a benzoquinone (BQ) group as the electron acceptor, whereas the second contains a substituted pyromellitimide (PI) group as the electron acceptor. Steady-state emission experiments indicated efficient quenching of the 3MLCT emission of the electronically excited Os(II)-BQ complexes (7-8) compared to both model complexes (3-4) and the Os(II)-PI complex 10. Femtosecond pump-probe absorption experiments on 7-8 yielded ultrafast electron transfer rate constants (kET) of approximately 2.0 x 10(11) s(-1) (7) and 1.3 x 10(10) s(-1) (8) that were in good agreement with the low emission quantum yield results. Charge-recombination (kCR) in these complexes was also quite rapid, with rate constants of approximately 6.7 x 10(10) s(-1) (7) and 1.2 x 10(10) s(-1) (8). The analogous Ru(II) complexes underwent charge separation with rate constants of 7.6 x 10(10) s(-1) (5) and approximately 2.3 x 10(10) s(-1) (6), while charge recombination in these complexes occurred with rate constants of approximately 2.1 x 10(10) s(-1) (5) and approximately 5.3 x 10(10) s(-1) (6). Electron transfer in the pyromellitimide-containing complexes occurred only for Os(II)-PI (10), which exhibited significantly slower electron transfer (approximately 4.3 x 10(6) s(-1)) and charge recombination (approximately 7.7 x 10(6) s(-1)) rate constants. The nearly thermoneutral free energy of electron transfer and short excited state lifetime in the case of Ru(II)-PI (9) presumably prevents electron transfer in this compound.
Alemán
Elvin A
EA
Department of Chemistry and The Center for Laser and Optical Spectroscopy, Knight Chemical Laboratory, The University of Akron, Akron, OH 44325-3601, USA.
Shreiner
Carol D
CD
Rajesh
Cheruvallil S
CS
Smith
Timothy
T
Garrison
Shana A
SA
Modarelli
David A
DA
D016227:Benzoquinones / Q000737:chemistry; D004563:Electrochemistry; D004579:Electron Transport; D005456:Fluorescent Dyes / Q000737:chemistry; D009992:Osmium / Q000737:chemistry*; D010777:Photochemistry; D011726:Pyridinium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013997:Time Factors
D016227:Benzoquinones; D005456:Fluorescent Dyes; D011726:Pyridinium Compounds; D009992:Osmium; C004532:quinone; D012428:Ruthenium