1998
DOI: 10.1021/ic9702429
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Nonradiative Transition of Phosphorescent Charge-Transfer States of Ruthenium(II)-to-2,2‘-Biquinoline and Ruthenium(II)-to-2,2‘:6‘,2‘‘-Terpyridine in the Solid State

Abstract: Temperature-dependent decays of the charge-transfer triplet excited states (3CT) of ruthenium(II) compounds have been investigated in a wide temperature range (77−480 K) for the crystals of Ru(biq)3(ClO4)2, Ru(bpy)2(biq)X2·2H2O, and Ru(tpy)2X2, (bpy = 2,2‘-bipyridine, tpy = 2,2‘:6‘,2‘‘-terpyridine, biq = 2,2‘-biquinoline, X = ClO4 -, PF6 -). The width of the 1CT absorption band and the peak of 3CT emission of the Ru(bpy)2(biq)X2·2H2O crystal at 298 K are unchanged from those of the ethanol/methanol solution sa… Show more

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Cited by 49 publications
(43 citation statements)
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“…All complexes 1-5 show an emission at 298 K with a maximum between 990 nm and 1010 nm. The blue shift that occurs for all of the complexes in the transition from fluid solution to frozen solvent glass is a common rigidochromic effect observed in many metal diamine complexes [21,22]. The emission spectra of complex 1 in ethanol-methanol mixed solvents at 77 and 298 K are presented in complex 1 exhibits an emission maximum at 990 nm, which is 50 nm red-shifted compared to that of the R1 emission and consistent with the shift in the lowest-MLCT absorption band.…”
Section: Resultsmentioning
confidence: 95%
See 1 more Smart Citation
“…All complexes 1-5 show an emission at 298 K with a maximum between 990 nm and 1010 nm. The blue shift that occurs for all of the complexes in the transition from fluid solution to frozen solvent glass is a common rigidochromic effect observed in many metal diamine complexes [21,22]. The emission spectra of complex 1 in ethanol-methanol mixed solvents at 77 and 298 K are presented in complex 1 exhibits an emission maximum at 990 nm, which is 50 nm red-shifted compared to that of the R1 emission and consistent with the shift in the lowest-MLCT absorption band.…”
Section: Resultsmentioning
confidence: 95%
“…The enhanced red absorption of these complexes renders them attractive candidates as panchromatic charge transfer sensitizers for DSCs. It is well known that the excited-state responsible for the luminescence of the Ru(II)-polypyridine compounds is the lowest-energy triplet metal-to-ligand charge-transfer ( 3 MLCT) state [21]. When excited at the charge transfer absorption band, complexes 1-5 show an intense emission at the 77 K ethanol-methanol glass matrix with a maximum between 930 and 970 nm.…”
Section: Resultsmentioning
confidence: 99%
“…After a transition to the Gibbs free energy surface of reactant, the nitrogen atoms of pyridyl groups get closer to the cobalt during its oxidation from 213 pm 32 to 193 pm 33 2+ , which was estimated to be 2.1 and 2.8 eV, respectively, from the temperature dependence of radiation-less transition rate of 3 -CT(Ru). 35,36 The peak energy of the triplet excited d-d transition of [Co(tpy) 2 ] 3+ is shifted from the 0-0 energy by the FranckCondon energy of optical transition, which is estimated to be 0.75 eV from the Stokes shift (1.5 eV ) 3.2 eV (the absorption peak) -1.7 eV (the phosphorescence)) in the case of [Co(CN) 6 ] 3-. 37 Since the weaker ligand-field of [Co(tpy) 2 ] 3+ than [Co(CN) 6 ] 3-is assumed to reduce the Franck-Condon energy of the optical singlet-triplet d-d transition to 0.4 eV, the enthalpy of the formation of lowest triplet state is close to 1 eV.…”
Section: Gibbs Free Energy Surfaces Of the Excited State And The Groumentioning
confidence: 99%
“…For [Ru(bpy) 3 ] 2+ , the 3 MC state was found to be energetically higher than the 3 MLCT state. 40,42,43 Therefore, the quenching of the 3 MLCT luminescence via the 3 MC state appears to be thermally activated. 44,45 However, the population of this intermediate state remains negligible at all times due to the much higher relaxation rate of 3 MC to 1 A 1 .…”
Section: Steady State Pes Study Of [Ru(bpy) 3 ] 2+ Dissolved In Ilsmentioning
confidence: 99%