Fluorescence from the second excited singlet of aromatic thioketones in solution

Mahaney, Mary; Huber, J. Robert

doi:10.1016/0301-0104(75)80075-9

Cited by 66 publications

(10 citation statements)

References 22 publications

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“…1). Absorption, emission, and excitation spectra of xanthione in fluid solution, in glasses, and in a Shpolskii matrix have been reported by Huber and coworkers (5,(12)(13)(14). These spectral studies and previous ODMR experiments (6) have been interpreted as indicating that the T , and T z states of xanthione are energetically very close and that the lowest triplet is of mixed n,m*-m,m* character.…”

Section: Introductionmentioning

confidence: 78%

“…The spectral data for TMIT and the other thiones examined in this work are summarized in Table 1. Data for xanthione is provided for comparison (5,(12)(13)(14).…”

Section: Resultsmentioning

confidence: 99%

“…By contrast the lowest excited singlet states of several larger organic thiones in solution have been shown to decay very rapidly via intersystem crossing to T I (+,,, -1). The lifetime of xanthione S ,, for example, has previously been estimated to be <lo-" s (13,35).…”

Section: A For the Aromatic Thiones Investigated Inmentioning

confidence: 99%

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Decay dynamics of aromatic thione triplet states in fluid solution

Safarzadeh–Amiri¹,

Verrall²,

Steer³

1983

Can. J. Chem.

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This paper is dedicated to Pro/e.ssor Harry E. Gunrling on the occasiorl a/ his 65th birthdayA. SAFARZADEH-AMIRI, R. E. VERRALL, and R. P. STEER. Can. J . Chem. 61. 894 (1983). Phosphorescence emission and excitation spectra, quantum yields, and lifetimes of several aromatic thiones have been measured in fluid solution at room temperature. Excitation to any of the excited electronic states accessible in the near-uv and visible regions of the spectrum results in population of the lowest triplet state with near unit quantum yield. Triplets of relatively inflexible thiones decay non-radiatively with rate constants of the order of lo5 s-' whereas thiones capable of higher amplitude flexion or group rotation exhibit non-radiative decay constants 2 lo7 S-I at infinite dilution in aprotic solvents. Self-quenching occurs at diffusion-controlled rates.A. SAFARZADEH-AMIRI, R. E. VERRALL et R. P. STEER. Can. J. Chem. 61, 894 (1983). On a mesure 1'Cmission par phosphorescence, les spectres d'excitation, les rendements quantiques et les temps de vie de plusieurs thiones aromatiques dans une solution fluide ii la tempkrature ambiante. L'excitation de n'importe quel Ctat Clectronique excitt, accessible dans les rtgions du proche uv et visible des spectres, conduit B une population du plus faible &tat triplet avec un rendement quantique proche de !'unit&. Les triplets des thiones relativement inflexibles se dtsintkgrent d'une manikre non radioactive avec des constantes de vitesse de I'ordre de 105 s-' tandis que les thiones qui peuvent subir une flexion de plus grande amplitude ou une rotation de groupe ont des constantes de dCsintCgration non radioactive de 2 lo7 s-' a dilution infinie dans des solvants aprotiques. L'arrCt automatique se produit B des vitesses contrdltes de diffusion. [Traduit par le journal] IntroductionThiocarbonyl compounds exhibit a number of photochemical and photophysical properties which are unusual compared with those of compounds containing only first and second row elements (1-3). For example, as a consequence of their relatively large S 2 -S , electronic energy gaps, some thiones fluoresce efficiently and react chemically from excited singlet states other than S I (1). The tetraatomic thiocarbonyl, thiophosgene, has been shown to undergo a unique excited singlet -excited singlet energy pooling reaction in the gas phase which can populate S z with high efficiency (4). There is also substantial evidence of strong spin-orbit coupling in thiones which leads to unusual physical and dynamic properties of their triplet states (5-7). Thus, thiones are among the few organic molecules which phosphoresce in fluid solution at room temperature.The T I +-S o absorption in aromatic thiones in fluid solution is often spectrally distinct from other electronic absorption systems and has an oscillator strength which is only about one order of magnitude smaller than that of the corresponding S I +-So transition (1). Thus T I may be populated either by direct absorption in the T I + So system or by intersystem crossing ...

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Section: Introductionmentioning

confidence: 78%

“…The spectral data for TMIT and the other thiones examined in this work are summarized in Table 1. Data for xanthione is provided for comparison (5,(12)(13)(14).…”

Section: Resultsmentioning

confidence: 99%

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Decay dynamics of aromatic thione triplet states in fluid solution

Safarzadeh–Amiri¹,

Verrall²,

Steer³

1983

Can. J. Chem.

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“…The fluorescence quantum yield (Φf ) was calculated using the Eq. (1) [17]. It was found that the fluorescence quantum yield (Φf ) around 0.72.…”

Section: Florescence Quantum Yieldmentioning

confidence: 99%

Amplified Spontaneous Emission (ASE) Properties of a laser dye (LD-473) in solid state

Ibnaouf

Taha

Idriss

et al. 2017

J. Eur. Opt. Soc.-Rapid Publ.

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The spectral characteristics of 1,2,3,8-tetrahydro-1,2,3,3,8-pentamethyl-5-(trifluoromethyl)-7H-pyrrolo[3,2-g]quinolin-7-one (LD-473) were demonstrated in liquid and solid states. For the liquid state, the absorption and fluorescence spectra of the LD-473 in Methyl Methacrylate showed bands at 385 and 420 nm, respectively. LD-473 in the solid state showed one absorption band at 530 nm, while the fluorescence spectra, under low concentration, showed one band at 615 nm. For higher concentrations, the fluorescence bands are shifted to the red. LD-473 in the solid state under an impulse of Nd: YAG laser showed dual amplified spontaneous emission (ASE) peaks at 605 and 650 nm. The longer wavelength coincided with a fluorescence peak while the shorter wavelength is an abnormal peak.

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“…It is now well known for a number of thioketones that the fluorescence occurs from the second excited state, S 2 . The S 2 fluorescence of alkylthioketones was reported first in 1975 independently by Huber and Mahaney and by Ware et al in solution [2][3][4]. These reports were followed by numerous studies on the emission properties of thioketones and their families in a variety of media as reviewed by Maciejewski and Steer in 1993 [1].…”

Section: Introductionmentioning

confidence: 97%

Photophysics of 2,6-dimethyl-4H-pyran-4-thione in the vapor phase

Itoh

2012

Journal of Photochemistry and Photobiology A: Chemistry

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Fluorescence from the second excited singlet of aromatic thioketones in solution

Cited by 66 publications

References 22 publications

Decay dynamics of aromatic thione triplet states in fluid solution

Decay dynamics of aromatic thione triplet states in fluid solution

Amplified Spontaneous Emission (ASE) Properties of a laser dye (LD-473) in solid state

Photophysics of 2,6-dimethyl-4H-pyran-4-thione in the vapor phase

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