Fluorescence yields of azulene derivatives

Murata, Shigeo; Iwanaga, C.; Toda, Takashi; Kokubun, Hiroshi

doi:10.1016/0009-2614(72)80054-x

Cited by 98 publications

(67 citation statements)

References 8 publications

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“…Fig. 3-top shows the S 2 fluorescence emission spectra of Azulene from SiFs and from glass at RT, consistent with previous reports [1][2][3] The enhanced fluorescence intensity was ≈ 1.5-fold brighter from the silver, (i.e. ratio of emission from SiFs/glass).…”

Section: Methodssupporting

confidence: 88%

“…As the first authentic example of a molecule which violates Kasha's rule, azulene has been the subject of numerous spectroscopic and photophysical investigations [3][4][5][6]. Beer and LonguetHiggins discovered the second excited level emits light upon excitation, producing the anomalous (S 2 to S 0 ) fluorescence of azulene in 1955 [6], whereas that normal S 1 to S 0 fluorescence and T 1 to T 0 phosphorescence were much too weak to be observed.…”

Section: Introductionmentioning

confidence: 99%

“…For most molecules, no excited singlet states (S 2 , S 3 …) have been observed to emit light upon excitation, the same being true for triplet states (T 2 , T 3 …). This is summarized in Kasha's rule: The emitting electronic level of a given multiplicity is the lowest excited level of that multiplicity [2].As the first authentic example of a molecule which violates Kasha's rule, azulene has been the subject of numerous spectroscopic and photophysical investigations [3][4][5][6]. Beer and LonguetHiggins discovered the second excited level emits light upon excitation, producing the anomalous (S 2 to S 0 ) fluorescence of azulene in 1955 [6], whereas that normal S 1 to S 0 fluorescence and T 1 to T 0 phosphorescence were much too weak to be observed.…”

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confidence: 99%

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Metal-enhanced S2 fluorescence from azulene

Zhang

Aslan

Previte

et al. 2006

Chemical Physics Letters

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In this paper, we report the first observation of metal-enhanced S 2 emission at room and low temperature (77K). The S 2 emission intensity of Azulene is enhanced by close proximity to Silver island films (SiFs). In this regard, a ≈ 2-fold higher S 2 fluorescence intensity of Azulene was observed from SiFs as compared to a glass control sample. This suggests that S 2 excited states can couple to surface plasmons and enhance S 2 fluorescence yields, a helpful observation in our understanding the interactions between plasmons and lumophores, and our continued efforts to develop a unified plasmon-lumophore/fluorophore theory. KeywordsS 2 emission; Metal-Enhanced S 2 Fluorescence; Radiative Decay Engineering; Surface Enhanced Fluorescence; Plasmon Controlled Fluorescence; Radiating Plasmons; Azulene; Metal-Enhanced Fluorescence IntroductionThe location of electronic energy levels in molecules and the probability and polarization of radiative transitions between ground and excited state can be accurately predicted by quantum mechanical theory [1]. For most molecules, no excited singlet states (S 2 , S 3 …) have been observed to emit light upon excitation, the same being true for triplet states (T 2 , T 3 …). This is summarized in Kasha's rule: The emitting electronic level of a given multiplicity is the lowest excited level of that multiplicity [2].As the first authentic example of a molecule which violates Kasha's rule, azulene has been the subject of numerous spectroscopic and photophysical investigations [3][4][5][6]. Beer and LonguetHiggins discovered the second excited level emits light upon excitation, producing the anomalous (S 2 to S 0 ) fluorescence of azulene in 1955 [6], whereas that normal S 1 to S 0 fluorescence and T 1 to T 0 phosphorescence were much too weak to be observed. The absence of S 1 to S 0 fluorescence suggests that S 1 to S 0 internal conversion is a very rapid progress in Azulene, this supposition being confirmed by the lifetime of the S 1 state being determined as 1.9 psec [7]. Compared with the analogous spacing of the isomer Naphthalene, Azulene has much wider spacing between its zero -point levels of the first two excited singlet states (S 1 , *Corresponding Author E-mail: geddes@umbi.umd.edu Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. [19], and the application of metallic surfaces to amplified (ultra fast and sensitive) assay detection [20]. Our laboratorys' current interpretation of MEF has been explained by a model whereby non-radiative energy transfer occurs from excited distal fluorophores, to the surface plasmon electrons in n...

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Section: Methodssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Metal-enhanced S2 fluorescence from azulene

Zhang

Aslan

Previte

et al. 2006

Chemical Physics Letters

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“…For the unusual photophysical properties of azulene, the large energetic difference between the S, and S, states (AE = 14,000 cm-I) as compared with the So -S, energy gap, appears to be most significant. This view is supported by the experimental relationship between &' and AE12 for azulene derivatives [16] manifesting that the S2 -S, internal conversion (IC) is mainly responsible for the nonradiative S, deactivation = 6 10' s-' [6]). …”

Section: Introductionmentioning

confidence: 98%

Non‐radiative deactivation of molecules. II. Theoretical study of the internal conversion rates in azulene

Gustav

Storch

1990

Int J of Quantum Chemistry

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Based on completely optimized molecular geometries of the photophysically relevant electronic states, the corresponding vibrational energies and wave functions and the theoretical rate constants for the internal conversion processes of azulene within the S, term system are presented. The influence of the promoting and accepting modes on the radiationless deactivation rates is discussed. An analysis of the active nonradiative modes is given. In context with the respective theoretical radiative rates, the efficiency of the different azulene fluorescences is interpreted.

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“…However, the full mechanism underlying the PAH hypothesis takes place on timescales up to seconds. To fully explore the dynamical behaviour of PAHs and (Siebrand 1967), squares are those for IC (internal conversion) measured neutral (azulene derivatives from Murata et al 1972 and phenanthrene from Ohta & Baba 1986) and cationic PAHs (for a detailed list of the references, see Salama 2007). Circles are for the neutral fullerenes.…”

Section: Discussionmentioning

confidence: 99%

Electronic Spectroscopy of PAHs

Pino

Carpentier

Féraud

et al. 2011

EAS Publications Series

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Abstract. Polycyclic aromatic hydrocarbons are a class of molecules of broad interest that has long been explored by various spectroscopic techniques. The electronic spectroscopy of these species is of particular interest since it provides a framework for the understanding of the electronic structure of large polyatomic molecules. Such studies also allow the systematic investigation of electronic relaxation mechanisms in large molecules. In this review, we focus on the gas-phase experimental work on such systems and present the latest progress. We also underline the challenges that remain to be tackled. A focus on the understanding of the electronic relaxation pathways at work in gas-phase PAHs will also be presented, as well as their possible manifestation in space.

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Fluorescence yields of azulene derivatives

Cited by 98 publications

References 8 publications

Metal-enhanced S2 fluorescence from azulene

Metal-enhanced S2 fluorescence from azulene

Non‐radiative deactivation of molecules. II. Theoretical study of the internal conversion rates in azulene

Electronic Spectroscopy of PAHs

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