Transient Excited-State Absorption and Gain Spectroscopy of a Two-Photon Absorbing Probe with Efficient Superfluorescent Properties

Belfield, Kevin D.; Bondar, Mykhailo V.; Morales, Alma R.; Yue, Xiling; Luchita, Gheorghe; Przhonska, Olga V.

doi:10.1021/jp302274v

Cited by 27 publications

(49 citation statements)

References 51 publications

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“…Observed changes in the optical density at λ ab max corresponded to first-order photoreaction under the employed irradiation conditions, and all detectable photoproducts appeared in the short wavelength range, at <λ ab max . Obtained values of Φ ph ≈ (2−5) × 10 −4 were comparable with corresponding parameters of known fluorescent labels 30 and acceptable for practical applications in fluorescence bioimaging.…”

Section: Resultssupporting

confidence: 68%

Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy of New Two-Photon Absorbing Diketopyrrolopyrrole Derivatives

et al. 2015

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The synthesis and comprehensive linear photophysical and nonlinear optical characterization of new diketopyrrolopyrrole derivatives, 2-(2-ethylhexyl)-3,6-di(pyridin-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (1) and 2-(10-azidodecyl)-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (2), are reported. The nature of the main linear absorption bands of 1 and 2 was ascertained based on experimental excitation anisotropy spectra and quantum chemical calculations. Threedimensional fluorescence maps, emission lifetimes, and photochemical decomposition quantum yields of the new derivatives were obtained in a number of organic solvents at room temperature. Two-photon absorption (2PA) spectra of 1 and 2 were measured over a broad spectral range using an open aperture Z-scan technique, revealing a maximum 2PA cross section of ∼100 GM. Transient absorption and stimulated emission pump−probe measurements with femtosecond time resolution revealed two different types of fast relaxations in the excited states of 1 and 2, and one-photon stimulated emission depletion (STED) spectra were determined. Efficient superfluorescence emission of 1 was observed under femtosecond transverse pumping conditions. A quantum-mechanical investigation of the electronic structure of the new compounds was performed using TD-DFT methodology. Simulated linear absorption spectra, including Franck−Condon band structure of the first excited states, were found in good agreement with experimental data, while 2PA cross sections obtained without vibronic contributions were considerably underestimated.

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Section: Resultssupporting

confidence: 68%

Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy of New Two-Photon Absorbing Diketopyrrolopyrrole Derivatives

et al. 2015

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“…91 The values of F M were in the range ∼10 6 −10 8 which are comparable with known efficient two-photon fluorescent labels. 65,68 3.3. Femtosecond Transient Absorption Spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

New Two-Photon Absorbing BODIPY-Based Fluorescent Probe: Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy

et al. 2016

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The synthesis and comprehensive linear spectroscopic and nonlinear optical properties of a new BODIPYbased fluorene-containing derivative 4,4-difluoro-8-(4-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}phenyl)-1,3,5,7-tetramethyl-2,6-di [(9,9-di{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-9H-fluoren-2-yl)ethynyl]-4-bora-3a,4a-diaza-s-indacene (1) are reported. The steady-state absorption, emission, and excitation anisotropy spectra along with fluorescence lifetimes of 1 were analyzed in organic solvents of different polarity. The degenerate two-photon absorption (2PA) spectrum of 1 was obtained over a broad spectral range by the open aperture Zscan method using 1 kHz femtosecond excitation, and the 2PA cross section had a maximum value of ∼400 GM. The onephoton stimulated emission depletion spectrum of 1 was determined by a fluorescence quenching method with values of stimulated emission cross sections close to the corresponding ones of the ground state linear absorption. The nature of ultrafast relaxation processes in 1 was analyzed by a transient absorption femtosecond pump−probe technique, and the characteristic times of intramolecular relaxations between the excited electronic states (<150 fs) and solvation dynamics (4−6 ps) were determined. Efficient superluminescence emission of 1 was observed in solution under one-and two-photon femtosecond pumping. Detailed analysis of the singlet excitations in 1 was performed by a time-dependent density functional theory (TD-DFT) method. Three one-photon and two two-photon absorbing states were predicted in the wavelength range investigated. A reactive handle was included in the meso-position of the BODIPY chromophore to facilitate future bioconjugation or functionalization for bioimaging applications.

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“…18,30 It is worth mentioning that some of the specific nonlinear optical properties such as superluminescence 36,37 (or amplified spontaneous emission) and lasing abilities were recently reported for symmetrical squaraines, 11 and can be employed in the development of a new generation of fluorescent labels with increased brightness and high spectral resolution. 38,39 Here we report the synthesis and comprehensive characterization of the linear spectroscopic, photochemical, and nonlinear optical properties of a three arm star-shaped squaraine derivative (1), including excitation anisotropy, two-photon absorption (2PA), femtosecond pump−probe spectroscopy, superluminescence, and symmetry breaking phenomena. The nature of the electronic characteristics of the molecular structure of 1 was also investigated by quantum-chemical calculations at DFTB 40 and ZINDO/S 41 levels of theory.…”

Section: Introductionmentioning

confidence: 99%

Linear Photophysics and Femtosecond Nonlinear Spectroscopy of a Star-Shaped Squaraine Derivative with Efficient Two-Photon Absorption

et al. 2016

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The synthesis, comprehensive linear photophysical and photochemical study, two-photon absorption (2PA) spectrum, ultrafast relaxation kinetics in the excited states, and efficient superluminescence properties of a new symmetrical three-armed star-shaped squaraine derivative (1) are presented. The steady-state spectral parameters of 1 in a number of organic solvents, including fluorescence excitation anisotropy spectra, revealed a weak interaction between the squaraine branches and the effect of symmetry breaking in the ground electronic state. The degenerate 2PA spectrum of 1 was obtained over a broad spectral range with a maximum cross section of ∼8000 GM using the open aperture Z-scan technique. The nature of the fast dynamic processes in the excited electronic states of 1 was investigated by the femtosecond transient absorption pump−probe method, revealing characteristic relaxation times of ∼3−4 ps. The efficient superluminescence emission of 1 was observed in relatively low concentration solution (≈ 2.3·10 −4 M) under femtosecond transverse pumping. A quantum-chemical study of 1 was performed using ZINDO/S//DFTB theory levels. Simulated 1PA and 2PA absorption spectra were found to be in a good agreement with experimental data. The figure of merit for 1 is ∼10 11 GM, 1 one of the highest values ever reported for two-photon fluorescence molecular probes, suggesting strong potential for its application in two-photon fluorescence microscopy and bioimaging.

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Transient Excited-State Absorption and Gain Spectroscopy of a Two-Photon Absorbing Probe with Efficient Superfluorescent Properties

Cited by 27 publications

References 51 publications

Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy of New Two-Photon Absorbing Diketopyrrolopyrrole Derivatives

Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy of New Two-Photon Absorbing Diketopyrrolopyrrole Derivatives

New Two-Photon Absorbing BODIPY-Based Fluorescent Probe: Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy

Linear Photophysics and Femtosecond Nonlinear Spectroscopy of a Star-Shaped Squaraine Derivative with Efficient Two-Photon Absorption

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