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Open accessJournal ArticleDOI: 10.1038/S41598-021-83791-Z

Ultrafast spectroscopy reveals singlet fission, ionization and excimer formation in perylene film.

04 Mar 2021-Scientific Reports (Springer Science and Business Media LLC)-Vol. 11, Iss: 1, pp 5220-5220
Abstract: Singlet exciton fission (SF) is a spin-allowed process whereby two triplet excitons are created from one singlet exciton. This phenomenon can offset UV photon energy losses and enhance the overall efficiency in photovoltaic devices. For this purpose, it requires photostable commercially available SF materials. Excited state dynamics in pure perylene film, ease of commercial production, is studied by time-resolved fluorescence and femtosecond transient absorption techniques under different photoexcitation energies. In film, polycrystalline regions contain perylene in H-type aggregate form. SF takes place from higher excited states of these aggregates in ultrafast time scale < 30 fs, reaching a triplet formation quantum yield of 108%. Moreover, at λex = 450 nm singlet fission was detected as a result of two-quantum absorption. Other competing relaxation channels are excimer (1 ps) and dimer radical cation formation (< 30 fs). Excimer radiatively relaxes within 19 ns and radical cation recombines in 3.2 ns. Besides, exciton self-trapping by crystal lattice distortions occurs within hundreds of picosecond. Our results highlight potential of simple-fabricated perylene films with similar properties as high-cost single crystal in SF based photovoltaic applications.

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Topics: Singlet fission (69%), Perylene (56%), Quantum yield (55%) ... show more

5 results found

Open accessJournal ArticleDOI: 10.1063/5.0069398
Wenjun Ni1, Gagik G. Gurzadyan2, Licheng Sun1, Licheng Sun2  +1 moreInstitutions (3)
Abstract: A long 0.9 ps lifetime of the upper excited singlet state in perylene is resolved by femtosecond pump–probe measurements under ultraviolet (4.96 eV) excitation and further validated by theoretical simulations of transient absorption kinetics. This finding prompts exploration and development of novel perylene-based materials for upper excited state photochemistry applications.

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Topics: Excited state (63%), Perylene (55%)

Open accessJournal ArticleDOI: 10.1021/ACS.JPCB.1C07045
Yichen Zhou1, Lin Ma2, Andrey V. Lunchev3, Saran Long1  +6 moreInstitutions (4)
Abstract: With the aim of constructing efficient photoelectric organic materials, a pyrido[3,2-g]quinoline derivative named LA17b has been synthesized, and its photodynamic relaxation processes in solvents and films were studied by time-resolved fluorescence and femtosecond transient absorption techniques. The steady-state fluorescence spectra show pronounced red-shift with the increase of the solvent polarity as well as in binary solvent hexane/ethanol by increasing ethanol concentration. However, the strong red-shift does not lead to quenching of the fluorescence. This is explained in terms of a twisted intramolecular charge transfer (TICT) state. The TICT state of LA17b in ethanol is highly emissive with a long fluorescence lifetime: 1.1 ns. TICT state was shown to play an important role in enhancement of intersystem crossing rate. TD-DFT calculations confirm the pathways of relaxation of locally excited state via TICT and triplet states. In films, the photodynamic properties are similar to that of LA17b in hexane and the TICT state vanishes due to the rigid environment. The obtained optical properties of this molecule suggest that it can be a promising candidate for various optoelectronic applications.

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Topics: Intersystem crossing (57%), Triplet state (55%), Quenching (fluorescence) (54%) ... show more

Journal ArticleDOI: 10.1016/J.DYEPIG.2021.109585
01 Oct 2021-Dyes and Pigments
Abstract: Amyloid fibrils, an aggregated form of proteins, are responsible for different types of neurological diseases. A constant effort is there for the search of a sensitive and selective probe for amyloid fibrils. Recently, it has been shown that a zwitterionic merocyanine dye, SYPRO Orange, can detect the amyloid fibrils with much higher sensitivity and with much preferred spectroscopic properties than present gold standard amyloid probe, Thioflavin T. In the present work, we have investigated the detailed photophysical properties of SYPRO Orange in different molecular solvents and solvent mixtures with wide range of properties to disentangle the fundamental processes that are responsible for its amyloid sensing activity. It has been shown that SYPRO Orange forms aggregates in water and results in extremely low emission quantum yield. The amyloid induced de-aggregation of SYPRO Orange is primarily responsible for enormous increase in its emission intensity upon binding with amyloid fibrils. Photophysical studies using steady state and time-resolved emission spectroscopy further enlighten us on the role of solvent polarity, solute-solvent H-bonding and solvent viscosity on its sensitivity towards amyloid fibrils. Thus, present results will be quite useful for the use of SYPRO Orange in different other spectroscopic applications.

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Topics: Amyloid (53%)

55 results found

Open accessJournal ArticleDOI: 10.18637/JSS.V049.I03
Abstract: In this work the software application called Glotaran is introduced as a Java-based graphical user interface to the R package TIMP, a problem solving environment for fitting superposition models to multi-dimensional data. TIMP uses a command-line user interface for the interaction with data, the specification of models and viewing of analysis results. Instead, Glotaran provides a graphical user interface which features interactive and dynamic data inspection, easier -- assisted by the user interface -- model specification and interactive viewing of results. The interactivity component is especially helpful when working with large, multi-dimensional datasets as often result from time-resolved spectroscopy measurements, allowing the user to easily pre-select and manipulate data before analysis and to quickly zoom in to regions of interest in the analysis results. Glotaran has been developed on top of the NetBeans rich client platform and communicates with R through the Java-to-R interface Rserve. The background and the functionality of the application are described here. In addition, the design, development and implementation process of Glotaran is documented in a generic way.

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Topics: User interface (67%), Graphical user interface testing (67%), 10-foot user interface (66%) ... show more

853 Citations

Journal ArticleDOI: 10.1021/ACS.CHEMREV.7B00581
Nicholas J. Hestand1, Frank C. Spano1Institutions (1)
17 Apr 2018-Chemical Reviews
Abstract: The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and “HJ” aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate ...

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Topics: Vibronic coupling (55%), Intermolecular force (51%)

503 Citations

Journal ArticleDOI: 10.1021/JO200990Y
Wanhua Wu1, Huimin Guo1, Wenting Wu1, Shaomin Ji1  +1 moreInstitutions (1)
Abstract: Triplet-triplet annihilation (TTA) based upconversions are attractive as a result of their readily tunable excitation/emission wavelength, low excitation power density, and high upconversion quantum yield. For TTA upconversion, triplet sensitizers and acceptors are combined to harvest the irradiation energy and to acquire emission at higher energy through triplet-triplet energy transfer (TTET) and TTA processes. Currently the triplet sensitizers are limited to the phosphorescent transition metal complexes, for which the tuning of UV-vis absorption and T(1) excited state energy level is difficult. Herein for the first time we proposed a library of organic triplet sensitizers based on a single chromophore of boron-dipyrromethene (BODIPY). The organic sensitizers show intense UV-vis absorptions at 510-629 nm (e up to 180,000 M(-1) cm(-1)). Long-lived triplet excited state (τ(T) up to 66.3 μs) is populated upon excitation of the sensitizers, proved by nanosecond time-resolved transient difference absorption spectra and DFT calculations. With perylene or 1-chloro-9,10-bis(phenylethynyl)anthracene (1CBPEA) as the triplet acceptors, significant upconversion (Φ(UC) up to 6.1%) was observed for solution samples and polymer films, and the anti-Stokes shift was up to 0.56 eV. Our results pave the way for the design of organic triplet sensitizers and their applications in photovoltaics and upconversions, etc.

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Topics: Triplet state (62%), Photon upconversion (56%), Phosphorescence (56%) ... show more

308 Citations

Journal ArticleDOI: 10.1021/ACS.ACCOUNTS.6B00576
Nicholas J. Hestand1, Frank C. Spano1Institutions (1)
Abstract: ConspectusThe transport and photophysical properties of organic molecular aggregates, films, and crystals continue to receive widespread attention, driven mainly by expanding commercial applications involving display and wearable technologies as well as the promise of efficient, large-area solar cells. The main blueprint for understanding how molecular packing impacts photophysical properties was drafted over five decades ago by Michael Kasha. Kasha showed that the Coulombic coupling between two molecules, as determined by the alignment of their transition dipoles, induces energetic shifts in the main absorption spectral peak and changes in the radiative decay rate when compared to uncoupled molecules. In H-aggregates, the transition dipole moments align “side-by-side” leading to a spectral blue-shift and suppressed radiative decay rate, while in J-aggregates, the transition dipole moments align “head-to-tail” leading to a spectral red-shift and an enhanced radiative decay rate. Although many examples of ...

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283 Citations