Nonadiabatic Molecular Dynamics Simulations Provide Evidence for Coexistence of Planar and Nonplanar Intramolecular Charge Transfer Structures in Fluorazene.

Fluorazene is a model compound for photoinduced intramolecular charge transfer (ICT) between aromatic moieties. Despite intensive studies, both spectroscopic and theoretical, a complete model of its photophysics is still lacking. Especially controversial is the geometry of its ICT structure, or structures.

An unprecedented roll-off ratio in high-performing red TADF OLED emitters featuring 2,3-indole-annulated naphthalene imide and auxiliary donors.

The capability of organic emitters to harvest triplet excitons a thermally activated delayed fluorescence (TADF) process has opened a new era in organic optoelectronics. Nevertheless, low brightness, and consequently an insufficient roll-off ratio, constitutes a bottleneck for their practical applications in the domain of organic light-emitting diodes (OLEDs). To address this formidable challenge, we developed a new design of desymmetrized naphthalimide (NMI) featuring an annulated indole with a set of auxiliary donors on its periphery.

Regioisomerism vs Conformation: Impact of Molecular Design on the Emission Pathway in Organic Light-Emitting Device Emitters.

Despite the design and proposal of several new structural motifs as thermally activated delayed fluorescent (TADF) emitters for organic light-emitting device (OLED) applications, the nature of their interaction with the host matrix in the emissive layer of the device and their influence on observed photophysical outputs remain unclear. To address this issue, we present, for the first time, the use of up to four regioisomers bearing a donor-acceptor-donor electronic structure based on the desymmetrized naphthalene benzimidazole scaffold, equipped with various electron-donating units and possessing distinguished conformational lability. Quantum chemical calculations allow us to identify the most favorable conformations adopted by the electron-rich groups across the entire pool of regioisomers.

Salicylideneaniline/Dithienylethene Hybrid Molecular Switches: Design, Synthesis, and Photochromism.

A hybrid molecular switch comprising salicylideneaniline (SA) and dithienylethene (DTE) moieties around a single benzene ring is reported. Due to an interplay between solvent-assisted enol-keto tautomerization in the former moiety and photochromic electrocyclization in the latter, this dithienylbenzene derivative was found to be photoresponsive at room temperature with a thermally stable closed form. The main photoproduct featuring ring-closed DTE and keto-enamine SA structures could be isolated and converted back to the starting material by irradiation with visible light.

Facile Functionalization of Ambipolar, Nitrogen-Doped PAHs toward Highly Efficient TADF OLED Emitters.

Despite promising optoelectronic features of N-doped polycyclic aromatic hydrocarbons (PAHs), their use as functional materials remains underdeveloped due to their limited post-functionalization. Facing this challenge, a novel design of N-doped PAHs with D-A-D electronic structure for thermally activated delayed fluorescence (TADF) emitters was performed. Implementing a set of auxiliary donors at the meta position of the protruding phenyl ring of quinoxaline triggers an increase in the charge-transfer property simultaneously decreasing the delayed fluorescence lifetime.

V-shaped donor-acceptor organic emitters. A new approach towards efficient TADF OLED devices.

We report the synthesis and characterization of a series of donor-acceptor TADF emitters with a new architecture, where the donor moiety and the dibenzazepine-based acceptor moiety are separated by a phenylene linker in a V-shaped spatial arrangement. Such spatial separation and electronic decoupling between the donor and the acceptor moieties leads to low singlet-triplet energy gaps and favors efficient exciton up-conversion.

Chromophore hydrolysis and release from photoactivated rhodopsin in native membranes.

For sustained vision, photoactivated rhodopsin (Rho*) must undergo hydrolysis and release of all--retinal, producing substrate for the visual cycle and apo-opsin available for regeneration with 11--retinal. The kinetics of this hydrolysis has yet to be described for rhodopsin in its native membrane environment. We developed a method consisting of simultaneous denaturation and chromophore trapping by isopropanol/borohydride, followed by exhaustive protein digestion, complete extraction, and liquid chromatography-mass spectrometry.

Tandem rigidification and π-extension as a key tool for the development of a narrow linewidth yellow hyperfluorescent OLED system.

Hyperfluorescence (HF), a relatively new phenomenon utilizing the transfer of excitons between two luminophores, requires careful pairwise tuning of molecular energy levels and is proposed to be the crucial step towards the development of new, highly effective OLED systems. To date, barely few HF yellow emitters with desired narrowband emission but moderate external quantum efficiency (EQE < 20%) have been reported. This is because a systematic strategy embracing both Förster resonance energy transfer (FRET) and triplet to singlet (TTS) transition as complementary mechanisms for effective exciton transfer has not yet been proposed.

Linear conjugated polymer photocatalysts with various linker units for photocatalytic hydrogen evolution from water.

Polymer photocatalysts have shown potential for light-driven hydrogen evolution from water. Here we studied the relative importance of the linker type in two series of conjugated polymers based on dibenzo[,]thiophene sulfone and dimethyl-9-fluorene. The alkenyl-linked polymers were found to be more active photocatalysts than their alkyl and alkyne-linked counterparts.

Simulation and analysis of the relaxation dynamics of a photochromic furylfulgide.

Furylfulgides, a class of photochromic organic compounds, show a complex system of photoinduced reactions. In the present study, the excited-state dynamics of the and isomers of a representative furylfulgide is modelled with the use of nonadiabatic molecular dynamics simulations. Moreover, a pattern recognition algorithm is employed in order to automatically identify relaxation pathways, and to quantify the photoproduct distributions.

Modular Nitrogen-Doped Concave Polycyclic Aromatic Hydrocarbons for High-Performance Organic Light-Emitting Diodes with Tunable Emission Mechanisms.

Although bowl-shaped N-pyrrolic polycyclic aromatic hydrocarbons (PAHs) can achieve excellent electron-donating ability, their application for optoelectronics is hampered by typically low photoluminescence quantum yields (PLQYs). To address this issue, we report the synthesis and characterization of a series of curved and fully conjugated nitrogen-doped PAHs. Through structural modifications to the electron-accepting moiety, we are able to switch the mechanism of luminescence between thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP), and to tune the overall PLQY in the range from 9 % to 86 %.

Simulation and Analysis of the Transient Absorption Spectrum of 4-(,-Dimethylamino)benzonitrile (DMABN) in Acetonitrile.

4-(,-Dimethylamino)benzonitrile (DMABN) is a well-known model compound for dual fluorescence-in sufficiently polar solvents, it exhibits two distinct fluorescence emission bands. The interpretation of its transient absorption (TA) spectrum in the visible range is the subject of a long-standing controversy. In the present study, we resolve this issue by calculating the TA spectrum on the basis of nonadiabatic molecular dynamics simulations.

Theoretical Study of the Photoisomerization Mechanism of All--Retinyl Acetate.

The compound 9--retinyl acetate (9--RAc) is a precursor to 9--retinal, which has potential application in the treatment of some hereditary diseases of the retina. An attractive synthetic route to 9--RAc is based on the photoisomerization reaction of the readily available all--RAc. In the present study, we examine the mechanism of the photoisomerization reaction with the use of state-of-the-art electronic structure calculations for two polyenic model compounds: -octatetraene and -2,6-dimethyl-1,3,5,7,9-decapentaene.

Photoinduced Double Proton Transfer in the Glyoxal-Methanol Complex Revisited: The Role of the Excited States.

Under irradiation in the visible range, the glyoxal-methanol complex in a cryogenic argon matrix undergoes a double proton transfer (DPT) reaction through which the glyoxal molecule isomerizes into hydroxyketene. In this work, we employ electronic structure simulations in order to shed more light on the underlying mechanism. Rewardingly, we find that the lowest singlet excited state (S) of the complex acts as a gateway to two previously unknown isomerization pathways, of which one takes place entirely in the singlet manifold and the other also involves the lowest triplet state (T).

Simulating the Nonadiabatic Relaxation Dynamics of 4-(,-Dimethylamino)benzonitrile (DMABN) in Polar Solution.

The compound 4-(,-dimethylamino)benzonitrile (DMABN) represents the archetypal system for dual fluorescence, a rare photophysical phenomenon in which a given fluorophore shows two distinct emission bands. Despite extensive studies, the underlying mechanism remains the subject of debate. In the present contribution, we address this issue by simulating the excited-state relaxation process of DMABN as it occurs in polar solution.

Theoretical Study of Ground- and Excited-State Charge Transfer in Fulvene-Based Donor-Acceptor Systems.

Donor-acceptor systems based on fulvene as the electron-accepting moiety are typified by exotic, strongly polar electronic structures. In this contribution, ab initio calculations have been performed to explore the ground- and excited-state properties of an archetypal compound of this class, which incorporates the exocyclic carbon atom of fulvene into a tetramethylimidazoline-like five-membered ring. In the electronic ground state, the compound under study has a pronounced zwitterionic character and is best described as consisting of a negatively charged cyclopentadienyl ring linked covalently to a positively charged tetramethylimidazolium ring.

Oscillatory Photoelectron Signal of N-Methylmorpholine as a Test Case for the Algebraic-Diagrammatic Construction Method of Second Order.

Motivated by recent progress in the application of time-resolved photoelectron spectroscopy (TRPES) to molecular Rydberg states, we report herein a detailed assessment of the performance of the second-order algebraic diagrammatic construction (ADC(2)) method in the simulation of their TRPES spectra. As the test case, we employ the tertiary aliphatic amine N-methylmorpholine (NMM), which is notable for the fact that the signal of its 3s state exhibits long-lived oscillations along the electron binding energy axis. The relaxation process of photoexcited NMM is simulated via the Born-Oppenheimer molecular dynamics method, and the resulting TRPES spectrum is generated on the basis of ionization energies and approximate Dyson orbital norms calculated with the continuum orbital technique.

Mechanism Underlying the Nucleobase-Distinguishing Ability of Benzopyridopyrimidine (BPP).

Benzopyridopyrimidine (BPP) is a fluorescent nucleobase analogue capable of forming base pairs with adenine (A) and guanine (G) at different sites. When incorporated into oligodeoxynucleotides, it is capable of differentiating between the two purine nucleobases by virtue of the fact that its fluorescence is largely quenched when it is base-paired to guanine, whereas base-pairing to adenine causes only a slight reduction of the fluorescence quantum yield. In the present article, the photophysics of BPP is investigated through computer simulations.

Theoretical Study of the Photophysics of 8-Vinylguanine, an Isomorphic Fluorescent Analogue of Guanine.

Paving the way for the application of the algebraic-diagrammatic construction scheme of second-order (ADC(2)) to systems based on the guanine chromophore, we demonstrate the this excited-state electronic structure method provides a realistic description of the photochemistry of 9H-guanine, in close agreement with the benchmark provided by the CASPT2 method. We then proceed to apply the ADC(2) method to the photochemistry of 8-vinylguanine (8vG), a minimally modified analogue of guanine which, unlike the naturally occurring nucleobase, displays intense fluorescence, indicative of a much longer-lived excited electronic state. The emissive electronic state of 8vG is identified as an ππ*-type intramolecular charge transfer (ICT) state, in which a charge of roughly -0.

Early Events in the Nonadiabatic Relaxation Dynamics of 4-(N,N-Dimethylamino)benzonitrile.

4-(N,N-Dimethylamino)benzonitrile (DMABN) is the archetypal system for dual fluorescence. Several past studies, both experimental and theoretical, have examined the mechanism of its relaxation in the gas phase following photoexcitation to the S2 state, without converging to a single description. In this contribution, we report first-principles simulations of the early events involved in this process performed using the nonadiabatic trajectory surface hopping (TSH) approach in combination with the ADC(2) electronic structure method.

Cold ablation driven by localized forces in alkali halides.

Laser ablation has been widely used for a variety of applications. Since the mechanisms for ablation are strongly dependent on the photoexcitation level, so called cold material processing has relied on the use of high-peak-power laser fluences for which nonthermal processes become dominant; often reaching the universal threshold for plasma formation of ~1 J cm(-2) in most solids. Here we show single-shot time-resolved femtosecond electron diffraction, femtosecond optical reflectivity and ion detection experiments to study the evolution of the ablation process that follows femtosecond 400 nm laser excitation in crystalline sodium chloride, caesium iodide and potassium iodide.

Ring-closing reaction in diarylethene captured by femtosecond electron crystallography.

The photoinduced ring-closing reaction in diarylethene, which serves as a model system for understanding reactive crossings through conical intersections, was directly observed with atomic resolution using femtosecond electron diffraction. Complementary ab initio calculations were also performed. Immediately following photoexcitation, subpicosecond structural changes associated with the formation of an open-ring excited-state intermediate were resolved.

Hybrid QM/QM simulations of photochemical reactions in the molecular crystal N-salicylidene-2-chloroaniline.

In this paper, we report the application of the QM/QM hybrid simulation technique to the photoisomerisation reactions of anils (i.e., Schiff bases of salicylaldehyde with aniline derivatives) in the solid state, on the example of the photochromic polymorph of N-salicylidene-2-chloroaniline.

Hybrid QM/QM Simulations of Excited-State Intramolecular Proton Transfer in the Molecular Crystal 7-(2-Pyridyl)-indole.

A subtractive implementation of the QM/QM hybrid method for the description of photochemical reactions occurring in molecular crystals is presented and tested by applying it in a simulation study of the ultrafast intramolecular excited-state proton transfer reaction in the crystal form of 7-(2-pyridyl)-indole, an organic compound featuring an intramolecular hydrogen bond within a six-membered ring. By propagating molecular dynamics on the excited-state potential energy surface, a mean proton transfer time was calculated as 80 fs. The reaction mechanism is discussed in terms of three-dimensional reaction coordinate diagrams.