Anion-Responsive Colorimetric and Fluorometric Red-Shift in Triarylborane Derivatives: Dual Role of Phenazaborine as Lewis Acid and Electron Donor.

Photophysical modulation of triarylboranes (TABs) through Lewis acid-base interactions is a fundamental approach for sensing anions. Yet, design principles for anion-responsive TABs displaying significant red-shift in absorption and photoluminescence (PL) have remained elusive. Herein, a new strategy for modulating the photophysical properties of TABs in a red-shift mode has been presented, by using a nitrogen-bridged triarylborane (1,4-phenazaborine: PAzB) with a contradictory dual role as a Lewis acid and an electron donor. Following the strategy, PAzB derivatives connected with an electron-deficient azaaromatic have been developed, and these compounds display a distinct red-shift in their absorption and PL in response to an anion. Spectroscopic analyses and quantum chemical calculations have revealed the formation of a tetracoordinate borate upon the addition of fluoride, narrowing the HOMO-LUMO gap and enhancing the charge-transfer character in the excited state. This approach has also been demonstrated in modulating the photophysical properties of solid-state films.

Modelling the quenching effect of chloroaluminum phthalocyanine and graphene oxide interactions: implications for phototherapeutic applications.

Photodynamic therapy (PDT) and photothermal therapy (PTT) are promising candidates for cancer treatment and their efficiency can be further enhanced by using a combination of both. While chloroaluminum phthalocyanine (AlClPc) has been studied extensively as a photosensitizer in PDT, nanographene oxide (nGO) has shown promise in PTT due to its high absorption of near-infrared radiation. In this work, we investigate the energy transport between AlClPc and nGO for their combined use in phototherapies. We use density functional theory (DFT) and time-dependent DFT to analyze the electronic structure of AlClPc and its interaction with nGO. Based on experimental parameters, we model the system's morphology and implement it in Kinetic Monte Carlo (KMC) simulations to investigate the energy transfer mechanism between the compounds. Our KMC calculations show that the experimentally observed fluorescence quenching requires modeling both the energy transfer from dyes to nGO and a molecular aggregation model. Our results provide insights into the underlying mechanisms responsible for the fluorescence quenching observed in AlClPc/nGO aggregates, which could impact the efficacy of photodynamic therapy.

Photophysics of Solvated Molecules: Computational Protocol Combining Nuclear Ensemble and Nonequilibrium State-Specific Solvation Methods.

Efficient calculations of the photophysical properties of molecules are essential for both understanding experimental results and accelerating materials discovery through computational simulations. However, to achieve accurate results, the effects of the surrounding medium must be taken into account. Here, we present a computational protocol that combines the nuclear ensemble method with a nonequilibrium state-specific polarizable continuum model to simulate absorption, fluorescence, phosphorescence, and intersystem crossing processes. Additionally, we introduced an extrapolation strategy that enables predictions for multiple solvents without incurring additional computational costs. We demonstrate the method's effectiveness by modeling the photophysical properties of a molecule that exhibits thermally activated delayed fluorescence, showcasing how these properties vary with solvent polarity. We also provide insight into the relationship between the solvent and photophysics by using ensemble analysis to rationalize simulation results. Furthermore, we introduce a metric for the intensity of the charge transfer character of electronic states and demonstrate how vibrations can significantly mix the electronic character of excited states. Overall, this work presents a computational approach that offers new insights into the photophysics of molecules and has the potential to advance materials discovery.

Diabatic Decomposition Perspective on the Role of Charge Transfer and Local Excitations in Thermally Activated Delayed Fluorescence.

Thermally activated delayed fluorescence (TADF) is a phenomenon that relies on the upconversion of triplet excitons to singlet excitons by means of reverse intersystem crossing (rISC). It has been shown both experimentally and theoretically that the TADF mechanism depends on the interplay between charge transfer and local excitations. However, the difference between the diabatic and adiabatic character of the involved excited states is rarely discussed in the literature. Here we develop a diabatization procedure to implement a four-state model Hamiltonian to a set of TADF molecules. We provide physical interpretations of the Hamiltonian elements and show their dependence on the electronic state of the equilibrium geometry. We also demonstrate how vibrations affect the TADF efficiency by modifying the diabatic decomposition of the molecule. Finally, we provide a simple model that connects the diabatic Hamiltonian to the electronic properties relevant to TADF and show how this relationship translates into different optimization strategies for rISC, fluorescence, and overall TADF performance.

Comparative study of thermally activated delayed fluorescent properties of donor-acceptor and donor-acceptor-donor architectures based on phenoxazine and dibenzo[a,j]phenazine.

A new thermally activated delayed fluorescence (TADF) compound based on a donor-acceptor (D-A) architecture (D = phenoxazine; A = dibenzo[a,j]phenazine) has been developed, and its photophysical properties were characterized. The D-A compound is applicable as an emitting material for efficient organic light-emitting diodes (OLEDs), and its external quantum efficiency (EQE) exceeds the theoretical maximum of those with prompt fluorescent emitters. Most importantly, comparative study of the D-A molecule and its D-A-D counterpart from the viewpoints of the experiments and theoretical calculations revealed the effect of the number of the electron donor on the thermally activated delayed fluorescent behavior.

Dual-photofunctional organogermanium compound based on donor-acceptor-donor architecture.

A dual-photofunctional organogermanium compound based on a donor-acceptor-donor architecture that exhibits thermally activated delayed fluorescence and mechano-responsive luminochromism has been developed. The developed compound was successfully applied as an emitter for efficient organic light-emitting diodes.

Unified Framework for Photophysical Rate Calculations in TADF Molecules.

One of the challenges in organic light-emitting diodes research is finding ways to increase device efficiency by making use of the triplet excitons that are inevitably generated in the process of electroluminescence. One way to do so is by thermally activated delayed fluorescence (TADF), a process in which triplet excitons undergo upconversion to singlet states, allowing them to relax radiatively. The discovery of this phenomenon has ensued a quest for new materials that are able to effectively take advantage of this mechanism. From a theoretical standpoint, this requires the capacity to estimate the rates of the various processes involved in the photophysics of candidate molecules, such as intersystem crossing, reverse intersystem crossing, fluorescence, and phosphorescence. Here, we present a method that is able to, within a single framework, compute all of these rates and predict the photophysics of new molecules. We apply the method to two TADF molecules and show that results compare favorably with other theoretical approaches and experimental results. Finally, we use a kinetic model to show how the calculated rates act in concert to produce different photophysical behavior.

Assessing the effects of increasing conjugation length on exciton diffusion: from small molecules to the polymeric limit.

Organic solar cells (OSC) generally contain long-chain π-conjugated polymers as donor materials, but, more recently, small-molecule donors have also attracted considerable attention. The nature of these compounds is of crucial importance concerning the various processes that determine device performance, among which singlet exciton diffusion is one of the most relevant. The efficiency of the diffusion mechanism depends on several aspects, from system morphology to electronic structure properties, which vary importantly with molecular size. In this work, we investigated the effects of conjugation length on the exciton diffusion length through electronic structure calculations and an exciton diffusion model. By applying extrapolation procedures to thiophene and phenylene vinylene oligomer series, we investigate their electronic and optical properties from the small-molecule point of view to the polymeric limit. Several properties are calculated as a function of oligomer size, including transition energies, absorption and emission spectra, reorganization energies, exciton coupling and Förster radii. Finally, an exciton diffusion model is used to estimate diffusion lengths as a function of oligomer size and for the polymeric limit showing agreement with experimental data. Results also show that longer conjugation lengths correlate with longer exciton diffusion lengths in spite of also being associated with shorter exciton lifetimes.

Charge localization and hopping in a topologically engineered graphene nanoribbon.

Graphene nanoribbons (GNRs) are promising quasi-one-dimensional materials with various technological applications. Recently, methods that allowed for the control of GNR's topology have been developed, resulting in connected nanoribbons composed of two distinct armchair GNR families. Here, we employed an extended version of the Su-Schrieffer-Heeger model to study the morphological and electronic properties of these novel GNRs. Results demonstrated that charge injection leads to the formation of polarons that localize strictly in the 9-AGNRs segments of the system. Its mobility is highly impaired by the system's topology. The polaron displaces through hopping between 9-AGNR portions of the system, suggesting this mechanism for charge transport in this material.

Kinetic Monte Carlo model for the COVID-19 epidemic: Impact of mobility restriction on a COVID-19 outbreak.

As the coronavirus disease 2019 (COVID-19) spreads worldwide, epidemiological models have been employed to evaluate possible scenarios and gauge the efficacy of proposed interventions. Considering the complexity of disease transmission dynamics in cities, stochastic epidemic models include uncertainty in their treatment of the problem, allowing the estimation of the probability of an outbreak, the distribution of epidemic magnitudes, and their expected duration. In this sense, we propose a kinetic Monte Carlo epidemic model that focuses on demography and on age-structured mobility data to simulate the evolution of the COVID-19 outbreak in the capital of Brazil, Brasilia, under several scenarios of mobility restriction. We show that the distribution of epidemic outcomes can be divided into short-lived mild outbreaks and longer severe ones. We demonstrate that quarantines have the effect of reducing the probability of a severe outbreak taking place but are unable to mitigate the magnitude of these outbreaks once they happen. Finally, we present the probability of a particular trajectory in the epidemic progression resulting in a massive outbreak as a function of the cumulative number of cases at the end of each quarantine period, allowing for the estimation of the risk associated with relaxing mobility restrictions at a given time.

Effective Mass of Quasiparticles in Armchair Graphene Nanoribbons.

Armchair graphene nanoribbons (AGNRs) may present intrinsic semiconducting bandgaps, being of potential interest in developing new organic-based optoelectronic devices. The induction of a bandgap in AGNRs results from quantum confinement effects, which reduce charge mobility. In this sense, quasiparticles' effective mass becomes relevant for the understanding of charge transport in these systems. In the present work, we theoretically investigate the drift of different quasiparticle species in AGNRs employing a 2D generalization of the Su-Schrieffer-Heeger Hamiltonian. Remarkably, our findings reveal that the effective mass strongly depends on the nanoribbon width and its value can reach 60 times the mass of one electron for narrow lattices. Such underlying property for quasiparticles, within the framework of gap tuning engineering in AGNRs, impact the design of their electronic devices.

Dynamical exciton decay in organic materials: the role of bimolecular recombination.

Excitons play a critical role in light emission when it comes to organic semiconductors. In high exciton concentration regimes, monomolecular and bimolecular routes for exciton recombination can yield different products affecting significantly the material's optical properties. Here, the dynamical decay of excitons is theoretically investigated using a kinetic Monte Carlo approach that addresses singlet exciton diffusion. Our numerical protocol includes two distinct exciton-exciton interaction channels: exciton annihilation and biexciton cascade emission. Our findings reveal that these channels produce different consequences concerning diffusion and spectroscopic properties, being able to explain diverging experimental observations. Importantly, we estimate critical exciton densities for which bimolecular recombination becomes dominant and investigate its effect on average exciton lifetimes and diffusion lengths.

Exciton Diffusion in Organic Nanofibers: A Monte Carlo Study on the Effects of Temperature and Dimensionality.

Organic nanofibers have found various applications in optoelectronic devices. In such devices, exciton diffusion is a major aspect concerning their efficiency. In the case of singlet excitons, Förster transfer is the mechanism responsible for this process. Temperature and morphology are factors known to influence exciton diffusion but are not explicitly considered in the expressions for the Förster rate. In this work, we employ a Kinetic Monte Carlo (KMC) model to investigate singlet exciton diffusion in para-hexaphenyl (P6P) and α-sexithiophene (6T) nanofibers. Building from previous experimental and theoretical studies that managed to obtain temperature dependent values for Förster radii, exciton average lifetimes and intermolecular distances, our model is able to indicate how these parameters translate into diffusion coefficients and diffusion lengths. Our results indicate that these features strongly depend on the coordination number in the material. Furthermore, we show how all these features influence the emitted light color in systems composed of alternating layers of P6P and 6T. Finally, we present evidence that the distribution of exciton displacements may result in overestimation of diffusion lengths in experimental setups.

Modeling temperature dependent singlet exciton dynamics in multilayered organic nanofibers.

Organic nanofibers have shown potential for application in optoelectronic devices because of the tunability of their optical properties. These properties are influenced by the electronic structure of the molecules that compose the nanofibers and also by the behavior of the excitons generated in the material. Exciton diffusion by means of Förster resonance energy transfer is responsible, for instance, for the change with temperature of colors in the light emitted by systems composed of different types of nanofibers. To study in detail this mechanism, we model temperature dependent singlet exciton dynamics in multilayered organic nanofibers. By simulating absorption and emission spectra, the possible Förster transitions are identified. Then, a kinetic Monte Carlo model is employed in combination with a genetic algorithm to theoretically reproduce time-resolved photoluminescence measurements for several temperatures. This procedure allows for the obtainment of different information regarding exciton diffusion in such a system, including temperature effects on the Förster transfer efficiency and the activation energy of the Förster mechanism. The method is general and may be employed for different systems where exciton diffusion plays a role.

Activation Energies and Diffusion Coefficients of Polarons and Bipolarons in Organic Conductors.

Intrachain diffusion of charge carriers in organic conductors is analyzed. Using a tight-binding model Hamiltonian that includes strong electron-phonon coupling combined with a Langevin equation, we simulate both polaron and bipolaron dynamics under quantum-corrected thermal effects. Nonadiabatic molecular time evolution is used to determine how these quasiparticles diffuse through a nondegenerate conjugated polymer. By means of a phenomenological approach, we evaluate the diffusion coefficient and activation energies for the motion of both polarons and bipolarons. The analysis of activation energies, in agreement with available experimental data, suggests that the presence of bipolarons may inhibit the efficiency of organic-based devices. The results presented here point to the importance of taking a closer look at the effects of bipolaron dynamics in organic devices.

Optical properties of P3HT and N2200 polymers: a performance study of an optimally tuned DFT functional.

The optical properties of systems composed of the polymers PolyeraActivInk™ N2200 and P3HT are experimentally and theoretically investigated using UV-Vis spectroscopy and time-dependent density functional theory calculations, respectively. From a theoretical point of view, we carried out an analysis considering several functionals and model oligomers of different sizes to mimic the polymers. As our studies were performed with and without solvents, a first important result regards the fact that, by considering solvent effects, a better agreement between theoretical and experimental results could be achieved. Our findings also show that an optimally tuned functional is better suited to describe the experimental absorption profile than a hybrid one for the flexible polymer (P3HT). For the almost rigid polymer considered here (N2200), on the other hand, hybrid functionals may perform better than tuned functionals.

A joint theoretical and experimental characterization of two acene-thiophene derivatives.

Acene-thiophenes compounds have been used successfully as active materials in thin-film transistors and photodetectors. This work aims at obtaining an adequate theoretical framework to accurately characterize the optical and electronic properties of two such compounds: NaT2 and NaT3. This is done by comparing the results of simulations with experimental absorption spectra. Basis size effects are investigated as well as the role of intramolecular vibrations in the simulated spectra. It is shown that the most important feature of a DFT calculation is the appropriate selection of long-range corrected functionals, which allows for the accurate description of the first absorption band of these molecules.

Modeling the Emission Spectra of Organic Molecules: A Competition between Franck-Condon and Nuclear Ensemble Methods.

The emission spectra of flexible and rigid organic molecules are theoretically investigated in the framework of the Franck-Condon (FC) and nuclear ensemble (NE) approaches, both of which rely on results from density functional theory but differ in the way vibrational contributions are taken into account. Our findings show that the emission spectra obtained using the NE approach are in better agreement with experiment than the ones produced by FC calculations considering both rigid and flexible molecules. Surprisingly, the description of a suitable balance between the vibronic progression and the emission spectra envelope shows dependency on the initial sampling for the NE calculations which must be judiciously selected. Our results intend to provide guidance for a better theoretical description of light emission properties of organic molecules with applications in organic electronic devices.