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.

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.

Density Functional Theory-Based Protocol to Calculate the Redox Potentials of First-row Transition Metal Complexes for Aqueous Redox Targeting Flow Batteries.

Transition metal complexes are a promising class of redox mediators for targeting redox flow batteries due to the tunability of their electrochemical potentials. However, reliable time-efficient tools for the prediction of their reduction potentials are needed. In this work, we establish a suitable density functional theory protocol for their prediction using an initial experimental data set of aqueous iron complexes with bidentate ligands. The approach is then cross-validated using different complexes found in the redox-flow literature. We find that the solvation model affects the prediction accuracy more than the functional or basis set. The smallest errors are obtained using the COSMO-RS solvation model (mean average error (MAE)=0.24 V). With implicit solvation models, a general deviation from experimental results is observed. For a set of similar ligands, they can be corrected using simple linear regression (MAE=0.051 V for the initial set of iron complexes).

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.

Gaining Insight into the Electrochemical Interface Dynamics in an Organic Redox Flow Battery with a Kinetic Monte Carlo Approach.

Finding low-cost and nontoxic redox couples for organic redox flow batteries is challenging due to unrevealed reaction mechanisms and side reactions. In this study, a 3D kinetic Monte Carlo model to study the electrode-anolyte interface of a methyl viologen-based organic redox flow battery is presented. This model captures various electrode processes, such as ionic displacement and degradation of active materials. The workflow consists of input parameters obtained from density functional theory calculations, a kinetic Monte Carlo algorithm to simulate the discharging process, and an electric double layer model to account for the electric field distribution near the electrode surface. Galvanostatic discharge is simulated at different anolyte concentrations and input current densities, which demonstrate that the model captured the formation of the electrical double layer due to ionic transport. The simulated electrochemical kinetics (potential, charge density) are found to be in agreement with the Nernst equation and the obtained EDL structure corresponded with published molecular dynamics results. The model's flexibility allows further applications of simulating the behavior of different redox couples and makes it possible to consider other molecular-scale phenomena. This study paves the way for computational screening of active species by assessing their potential kinetics in electrochemical environments.

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.

The Role of Oxygenic Groups and sp3 Carbon Hybridization in Activated Graphite Electrodes for Vanadium Redox Flow Batteries.

Graphite felt is a widely used electrode material for vanadium redox flow batteries. Electrode activation leads to the functionalization of the graphite surface with epoxy, OH, C=O, and COOH oxygenic groups and changes the carbon surface morphology and electronic structure, thereby improving the electrode's electroactivity relative to the untreated graphite. In this study, density functional theory (DFT) calculations are conducted to evaluate functionalization's contribution towards the positive half-cell reaction of the vanadium redox flow battery. The DFT calculations show that oxygenic groups improve the graphite felt's affinity towards the VO2+ /VO2 + redox couple in the following order: C=O>COOH>OH> basal plane. Projected density-of-states (PDOS) calculations show that these groups increase the electrode's sp3 hybridization in the same order, indicating that the increase in sp3 hybridization is responsible for the improved electroactivity, whereas the oxygenic groups' presence is responsible for this sp3 increment. These insights can aid the selection of activation processes and optimization of their parameters.

The Impact of C2 Insertion into a Carbazole Donor on the Physicochemical Properties of Dibenzo[a,j]phenazine-Cored Donor-Acceptor-Donor Triads.

Novel electron donor-acceptor-donor (D-A-D) compounds comprising dibenzo[a,j]phenazine as the central acceptor core and two 7-membered diarylamines (iminodibenzyl and iminostilbene) as the donors have been designed and synthesized. Investigation of their physicochemical properties revealed the impact of C2 insertion into well-known carbazole electron donors on the properties of previously reported twisted dibenzo[a,j]phenazine-core D-A-D triads. Slight structural modification caused a drastic change in conformational preference, allowing unique photophysical behavior of dual emission derived from room-temperature phosphorescence and triplet-triplet annihilation. Furthermore, electrochemical analysis suggested sigma-dimer formation and electrochemical polymerization on the electrode. Quantum chemical calculations also rationalized the experimental results.

A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials.

Discovering new materials for energy storage requires reliable and efficient protocols for predicting key properties of unknown compounds. In the context of the search for new organic electrolytes for redox flow batteries, we present and validate a robust procedure to calculate the redox potentials of organic molecules at any pH value, using widely available quantum chemistry and cheminformatics methods. Using a consistent experimental data set for validation, we explore and compare a few different methods for calculating reaction free energies, the treatment of solvation, and the effect of pH on redox potentials. We find that the B3LYP hybrid functional with the COSMO solvation method, in conjunction with thermal contributions evaluated from BLYP gas-phase harmonic frequencies, yields a good prediction of pH = 0 redox potentials at a moderate computational cost. To predict how the potentials are affected by pH, we propose an improved version of the Alberty-Legendre transform that allows the construction of a more realistic Pourbaix diagram by taking into account how the protonation state changes with pH.

Heavy-Atom-Free Room-Temperature Phosphorescent Organic Light-Emitting Diodes Enabled by Excited States Engineering.

Room temperature phosphorescence materials offer great opportunities for applications in optoelectronics, due to their unique photophysical characteristics. However, heavy-atom-free organic emitters that can realize distinct electrophosphorescence are rarely exploited. Herein a new approach for designing heavy-atom-free organic room temperature phosphorescence emitters for organic light-emitting diodes is presented. The subtle tuning of the singlet and triplet excited states energies by appropriate choice of host matrix allows tailored emission properties and switching of emission channels between thermally activated delayed fluorescence and room temperature phosphorescence. Moreover, an efficient and heavy-atom-free room temperature phosphorescence organic light-emitting diode using the developed emitter is realized.

Revealing Topological Influence of Phenylenediamine Unit on Physicochemical Properties of Donor-Acceptor-Donor-Acceptor Thermally Activated Delayed Fluorescent Macrocycles.

A new thermally activated delayed fluorescence (TADF)-displaying macrocyclic compound m-1 comprising of two electron-donors (N,N'-diphenyl-m-phenylenediamine) and two electron-acceptors (dibenzo[a,j]phenazine) has been synthesized. The macrocycle developed herein is regarded as a regioisomer of the previously reported TADF macrocycle p-1, which has two N,N'-diphenyl-p-phenylenediamines as the donors. To understand the influence of the topology of the phenylenediamine donors on physicochemical properties of TADF-active macrocycles, herein the molecular structure in the single crystals, photophysical properties, electrochemical behavior, and TADF properties of m-1 have been investigated compared with those of p-1. The substitution of p-phenylene donor with m-phenylene donor led to distinct positive solvatoluminochromism over the full visible-color range, unique oxidative electropolymerization, and slightly lower contribution of TADF, due to the lower CT character in the excited states.

Crystallization and Organic Field-Effect Transistor Performance of a Hydrogen-Bonded Quaterthiophene.

Crystalline thin films of π-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.

Unexpectedly Large Couplings Between Orthogonal Units in Anthraquinone Polymers.

The unusual electronic properties of directly linked 1,4-polyanthraquinones (14PAQs) are investigated. The dihedral angle between the molecular planes of anthraquinones (AQs) is found to be close to 90°. Contrary to the prevailing notion that the interaction between orthogonal units is negligible due to broken π-electron conjugation, the coupling between neighboring AQ units does not have a minimum at 90° and is much larger than that expected. The unexpectedly large electronic coupling between orthogonal AQ units is explained by the interaction between the lone pairs of the carbonyl oxygen and the π system of the neighboring unit, which allows favorable overlap between frontier molecular orbitals at the orthogonal geometry. It is shown that this effect, which is described computationally for the first time, can be strengthened by adding more quinone units. The effect of thermal fluctuations on the couplings is assessed through ab initio molecular dynamics simulations. The distributions of the couplings reveal that electron transport is resilient to dynamic disorder in all systems considered, whereas the hole couplings are much more sensitive to disorder. Lone pair-π interactions are described, as a previously largely overlooked conjugation mechanism, for incorporation into a new class of disorder-resilient semiconducting redox polymers.

Inverted Singlet-Triplet Gaps and Their Relevance to Thermally Activated Delayed Fluorescence.

The basic design principle for emitters exhibiting thermally activated delayed fluorescence (TADF) is the minimization of the singlet-triplet gap. While typically this gap is positive, a possible inversion of states has been proposed as a pathway to improve the efficiency of organic light-emitting diodes. Despite the efforts to design such emitters, there are very few reports indicating that it is at all possible. We analyze the problem of the gap inversion from the perspective of the electronic structure theory. The key result is that inversion is possible but requires a substantial contribution of double excitations and that commonly used cheap electronic structure methods would fail to predict it.

Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules.

Density functional theory (DFT) is the method of choice for predicting structures and reaction energies of molecular systems. However, it remains a daunting task to systematically improve the accuracy of an approximate density functional. The recently proposed many-pair expansion (MPE) [ Phys. Rev. B 2016, 93, 201108] is a density functional hierarchy that systematically corrects any deficiencies of an approximate functional to converge to the exact energy, and was shown to give accurate results for lattice models. In this work, we extend MPE to molecular systems and implement it using Gaussian basis sets. The self-attractive Hartree (SAH) decomposition [ J. Chem. Theory Comput. 2018, 14, 92-103] is employed to generate localized v-representable pair densities for performing MPE calculations. We demonstrate that MPE at the second order (MPE2) already predicts accurate molecular and reaction energies for a series of small molecules and hydrogen chains, with the EXX functional as its starting point. We also show that MPE correctly describes the symmetric bond breaking in hydrogen rings, indicating its ability to remove strong correlation errors. MPE thus provides a promising framework to systematically improve density functional calculations of molecules.

QM/MM Study of Static and Dynamic Energetic Disorder in the Emission Layer of an Organic Light-Emitting Diode.

Static and dynamic energetic disorder in emission layers of organic light-emitting diodes (OLEDs) is investigated through combined molecular dynamics and hybrid quantum mechanics/molecular mechanics (QM/MM) calculations. The analysis is based on a comparison of ensemble and time distributions of site energies of guest and host components in an emission layer. The law of total variance is applied to decompose the total disorder into its static and dynamic contributions. It is found that both contributions are of the same order of magnitude. While the dynamic disorder is not affected by intermolecular interactions, the static disorder for both guests and hosts is determined by the polarity of host molecules. The amount of static disorder affects charge-transport properties and exciton formation pathways, which consequently influence the overall efficiency of an OLED device. The simulations indicate that the amount of static disorder induced by the host should be considered for the optimization of the emission layer.

Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments.

Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding.

Shorter Exciton Lifetimes via an External Heavy-Atom Effect: Alleviating the Effects of Bimolecular Processes in Organic Light-Emitting Diodes.

Multiexcited-state phenomena are believed to be the root cause of two exigent challenges in organic light-emitting diodes; namely, efficiency roll-off and degradation. The development of novel strategies to reduce exciton densities under heavy load is therefore highly desirable. Here, it is shown that triplet exciton lifetimes of thermally activated delayed-fluorescence-emitter molecules can be manipulated in the solid state by exploiting intermolecular interactions. The external heavy-atom effect of brominated host molecules leads to increased spin-orbit coupling, which in turn enhances intersystem crossing rates in the guest molecule. Wave function overlap between the host and the guest is confirmed by combined molecular dynamics and density functional theory calculations. Shorter triplet exciton lifetimes are observed, while high photoluminescence quantum yields and essentially unaltered emission spectra are maintained. A change in the intersystem crossing rate ratio due to increased dielectric constants leads to almost 50% lower triplet exciton densities in the emissive layer in the steady state and results in an improved onset of the photoluminescence quantum yield roll-off at high excitation densities. Efficient organic light-emitting diodes with better roll-off behavior based on these novel hosts are fabricated, demonstrating the suitability of this concept for real-world applications.