Ab Initio Simulations of Poorly and Well Equilibrated (CH3CN)n- Cluster Anions: Assigning Experimental Photoelectron Peaks to Surface-Bound Electrons and Solvated Monomer and Dimer Anions.

Excess electrons in liquid acetonitrile are of particular interest because they exist in two different forms in equilibrium: they can be present as traditional solvated electrons in a cavity, and they can form some type of solvated molecular anion. Studies of small acetonitrile cluster anions in the gas phase show two isomers with distinct vertical detachment energies, and it is tempting to presume that the two gas-phase cluster anion isomers are precursors of the two excess electron species present in bulk solution. In this paper, we perform DFT-based ab initio molecular dynamics simulations of acetonitrile cluster anions to understand the electronic species that are present and why they have different binding energies. Using a long-range-corrected density functional that was optimally tuned to describe acetonitrile cluster anion structures, we have theoretically explored the chemistry of (CH3CN)n- cluster anions with sizes n = 5, 7, and 10. Because the temperature of the experimental cluster anions is not known, we performed two sets of simulations that investigated how the way in which the cluster anions are prepared affects the excess electron binding motif: one set of simulations simply attached excess electrons to neutral (CH3CN)n clusters, providing little opportunity for the clusters to relax in the presence of the excess electron, while the other set allowed the cluster anions to thermally equilibrate near room temperature. We find that both sets of simulations show three distinct electron binding motifs: electrons can attach to the surface of the cluster (dipole-bound) or be present either as solvated monomer anions, CH3CN-, or as solvated molecular dimer anions, (CH3CN)2-. All three species have higher binding energies at larger cluster sizes. Thermal equilibration strongly favors the formation of the valence-bound molecular anions relative to surface-bound excess electrons, and the dimer anion becomes more stable than the monomer anion and surface-bound species as the cluster size increases. The calculated photoelectron spectra from our simulations in which there was poor thermal equilibration are in good agreement with experiment, suggesting assignment of the two experimental cluster anion isomers as the surface-bound electron and the solvated molecular dimer anion. The simulations also suggest that the shoulder seen experimentally on the low-energy isomer's detachment peak is not part of a vibronic progression but instead results from molecular monomer anions. Nowhere in the size range that we explore do we see evidence for a nonvalence, cavity-bound interior-solvated electron, indicating that this species is likely only accessible at larger sizes with good thermal equilibration.

Tunable Dopants with Intrinsic Counterion Separation Reveal the Effects of Electron Affinity on Dopant Intercalation and Free Carrier Production in Sequentially Doped Conjugated Polymer Films.

Carrier mobility in doped conjugated polymers is limited by Coulomb interactions with dopant counterions. This complicates studying the effect of the dopant's oxidation potential on carrier generation because different dopants have different Coulomb interactions with polarons on the polymer backbone. Here, dodecaborane (DDB)-based dopants are used, which electrostatically shield counterions from carriers and have tunable redox potentials at constant size and shape. DDB dopants produce mobile carriers due to spatial separation of the counterion, and those with greater energetic offsets produce more carriers. Neutron reflectometry indicates that dopant infiltration into conjugated polymer films is redox-potential-driven. Remarkably, X-ray scattering shows that despite their large 2-nm size, DDBs intercalate into the crystalline polymer lamellae like small molecules, indicating that this is the preferred location for dopants of any size. These findings elucidate why doping conjugated polymers usually produces integer, rather than partial charge transfer: dopant counterions effectively intercalate into the lamellae, far from the polarons on the polymer backbone. Finally, it is shown that the IR spectrum provides a simple way to determine polaron mobility. Overall, higher oxidation potentials lead to higher doping efficiencies, with values reaching 100% for driving forces sufficient to dope poorly crystalline regions of the film.

Ultrafast transient absorption spectroscopy of doped P3HT films: distinguishing free and trapped polarons.

It is generally presumed that the vast majority of carriers created by chemical doping of semiconducting polymer films are coulombically trapped by the counteranion, with only a small fraction that are free and responsible for the increased conductivity essential for organic electronic applications. At higher doping levels, it is also possible for bipolarons to form, which are expected to be less conductive than single polarons. Unfortunately, there is no simple way to distinguish free polarons, trapped polarons and bipolarons using steady-state spectroscopy. Thus, in this work, we use ultrafast transient absorption spectroscopy to study the dynamics of polarons in 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TNCQ)-doped films of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a function of dopant concentration and excitation wavelength. When exciting on the red side of the polaron P1 transition, our transient absorption spectra and kinetics match well with what is expected for free 2-D-delocalized polarons; the measurements are not consistent with a recent theory of doped conjugated polymer electronic structure that suggests that the half-filled state lies deeper in the conduction band rather than in the bandgap. As we tune the excitation wavelength to the blue, our measurements reveal an increasing amount of slower transient kinetics that are consistent with the presence of coulombically-trapped polarons rather than bipolarons. Taking advantage of their distinct ultrafast relaxation kinetics as a type of action spectroscopy, we are able to extract the steady-state absorption spectra of free and trapped polarons as a function of dopant concentration. By comparing the results to theoretical models, we determine that in F4TCNQ-doped P3HT films, trapped polarons sit ∼0.4 nm away from the anion while free polarons reside between 0.7 and 0.9 nm from the counteranion. Perhaps counterintuitively, the ratio of trapped to free polarons increases at higher doping levels, an observation that is consistent with a plateau in the concentration-dependent conductivity of F4TCNQ-doped P3HT films.

Temperature dependence of the hydrated electron's excited-state relaxation. I. Simulation predictions of resonance Raman and pump-probe transient absorption spectra of cavity and non-cavity models.

We use one-electron non-adiabatic mixed quantum/classical simulations to explore the temperature dependence of both the ground-state structure and the excited-state relaxation dynamics of the hydrated electron. We compare the results for both the traditional cavity picture and a more recent non-cavity model of the hydrated electron and make definite predictions for distinguishing between the different possible structural models in future experiments. We find that the traditional cavity model shows no temperature-dependent change in structure at constant density, leading to a predicted resonance Raman spectrum that is essentially temperature-independent. In contrast, the non-cavity model predicts a blue-shift in the hydrated electron's resonance Raman O-H stretch with increasing temperature. The lack of a temperature-dependent ground-state structural change of the cavity model also leads to a prediction of little change with temperature of both the excited-state lifetime and hot ground-state cooling time of the hydrated electron following photoexcitation. This is in sharp contrast to the predictions of the non-cavity model, where both the excited-state lifetime and hot ground-state cooling time are expected to decrease significantly with increasing temperature. These simulation-based predictions should be directly testable by the results of future time-resolved photoelectron spectroscopy experiments. Finally, the temperature-dependent differences in predicted excited-state lifetime and hot ground-state cooling time of the two models also lead to different predicted pump-probe transient absorption spectroscopy of the hydrated electron as a function of temperature. We perform such experiments and describe them in Paper II [E. P. Farr et al., J. Chem. Phys. 147, 074504 (2017)], and find changes in the excited-state lifetime and hot ground-state cooling time with temperature that match well with the predictions of the non-cavity model. In particular, the experiments reveal stimulated emission from the excited state with an amplitude and lifetime that decreases with increasing temperature, a result in contrast to the lack of stimulated emission predicted by the cavity model but in good agreement with the non-cavity model. Overall, until ab initio calculations describing the non-adiabatic excited-state dynamics of an excess electron with hundreds of water molecules at a variety of temperatures become computationally feasible, the simulations presented here provide a definitive route for connecting the predictions of cavity and non-cavity models of the hydrated electron with future experiments.

Temperature dependence of the hydrated electron's excited-state relaxation. II. Elucidating the relaxation mechanism through ultrafast transient absorption and stimulated emission spectroscopy.

The structure of the hydrated electron, particularly whether it exists primarily within a cavity or encompasses interior water molecules, has been the subject of much recent debate. In Paper I [C.-C. Zho et al., J. Chem. Phys. 147, 074503 (2017)], we found that mixed quantum/classical simulations with cavity and non-cavity pseudopotentials gave different predictions for the temperature dependence of the rate of the photoexcited hydrated electron's relaxation back to the ground state. In this paper, we measure the ultrafast transient absorption spectroscopy of the photoexcited hydrated electron as a function of temperature to confront the predictions of our simulations. The ultrafast spectroscopy clearly shows faster relaxation dynamics at higher temperatures. In particular, the transient absorption data show a clear excess bleach beyond that of the equilibrium hydrated electron's ground-state absorption that can only be explained by stimulated emission. This stimulated emission component, which is consistent with the experimentally known fluorescence spectrum of the hydrated electron, decreases in both amplitude and lifetime as the temperature is increased. We use a kinetic model to globally fit the temperature-dependent transient absorption data at multiple temperatures ranging from 0 to 45 °C. We find the room-temperature lifetime of the excited-state hydrated electron to be 137±40 fs, in close agreement with recent time-resolved photoelectron spectroscopy (TRPES) experiments and in strong support of the "non-adiabatic" picture of the hydrated electron's excited-state relaxation. Moreover, we find that the excited-state lifetime is strongly temperature dependent, changing by slightly more than a factor of two over the 45 °C temperature range explored. This temperature dependence of the lifetime, along with a faster rate of ground-state cooling with increasing bulk temperature, should be directly observable by future TRPES experiments. Our data also suggest that the red side of the hydrated electron's fluorescence spectrum should significantly decrease with increasing temperature. Overall, our results are not consistent with the nearly complete lack of temperature dependence predicted by traditional cavity models of the hydrated electron but instead agree qualitatively and nearly quantitatively with the temperature-dependent structural changes predicted by the non-cavity hydrated electron model.

Resonance Raman and temperature-dependent electronic absorption spectra of cavity and noncavity models of the hydrated electron.

Most of what is known about the structure of the hydrated electron comes from mixed quantum/classical simulations, which depend on the pseudopotential that couples the quantum electron to the classical water molecules. These potentials usually are highly repulsive, producing cavity-bound hydrated electrons that break the local water H-bonding structure. However, we recently developed a more attractive potential, which produces a hydrated electron that encompasses a region of enhanced water density. Both our noncavity and the various cavity models predict similar experimental observables. In this paper, we work to distinguish between these models by studying both the temperature dependence of the optical absorption spectrum, which provides insight into the balance of the attractive and repulsive terms in the potential, and the resonance Raman spectrum, which provides a direct measure of the local H-bonding environment near the electron. We find that only our noncavity model can capture the experimental red shift of the hydrated electron's absorption spectrum with increasing temperature at constant density. Cavity models of the hydrated electron predict a solvation structure similar to that of the larger aqueous halides, leading to a Raman O-H stretching band that is blue-shifted and narrower than that of bulk water. In contrast, experiments show the hydrated electron has a broader and red-shifted O-H stretching band compared with bulk water, a feature recovered by our noncavity model. We conclude that although our noncavity model does not provide perfect quantitative agreement with experiment, the hydrated electron must have a significant degree of noncavity character.

Using Machine Learning to Understand the Causes of Quantum Decoherence in Solution-Phase Bond-Breaking Reactions.

Decoherence is a fundamental phenomenon that occurs when an entangled quantum state interacts with its environment, leading to collapse of the wave function. The inevitability of decoherence provides one of the most intrinsic limits of quantum computing. However, there has been little study of the precise chemical motions from the environment that cause decoherence. Here, we use quantum molecular dynamics simulations to explore the photodissociation of Na2+ in liquid Ar, in which solvent fluctuations induce decoherence and thus determine the products of chemical bond breaking. We use machine learning to characterize the solute-solvent environment as a high-dimensional feature space that allows us to predict when and onto which photofragment the bonding electron will localize. We find that reaching a requisite photofragment separation and experiencing out-of-phase solvent collisions underlie decoherence during chemical bond breaking. Our work highlights the utility of machine learning for interpreting complex solution-phase chemical processes as well as identifies the molecular underpinnings of decoherence.

Partial Molar Solvation Volume of the Hydrated Electron Simulated Via DFT.

Different simulation models of the hydrated electron produce different solvation structures, but it has been challenging to determine which simulated solvation structure, if any, is the most comparable to experiment. In a recent work, Neupane et al. [J. Phys. Chem. B 2023, 127, 5941-5947] showed using Kirkwood-Buff theory that the partial molar volume of the hydrated electron, which is known experimentally, can be readily computed from an integral over the simulated electron-water radial distribution function. This provides a sensitive way to directly compare the hydration structure of different simulation models of the hydrated electron with experiment. Here, we compute the partial molar volume of an ab-initio-simulated hydrated electron model based on density-functional theory (DFT) with a hybrid functional at different simulated system sizes. We find that the partial molar volume of the DFT-simulated hydrated electron is not converged with respect to the system size for simulations with up to 128 waters. We show that even at the largest simulation sizes, the partial molar volume of DFT-simulated hydrated electrons is underestimated by a factor of 2 with respect to experiment, and at the standard 64-water size commonly used in the literature, DFT-based simulations underestimate the experimental solvation volume by a factor of ∼3.5. An extrapolation to larger box sizes does predict the experimental partial molar volume correctly; however, larger system sizes than those explored here are currently intractable without the use of machine-learned potentials. These results bring into question what aspects of the predicted hydrated electron radial distribution function, as calculated by DFT-based simulations with the PBEh-D3 functional, deviate from the true solvation structure.

Using Bulky Dodecaborane-Based Dopants to Produce Mobile Charge Carriers in Amorphous Semiconducting Polymers.

Conjugated polymers are a versatile class of electronic materials featured in a variety of next-generation electronic devices. The utility of such polymers is contingent in large part on their electrical conductivity, which depends both on the density of charge carriers (polarons) and on the carrier mobility. Carrier mobility, in turn, is largely controlled by the separation between the polarons and dopant counterions, as counterions can produce Coulombic traps. In previous work, we showed that large dopants based on dodecaborane (DDB) clusters were able to reduce Coulombic binding and thus increase carrier mobility in regioregular (RR) poly(3-hexylthiophene-2,5-diyl) (P3HT). Here, we use a DDB-based dopant to study the effects of polaron-counterion separation in chemically doped regiorandom (RRa) P3HT, which is highly amorphous. X-ray scattering shows that the DDB dopants, despite their large size, can partially order the RRa P3HT during doping and produce a doped polymer crystal structure similar to that of DDB-doped RR P3HT; Alternating Field (AC) Hall measurements also confirm a similar hole mobility. We also show that use of the large DDB dopants successfully reduces Coulombic binding of polarons and counterions in amorphous polymer regions, resulting in a 77% doping efficiency in RRa P3HT films. The DDB dopants are able to produce RRa P3HT films with a 4.92 S/cm conductivity, a value that is ∼200× higher than that achieved with 3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the traditional dopant molecule. These results show that tailoring dopants to produce mobile carriers in both the amorphous and semicrystalline regions of conjugated polymers is an effective strategy for increasing achievable polymer conductivities, particularly in low-cost polymers with random regiochemistry. The results also emphasize the importance of dopant size and shape for producing Coulombically unbound, mobile polarons capable of electrical conduction in less-ordered materials.

Novel WRN Helicase Inhibitors Selectively Target Microsatellite Unstable Cancer Cells.

Microsatellite-unstable (MSI) cancers require WRN helicase to resolve replication stress due to expanded DNA (TA)n-dinucleotide repeats. WRN is a promising synthetic lethal target for MSI tumours, and WRN inhibitors are in development. Here, we used CRISPR-Cas9 base editing to map WRN residues critical for MSI cells, validating the helicase domain as the primary drug target. Fragment-based screening led to the development of potent and highly selective WRN helicase covalent inhibitors. These compounds selectively suppressed MSI model growth In vitro and In vivo by mimicking WRN loss, inducing DNA double-strand breaks at expanded TA-repeats and DNA damage. Assessment of biomarkers in preclinical models linked TA-repeat expansions and mismatch repair (MMR) alterations to compound activity. Efficacy was confirmed in immunotherapy-resistant organoids and patient-derived xenograft (PDX) models. The discovery of potent, selective covalent WRN inhibitors provides proof of concept for synthetic-lethal targeting of WRN in MSI cancer and tools to dissect WRN biology.

Activation of snap-top capped mesoporous silica nanocontainers using two near-infrared photons.

Photoactivation of "snap-top" stoppers over the pore openings of mesoporous silica nanoparticles releases intact cargo molecules from the pores. The on-command release can be stimulated by either one UV photon or two coherent near-IR photons. Two-photon activation is particularly desirable for use in biological systems because it enables good tissue penetration and precise spatial control. Stoppers were assembled by first binding photolabile coumarin-based molecules to the nanoparticle surface. Then, after the particles were loaded with cargo, bulky ß-cyclodextrin (CD) molecules were noncovalently associated with the substituted coumarin molecule, blocking the pores and preventing the cargo from escaping. One-photon excitation at 376 nm or two-photon excitation at 800 nm cleaves the bond holding the coumarin to the nanopore, releasing both the CD cap and the cargo. The dynamics of both the cleavage of the cap and the cargo release was monitored using fluorescence spectroscopy. This system traps intact cargo molecules without the necessity of chemical modification, releases them with tissue-penetrating near-IR light, and has possible applications in photostimulated drug delivery.

Going beyond the frozen core approximation: development of coordinate-dependent pseudopotentials and application to Na2(+).

Mixed quantum/classical (MQC) simulations treat the majority of a system classically and reserve quantum mechanics only for a few degrees of freedom that actively participate in the chemical process(es) of interest. In MQC calculations, the quantum and classical degrees of freedom are coupled together using pseudopotentials. Although most pseudopotentials are developed empirically, there are methods for deriving pseudopotentials using the results of quantum chemistry calculations, which guarantee that the explicitly-treated valence electron wave functions remain orthogonal to the implicitly-treated core electron orbitals. Whether empirical or analytically derived in nature, to date all such pseudopotentials have been subject to the frozen core approximation (FCA) that ignores how changes in the nuclear coordinates alter the core orbitals, which in turn affects the wave function of the valence electrons. In this paper, we present a way to go beyond the FCA by developing pseudopotentials that respond to these changes. In other words, we show how to derive an analytic expression for a pseudopotential that is an explicit function of nuclear coordinates, thus accounting for the polarization effects experienced by atomic cores in different chemical environments. We then use this formalism to develop a coordinate-dependent pseudopotential for the bonding electron of the sodium dimer cation molecule and we show how the analytic representation of this potential can be used in one-electron MQC simulations that provide the accuracy of a fully quantum mechanical Hartree-Fock (HF) calculation at all internuclear separations. We also show that one-electron MQC simulations of Na(2)(+) using our coordinate-dependent pseudopotential provide a significant advantage in accuracy compared to frozen core potentials with no additional computational expense. This is because use of a frozen core potential produces a charge density for the bonding electron of Na(2)(+) that is too localized on the molecule, leading to significant overbinding of the valence electron. This means that FCA calculations are subject to inaccuracies of order ~10% in the calculated bond length and vibrational frequency of the molecule relative to a full HF calculation; these errors are fully corrected by using our coordinate-dependent pseudopotential. Overall, our findings indicate that even for molecules like Na(2)(+), which have a simple electronic structure that might be expected to be well-treated within the FCA, the importance of including the effects of the changing core molecular orbitals on the bonding electrons cannot be overlooked.

Response to "Comment on 'Going beyond the frozen core approximation: development of coordinate-dependent pseudopotentials and application to Na2(+)'" [J. Chem. Phys. 139, 147101 (2013)].

Stoll, Fuentealba, and Szentpály (SFS) argue that the coordinate-dependent pseudopotential we developed for the sodium dimer cation molecule is inferior to other potentials that have been presented in the literature for this molecule. The goal of our work, however, was to present a novel method for the development of rigorous coordinate-dependent pseudopotentials. Our method is designed to reproduce all-electron Hartree-Fock calculations without the inclusion of adjustable parameters. Moreover, our method starts from the superposition of unoptimized, non-norm-conserved atomic potentials, so that when complete, the resulting norm-conserving potential can reproduce an all-electron Hartree-Fock calculation without the inclusion of adjustable parameters. We chose the sodium dimer cation system as a proof of principle for our method, and showed that our method does indeed allow a one-electron calculation to correctly reproduce the all-electron Hartree-Fock calculation from bonding to the dissociation limit. Our purpose in developing this method is to use such potentials in condensed-phase mixed quantum/classical molecular dynamics simulations, where inclusion of valence polarization effects is unimportant or can be added on after the fact. Thus we do not claim that our method provides a potential that is superior to potentials that have been specifically constructed to go beyond the static exchange approximation and/or include valence polarization effects-such potentials are beyond the scope of our work. We also note that although we made a numerical error in the application of our method to Na2(+) in our original work [A. Kahros and B. J. Schwartz, J. Chem. Phys. 138, 054110 (2013)] that led to an overestimation of the magnitude of core polarization effects for this particular molecule, out method does work as derived for this molecule and the error does not affect the significance of our method or its general applicability.

How Ions Break Local Symmetry: Simulations of Polarized Transient Hole Burning for Different Models of the Hydrated Electron in Contact Pairs with Na.

The hydrated electron (eaq-) is known via polarized transient hole-burning (pTHB) experiments to have a homogeneously broadened absorption spectrum. Here, we explore via quantum simulation how the pTHB spectroscopy of different eaq- models changes in the presence of electrolytes. The idea is that cation-eaq- pairing can break the local symmetry and, thus, induce persistent inhomogeneity. We find that a "hard" cavity model shows a modest increase in the pTHB recovery time in the presence of salt, while a "soft" cavity model remains homogeneously broadened independent of the salt concentration. We also explore the orientational anisotropy of a fully ab initio density functional theory-based model of the eaq-, which is strongly inhomogeneously broadened without salt and which becomes significantly more inhomogeneously broadened in the presence of salt. The results provide a direct prediction for experiments that can distinguish between different models and, thus, help pin down the hydration structure and dynamics of the eaq-.

Does the Traditional Band Picture Describe the Electronic Structure of Doped Conjugated Polymers? TD-DFT and Natural Transition Orbital Study of Doped P3HT.

Polarons and bipolarons are created when one or two electrons are removed from the π-system of a p-type conjugated polymer, respectively. In the traditional band picture, the creation of a polaron causes two electronic energy levels to move into the band gap. The removal of a second electron to form a bipolaron causes the two intragap states to move further into the gap. Several groups, however, who looked at the energies of the Kohn-Sham orbitals from DFT calculations, have recently argued that the traditional band picture is incorrect for explaining the spectroscopy of doped conjugated polymers. Instead, the DFT calculations suggest that polaron creation causes only one unoccupied state to move into the band gap near the valence band edge while half-filled state in the valence band and the conduction band bend downward in energy. To understand the discrepancy, we performed TD-DFT calculations of polarons and bipolarons on poly(3-hexylthiophene) (P3HT). Not only do the TD-DFT-calculated absorption spectra match the experimental absorption spectra, but an analysis using natural transitional orbitals (NTOs), which provides an approximate one-electron picture from the many-electron TD-DFT results, supports the traditional band picture. Our TD-DFT/NTO analysis indicates that the traditional band picture also works for bipolarons, a system for which DFT calculations were unable to determine the electronic structure.

Ab Initio Studies of Hydrated Electron/Cation Contact Pairs: Hydrated Electrons Simulated with Density Functional Theory Are Too Kosmotropic.

We have performed the first DFT-based ab initio MD simulations of a hydrated electron (eaq-) in the presence of Na+, a system chosen because ion-pairing behavior in water depends sensitively on the local hydration structure. Experiments show that eaq-'s interact weakly with Na+; the eaq-'s spectrum blue shifts by only a few tens of meV upon ion pairing without changing shape. We find that the spectrum of the DFT-simulated eaq- red shifts and changes shape upon interaction with Na+, in contrast with experiment. We show that this is because the hydration structure of the DFT-simulated eaq- is too ordered or kosmotropic. Conversely, simulations that produce eaq-'s with a less ordered or chaotropic hydration structure form weaker ion pairs with Na+, yielding predicted spectral blue shifts in better agreement with experiment. Thus, ab initio simulations based on hybrid GGA DFT functionals fail to produce the correct solvation structure for the hydrated electron.

Facile synthesis of 2-aza-9,10-diphenylanthracene and the effect of precise nitrogen atom incorporation on OLED emitters performance.

Polycyclic aromatic hydrocarbons (PAHs) are important compounds in materials chemistry, particularly for optoelectronic applications. One strategy for tuning PAH properties involves the net exchange of carbon atoms for heteroatoms, such as nitrogen. We report a comparative study of the well-known fluorophore 9,10-diphenylanthracene with an aza analog. The latter compound is accessed using a short sequence involving the use of two strained cyclic alkynes, benzyne and a 3,4-piperidyne, in Diels-Alder cycloaddition sequences. Comparative studies of 9,10-diphenylanthracene and the aza-analog show how the addition of a single nitrogen atom impacts electrochemical and optical properties. Organic light-emitting diode (OLED) devices were prepared using both compounds, which showed that nitrogen substitution leads to an unexpected red shift in electroluminescence, likely due to exciplex formation between the active layer and the 4,4'-N,N'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) hole-transport layer. These studies highlight a unique approach to accessing heteroatom-containing PAHs, while underscoring the impact of heteroatoms on OLED device performance.

Crystal-packing trends for a series of 6,9,12,15,18-pentaaryl-1-hydro[60]fullerenes.

The relationship between the size of the substituents of aryl groups in a series of fifteen 6,9,12,15,18-pentaaryl-1-hydro[60]fullerenes and the solid-state structures and packing motifs of these compounds has been analyzed. Pentaarylfullerenes have a characteristic "badminton shuttlecock" shape that causes several derivatives to crystallize into columnar stacks. However, many pentaarylfullerenes form non-stacked structures with, for example, dimeric, layered, diamondoid, or feather-in-cavity relationships between molecules. Computational modeling gave a qualitative estimate of the best shape match between the ball and socket surfaces of each pentaarylfullerene. The best match was for pentaarylfullerenes with large, spherically shaped para-substituents on the aryl groups. The series of pentaarylfullerenes was characterized by single-crystal X-ray diffraction. A total of 34 crystal structures were obtained as various solvates and were categorized by their packing motifs.

Bond-Breaking Reactions Encounter Distinct Solvent Environments Causing Breakdown of Linear Response.

Solvent effects are important for understanding solution-phase chemical reactions. Surprisingly, very few studies have explored how solvent dynamics change during the course of a reaction with solutes that encounter a wide range of configurations. Here, we use quantum simulation methods to explore the solvent dynamics during a solution-phase bond-breaking reaction: the photodissociation of Na2+ in liquid Ar. We find that the solute experiences a small number of distinct solvent environments that change in a discrete fashion as the bond lengthens. In characterizing the solvent environments, we show also that linear response fails by all measures, even when nonstationarity of solvent dynamics is considered. This observation of distinct solvent response environments with a solvent that can undergo only translational motions highlights the complexity of solute-solvent interactions, but that there are only a few environments gives hope to the idea that solvation dynamics can be understood for solution-phase reactions that explore a wide configuration space.