Experimentally Delineating the Catalytic Effect of a Single Water Molecule in the Photochemical Rearrangement of the Phenylperoxy Radical to the Oxepin-2(5H)-one-5-yl Radical.

Catalysis plays a pivotal role in both chemistry and biology, primarily attributed to its ability to stabilize transition states and lower activation free energies, thereby accelerating reaction rates. While computational studies have contributed valuable mechanistic insights, there remains a scarcity of experimental investigations into transition states. In this work, we embark on an experimental exploration of the catalytic energy lowering associated with transition states in the photorearrangement of the phenylperoxy radical-water complex to the oxepin-2(5H)-one-5-yl radical. Employing matrix isolation spectroscopy, density functional theory, and post-HF computations, we scrutinize the (photo)catalytic impact of a single water molecule on the rearrangement. Our computations indicate that the barrier heights for the water-assisted unimolecular isomerization steps are approximately 2-3 kcal mol-1 lower compared to the uncatalyzed steps. This decrease directly coincides with the energy difference in the required wavelength during the transformation (Δλ = λ546 nm - λ579 nm ≡ 52.4-49.4 = 3.0 kcal mol-1), allowing us to elucidate the differential transition state energy in the photochemical rearrangement of the phenylperoxy radical catalyzed by a single water molecule. Our work highlights the important role of water catalysis and has, among others, implications for understanding the mechanism of organic reactions under atmospheric conditions.

Silicon Radical-Induced CH4 Dissociation for Uniform Graphene Coating on Silica Surface.

Due to the manufacturability of highly well-defined structures and wide-range versatility in its microstructure, SiO2 is an attractive template for synthesizing graphene frameworks with the desired pore structure. However, its intrinsic inertness constrains the graphene formation via methane chemical vapor deposition. This work overcomes this challenge by successfully achieving uniform graphene coating on a trimethylsilyl-modified SiO2 (denote TMS-MPS). Remarkably, the onset temperature for graphene growth dropped to 720 °C for the TMS-MPS, as compared to the 885 °C of the pristine SiO2. This is found to be mainly from the Si radicals formed from the decomposition of the surface TMS groups. Both experimental and computational results suggest a strong catalytic effect of the Si radicals on the CH4 dissociation. The surface engineering of SiO2 templates facilitates the synthesis of high-quality graphene sheets. As a result, the graphene-coated SiO2 composite exhibits a high electrical conductivity of 0.25 S cm-1. Moreover, the removal of the TMP-MPS template has released a graphene framework that replicates the parental TMS-MPS template on both micro- and nano- scales. This study provides tremendous insights into graphene growth chemistries as well as establishes a promising methodology for synthesizing graphene-based materials with pre-designed microstructures and porosity.

Performance of point charge embedding schemes for excited states in molecular organic crystals.

Modeling excited state processes in molecular crystals is relevant for several applications. A popular approach for studying excited state molecular crystals is to use cluster models embedded in point charges. In this paper, we compare the performance of several embedding models in predicting excited states and S1-S0 optical gaps for a set of crystals from the X23 molecular crystal database. The performance of atomic charges based on ground or excited states was examined for cluster models, Ewald embedding, and self-consistent approaches. We investigated the impact of various factors, such as the level of theory, basis sets, embedding models, and the level of localization of the excitation. We consider different levels of theory, including time-dependent density functional theory and Tamm-Dancoff approximation (TDA) (DFT functionals: ωB97X-D and PBE0), CC2, complete active space self-consistent field, and CASPT2. We also explore the impact of selection of the QM region, charge leakage, and level of theory for the description of different kinds of excited states. We implemented three schemes based on distance thresholds to overcome overpolarization and charge leakage in molecular crystals. Our findings are compared against experimental data, G0W0-BSE, periodic TDA, and optimally tuned screened range-separated functionals.

Advanced Catalyst Design and Reactor Configuration Upgrade in Electrochemical Carbon Dioxide Conversion.

Electrochemical carbon dioxide reduction reaction (CO2 RR) driven by renewable energy shows great promise in mitigating and potentially reversing the devastating effects of anthropogenic climate change and environmental degradation. The simultaneous synthesis of energy-dense chemicals can meet global energy demand while decoupling emissions from economic growth. However, the development of CO2 RR technology faces challenges in catalyst discovery and device optimization that hinder their industrial implementation. In this contribution, a comprehensive overview of the current state of CO2 RR research is provided, starting with the background and motivation for this technology, followed by the fundamentals and evaluated metrics. Then the underlying design principles of electrocatalysts are discussed, emphasizing their structure-performance correlations and advanced electrochemical assembly cells that can increase CO2 RR selectivity and throughput. Finally, the review looks to the future and identifies opportunities for innovation in mechanism discovery, material screening strategies, and device assemblies to move toward a carbon-neutral society.

Multiconfigurational Calculations and Photodynamics Describe Norbornadiene Photochemistry.

Storing solar energy is a vital component of using renewable energy sources to meet the growing demands of the global energy economy. Molecular solar thermal (MOST) energy storage is a promising means to store solar energy with on-demand energy release. The light-induced isomerization reaction of norbornadiene (NBD) to quadricyclane (QC) is of great interest because of the generally high energy storage density (0.97 MJ kg-1) and long thermal reversion lifetime (t1/2,300K = 8346 years). However, the mechanistic details of the ultrafast excited-state [2 + 2]-cycloaddition are largely unknown due to the limitations of experimental techniques in resolving accurate excited-state molecular structures. We now present a full computational study on the excited-state deactivation mechanism of NBD and its dimethyl dicyano derivative (DMDCNBD) in the gas phase. Our multiconfigurational calculations and nonadiabatic molecular dynamics simulations have enumerated the possible pathways with 557 S2 trajectories of NBD for 500 fs and 492 S1 trajectories of DMDCNBD for 800 fs. The simulations predicted the S2 and S1 lifetimes of NBD (62 and 221 fs, respectively) and the S1 lifetime of DMDCNBD (190 fs). The predicted quantum yields of QC and DCQC are 10 and 43%, respectively. Our simulations also show the mechanisms of forming other possible reaction products and their quantum yields.

Modeling Excited States of Molecular Organic Aggregates for Optoelectronics.

Light-driven phenomena in organic molecular aggregates underpin several mechanisms relevant to optoelectronic applications. Modeling these processes is essential for aiding the design of new materials and optimizing optoelectronic devices. In this review, we cover the use of different atomistic models, excited-state dynamics, and transport approaches for understanding light-activated phenomena in molecular aggregates, including radiative and nonradiative decay pathways. We consider both intra- and intermolecular mechanisms and focus on the role of conical intersections as facilitators of internal conversion. We explore the use of the exciton models for Frenkel and charge transfer states and the electronic structure methods and algorithms commonly applied for excited-state dynamics. Throughout the review, we analyze the approximations employed for the simulation of internal conversion, intersystem crossing, and reverse intersystem crossing rates and analyze the molecular processes behind single fission, triplet-triplet annihilation, Dexter energy transfer, and Förster energy transfer.

Single-Atom Iridium on Hematite Photoanodes for Solar Water Splitting: Catalyst or Spectator?

Single-atom catalysts (SACs) on hematite photoanodes are efficient cocatalysts to boost photoelectrochemical performance. They feature high atom utilization, remarkable activity, and distinct active sites. However, the specific role of SACs on hematite photoanodes is not fully understood yet: Do SACs behave as a catalytic site or as a spectator? By combining spectroscopic experiments and computer simulations, we demonstrate that single-atom iridium (sIr) catalysts on hematite (α-Fe2O3/sIr) photoanodes act as a true catalyst by trapping holes from hematite and providing active sites for the water oxidation reaction. In situ transient absorption spectroscopy showed a reduced number of holes and shortened hole lifetime in the presence of sIr. This was particularly evident on the second timescale, indicative of fast hole transfer and depletion toward water oxidation. Intensity-modulated photocurrent spectroscopy evidenced a faster hole transfer at the α-Fe2O3/sIr/electrolyte interface compared to that at bare α-Fe2O3. Density functional theory calculations revealed the mechanism for water oxidation using sIr as a catalytic center to be the preferred pathway as it displayed a lower onset potential than the Fe sites. X-ray photoelectron spectroscopy demonstrated that sIr introduced a mid-gap of 4d state, key to the fast hole transfer and hole depletion. These combined results provide new insights into the processes controlling solar water oxidation and the role of SACs in enhancing the catalytic performance of semiconductors in photo-assisted reactions.

Photochemical Fingerprinting Is a Sensitive Probe for the Detection of Synthetic Cannabinoid Receptor Agonists; toward Robust Point-of-Care Detection.

With synthetic cannabinoid receptor agonist (SCRA) use still prevalent across Europe and structurally advanced generations emerging, it is imperative that drug detection methods advance in parallel. SCRAs are a chemically diverse and evolving group, which makes rapid detection challenging. We have previously shown that fluorescence spectral fingerprinting (FSF) has the potential to provide rapid assessment of SCRA presence directly from street material with minimal processing and in saliva. Enhancing the sensitivity and discriminatory ability of this approach has high potential to accelerate the delivery of a point-of-care technology that can be used confidently by a range of stakeholders, from medical to prison staff. We demonstrate that a range of structurally distinct SCRAs are photochemically active and give rise to distinct FSFs after irradiation. To explore this in detail, we have synthesized a model series of compounds which mimic specific structural features of AM-694. Our data show that FSFs are sensitive to chemically conservative changes, with evidence that this relates to shifts in the electronic structure and cross-conjugation. Crucially, we find that the photochemical degradation rate is sensitive to individual structures and gives rise to a specific major product, the mechanism and identification of which we elucidate through density-functional theory (DFT) and time-dependent DFT. We test the potential of our hybrid "photochemical fingerprinting" approach to discriminate SCRAs by demonstrating SCRA detection from a simulated smoking apparatus in saliva. Our study shows the potential of tracking photochemical reactivity via FSFs for enhanced discrimination of SCRAs, with successful integration into a portable device.

Competition between ultralong organic phosphorescence and thermally activated delayed fluorescence in dichloro derivatives of 9-benzoylcarbazole.

Optoelectronic materials based on metal-free organic molecules represent a promising alternative to traditional inorganic devices. Significant attention has been devoted to the development of the third generation of OLEDs which are based on the temperature-activated delayed fluorescence (TADF) mechanism. In the last few years, several materials displaying ultra-long organic phosphorescence (UOP) have been designed using strategies such as crystal engineering and halogen functionalisation. Both TADF and UOP are controlled by the population of triplet states and the energy gaps between the singlet and triplet manifolds. In this paper, we explore the competition between TADF and UOP in the molecular crystals of three dichloro derivatives of 9H-carbazol-3-yl(phenyl)methanone. We investigate the excited state mechanisms in solution and the crystalline phase and address the effects of exciton transport and temperature on the rates of direct and reverse intersystem crossing under the Marcus-Levich-Jortner model. We also analyse how the presence of isomeric impurities and the stabilisation of charge transfer states affect these processes. Our simulations explain the different mechanisms observed for the three derivatives and highlight the role of intramolecular rotation and crystal packing in determining the energy gaps. This work contributes to a better understanding of the connection between chemical and crystalline structures that will enable the design of efficient materials.

Newton-X Platform: New Software Developments for Surface Hopping and Nuclear Ensembles.

Newton-X is an open-source computational platform to perform nonadiabatic molecular dynamics based on surface hopping and spectrum simulations using the nuclear ensemble approach. Both are among the most common methodologies in computational chemistry for photophysical and photochemical investigations. This paper describes the main features of these methods and how they are implemented in Newton-X. It emphasizes the newest developments, including zero-point-energy leakage correction, dynamics on complex-valued potential energy surfaces, dynamics induced by incoherent light, dynamics based on machine-learning potentials, exciton dynamics of multiple chromophores, and supervised and unsupervised machine learning techniques. Newton-X is interfaced with several third-party quantum-chemistry programs, spanning a broad spectrum of electronic structure methods.

The carbon chain growth during the onset of CVD graphene formation on γ-Al2O3 is promoted by unsaturated CH2 ends.

Chemical vapor deposition of methane onto a template of alumina (Al2O3) nanoparticles is a prominent synthetic strategy of graphene meso-sponge, a new class of nano porous carbon materials consisting of single-layer graphene walls. However, the elementary steps controlling the early stages of graphene growth on Al2O3 surfaces are still not well understood. In this study, density functional theory calculations provide insights into the initial stages of graphene growth. We have modelled the mechanism of CH4 dissociation on the (111), (110), (100), and (001) γ-Al2O3 surfaces. Subsequently, we have considered the reaction pathway leading to the formation of a C6 ring. The γ-Al2O3(110) and γ-Al2O3(100) are both active for CH4 dissociation, but the (100) surface has higher catalytic activity towards the carbon growth reaction. The overall mechanism involves the formation of the reactive intermediate CH2* that then can couple to form CnH2n* (n = 2-6) intermediates with unsaturated CH2 ends. The formation of these species, which are not bound to the surface-active sites, promotes the sustained carbon growth in a nearly barrierless process. Also, the short distance between terminal carbon atoms leads to strong interactions, which might lead to the high activity between unsaturated CH2* of the hydrocarbon chain. Analysis of the electron localization and geometries of the carbon chains reveals the formation of C-Al-σ bonds with the chain growing towards the vacuum rather than C-Al-π bonds covering the γ-Al2O3(100) surface. This growth behaviour prevents catalyst poisoning during the initial stage of graphene nucleation.

Porous nanographene formation on γ-alumina nanoparticles via transition-metal-free methane activation.

γ-Al2O3 nanoparticles promote pyrolytic carbon deposition of CH4 at temperatures higher than 800 °C to give single-walled nanoporous graphene (NPG) materials without the need for transition metals as reaction centers. To accelerate the development of efficient reactions for NPG synthesis, we have investigated early-stage CH4 activation for NPG formation on γ-Al2O3 nanoparticles via reaction kinetics and surface analysis. The formation of NPG was promoted at oxygen vacancies on (100) surfaces of γ-Al2O3 nanoparticles following surface activation by CH4. The kinetic analysis was well corroborated by a computational study using density functional theory. Surface defects generated as a result of surface activation by CH4 make it kinetically feasible to obtain single-layered NPG, demonstrating the importance of precise control of oxygen vacancies for carbon growth.

Emission Quenching in Tetraphenylfuran Crystal: Why This Propeller-Shaped Molecule Does Not Emit in the Condensed Phase.

Due to their substantial fluorescence quantum yields in the crystalline phase, propeller-shaped molecules have recently gained significant attention as potential emissive materials for optoelectronic applications. For the family of cyclopentadiene derivatives, light-emission is highly dependent on the nature of heteroatomic substitutions. In this paper, we investigate excited state relaxation pathways in the tetraphenyl-furan molecule (TPF), which in contrast with other molecules in the family, shows emission quenching in the solid-state. For the singlet manifold, our calculations show nonradiative pathways associated with C-O elongation are blocked in both vacuum and the solid state. A fraction of the population can be transferred to the triplet manifold and, subsequently, to the ground state in both phases. This process is expected to be relatively slow due to the small spin-orbit couplings between the relevant singlet-triplet states. Emission quenching in crystalline TPF seems to be in line with more efficient exciton hopping rates. Our simulations help clarify the role of conical intersections, population of the triplet states and crystalline structure in the emissive response of propeller-shaped molecules.

Understanding the solid state luminescence and piezochromic properties in polymorphs of an anthracene derivative.

Luminescent molecular crystals have gained significant research interest for optoelectronic applications. However, fully understanding their structural and electronic relationships in the condensed phase and under external stimuli remains a significant challenge. Here, piezochromism in the molecular crystal 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene (BP4VA) is studied using a combination of density functional theory (DFT) and time-dependent TD-DFT. We investigate the effects that molecular packing and geometry have on the electronic and phonon structure and the excited state properties in this archetypal system. We find that the luminescence properties are red-shifted with the transition from a herringbone to a sheet packing arrangement. An almost continuous red-shift in the band gap is found with the application of an external pressure through the enhancement of π-π and CH-π interactions, and is a mechanism in fine tuning an emissive response. The analysis of the phonon structure of the molecular crystal suggests restriction of motion in the herringbone packing arrangement, with motion restricted at higher pressure. This is supported by the Huang-Rhys factors which show a decrease in the reorganisation energy with the application of pressure. Ultimately, a balance between the decrease in reorganisation energies and the increase in exciton coupling will determine whether nonradiative decay is enhanced or decreased with the increase in pressure in these systems.

Rotaxane CoII Complexes as Field-Induced Single-Ion Magnets.

Mechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of CoII -based single-ion magnets. Using multi-frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for five-coordinate CoII complexes to date. The predictable coordination behaviour of the interlocked ligands allowed the magnetic properties of their CoII complexes to be evaluated computationally a priori and our combined experimental and theoretical approach enabled us to rationalize the observed trends. The predictable magnetic behaviour of the rotaxane CoII complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.

Role of Conical Intersections on the Efficiency of Fluorescent Organic Molecular Crystals.

Organic molecular crystals are attractive materials for luminescent applications because of their promised tunability. However, the link between the chemical structure and emissive behavior is poorly understood because of the numerous interconnected factors which are at play in determining radiative and nonradiative behaviors at the solid-state level. In particular, the decay through conical intersection dominates the nonadiabatic regions of the potential energy surface, and thus, their accessibility is a telling indicator of the luminosity of the material. In this study, we investigate the radiative mechanism for five organic molecular crystals which display a solid-state emission, with a focus on the role of conical intersections in their photomechanisms. The objective is to situate the importance of the accessibility of conical intersections with regards to emissive behavior, taking into account other nonradiative decay channels, namely, vibrational decay, and exciton hopping. We begin by giving a brief overview of the structural patterns of the five systems within a larger pool of 13 crystals for a richer comparison. We observe that because of the prevalence of sheet like and herringbone packing in organic molecular crystals, the conformational diversity of crystal dimers is limited. Additionally, similarly spaced dimers have exciton coupling values of a similar order within a 50 meV interval. Next, we focus on three exemplary cases, where we disentangle the role of nonradiative decay mechanisms and show how rotational minimum energy conical intersections in vacuum lead to puckered ones in the crystal, increasing their instability upon crystallization in typical packing motifs. In contrast, molecules with puckered conical intersections in vacuum tend to conserve this trait upon crystallization, and therefore, their quantum yield of fluorescence is determined predominantly by other nonradiative decay mechanisms.

fromage: A library for the study of molecular crystal excited states at the aggregate scale.

The study of photoexcitations in molecular aggregates faces the twofold problem of the increased computational cost associated with excited states and the complexity of the interactions among the constituent monomers. A mechanistic investigation of these processes requires the analysis of the intermolecular interactions, the effect of the environment, and 3D arrangements or crystal packing on the excited states. A considerable number of techniques have been tailored to navigate these obstacles; however, they are usually restricted to in-house codes and thus require a disproportionate effort to adopt by researchers approaching the field. Herein, we present the FRamewOrk for Molecular AGgregate Excitations (fromage), which implements a collection of such techniques in a Python library complemented with ready-to-use scripts. The program structure is presented and the principal features available to the user are described: geometrical analysis, exciton characterization, and a variety of ONIOM schemes. Each is illustrated by examples of diverse organic molecules in condensed phase settings. The program is available at https://github.com/Crespo-Otero-group/fromage.

Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores.

Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

An alternative modular 'click-SNAr-click' approach to develop subcellular localised fluorescent probes to image mobile Zn2+ .

Zn2+ is involved in a number of biological processes and its wide-ranging roles at the subcellular level, especially in specific organelles, have not yet been fully established due to a lack of tools to image it effectively. We report a new and efficient modular double 'click' approach towards a range of sub-cellular localised probes for mobile zinc. Through this methodology, endoplasmic reticulum, mitochondria and lysosome localised probes were successfully prepared which show good fluorescence responses to mobile Zn2+in vitro and in cellulo whilst a non-targeting probe was synthesized as a control. The methodology appears to have wide-utility for the generation of sub-cellular localised probes by incorporating specific organelle targeting vectors for mobile Zn2+ imaging.

Ultrafast Photoinduced Dynamics of 1,3-Cyclohexadiene Using XMS-CASPT2 Surface Hopping.

A full-dimensional simulation of the photodissociation of 1,3-cyclohexadiene in the manifold of three electronic states was performed via nonadiabatic surface hopping dynamics using extended multistate complete active space second-order perturbation (XMS-CASPT2) electronic structure theory with fully analytic nonadiabatic couplings. With the 47 ± 8% product quantum yield calculated from the 136 trajectories, generally 400 fs-long, and an estimated excited lifetime of 89 ± 9 fs, our calculations provide a detailed description of the nonadiabatic deactivation mechanism, showing the existence of an extended conical intersection seam along the reaction coordinate. The nature of the preferred reaction pathways on the ground state is discussed and extensive comparison to the previously published full dimensional dynamics calculations is provided.