Squeezed Protons and Infrared Plasmonic Resonance Energy Transfer.

Unusual nuclear quantum effects may emerge near noble metal nanostructures such as squeezed vibrational states in molecular junctions and plasmonic resonance energy transfer in the infrared domain. Herein, nuclear quantum effects near heavy metals are studied by nuclear-electronic orbital density functional theory (NEO-DFT) with an effective core potential. For a quantum proton sandwiched between a pair of gold tips modeled by two Au6 clusters, NEO-DFT calculations suggest that the quantum proton density can be squeezed as the tip distance decreases. For an HF molecule placed near a one-dimensional Au nanowire composed of up to 34 Au atoms, real-time NEO time-dependent density functional theory (RT-NEO-TDDFT) shows that the infrared plasmonic motion within the Au nanowire may resonantly transfer electronic energy to the HF proton vibrational stretch mode. Overall, these calculations illustrate the advantages of the NEO approach for probing nuclear quantum effects, such as squeezed proton vibrational states and infrared plasmonic resonance energy transfer.

Robustness of Threshold Collision-Induced Dissociation Simulations for Bond Dissociation Energies.

The threshold collision-induced dissociation (T-CID) method is the workhorse for gas-phase bond dissociation energy (BDE) measurements. However, T-CID does not measure BDEs directly; instead, BDEs are obtained by fitting simulated data to the experimental data. We previously observed several large discrepancies between the computed and experimental BDEs. To analyze the reliability of the experimental values, we previously reported a study of the dissociation rate models in the simulation. Here, we report a study of the collision simulation part, specifically in the L-CID (ligand CID) program. We show that the BDE values are robust even to intentionally introduced mistakes in the simulations, varying in most cases by less than 3 kcal mol-1. The most significant exception is the collisional energy transfer (CET) simulation, which led to deviations larger than 10 kcal mol-1. However, we found that the BDEs obtained with explicitly simulated CET distributions deviated by only 3 kcal mol-1 from those simulated with the original model. Collectively, our results suggest that the T-CID-derived BDE values are robust and are likely to be accurate.

The COMPAS Project: A Computational Database of Polycyclic Aromatic Systems. Phase 1: cata-Condensed Polybenzenoid Hydrocarbons.

Chemical databases are an essential tool for data-driven investigation of structure-property relationships and for the design of novel functional compounds. We introduce the first phase of the COMPAS Project─a COMputational database of Polycyclic Aromatic Systems. In this phase, we developed two data sets containing the optimized ground-state structures and a selection of molecular properties of ∼34k and ∼9k cata-condensed polybenzenoid hydrocarbons (at the GFN2-xTB and B3LYP-D3BJ/def2-SVP levels, respectively) and placed them in the public domain. Herein, we describe the process of the data set generation, detail the information available within the data sets, and show the fundamental features of the generated data. We analyze the correlation between the two types of computations as well as the structure-property relationships of the calculated species. The data and insights gained from them can inform rational design of novel functional aromatic molecules for use in, e.g., organic electronics, and can provide a basis for additional data-driven machine- and deep-learning studies in chemistry.

Simple and efficient visualization of aromaticity: bond currents calculated from NICS values.

Aromaticity is a fundamental concept in chemistry, underpinning the properties and reactivity of many organic compounds and materials. The ability to easily and accurately discern aromatic behavior is key to leveraging it as a design element, yet most aromaticity metrics struggle to combine accurate quantitative evaluation, intuitive interpretability, and user-friendliness. We introduce a new method, NICS2BC, which uses simple and inexpensive NICS calculations to generate information-rich and easily-interpreted bond-current graphs. We test the quantitative and qualitative characterizations afforded by NICS2BC for a selection of molecules of varying structural and electronic complexity, to demonstrate its accuracy and ease of analysis. Moreover, we show that NICS2BC successfully identifies ring-current patterns in molecules known to be difficult cases to interpret with NICS and enables deeper understanding of local aromaticity trends, demonstrating that our method adds additional insight.

Extensive Redox Non-Innocence in Iron Bipyridine-Diimine Complexes: a Combined Spectroscopic and Computational Study.

Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]3+ to the monoanion [Fe(BDI]-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., 57Fe Mössbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.

Modeling Gas-Phase Unimolecular Dissociation for Bond Dissociation Energies: Comparison of Statistical Rate Models within RRKM Theory.

The Rice-Ramsperger-Kassel-Marcus (RRKM) theory provides a simple yet powerful rate theory for calculating microcanonical rate constants. In particular, it has found widespread use in combination with gas-phase kinetic experiments of unimolecular dissociations to extract experimental bond dissociation energies (BDEs). We have previously found several discrepancies between the computed BDE values and the respective experimental ones, obtained with our empirical rate model, named L-CID. To investigate the reliability of our rate model, we conducted a theoretical analysis and comparison of the performance of conventional rate models and L-CID within the RRKM framework. Using the previously published microcanonical rate data as well as reaction cross-section data, we show that the BDE values obtained with the L-CID model agree with the ones from the other rate models within the expected uncertainty bounds. Based on this agreement, we discuss the possible rationalization of the good performance of the L-CID model.

Predicting bond-currents in polybenzenoid hydrocarbons with an additivity scheme.

We report on the construction and application of a new bond-current additivity scheme for polybenzenoid hydrocarbons. The method is based on identification of the smaller substructures contained in the system, up to tricyclic subunits. Thus, it enables the prediction of any cata-condensed unbranched polybenzenoid hydrocarbon, using a library consisting of only four building blocks. The predicted bond-currents can then be used to generate Nucleus Independent Chemical Shift (NICS) values, the results of which validate previous observations of additivity with NICS-XY-Scans. The limitations of the method are probed, leading to clearly delineated and apparently constant error boundaries, which are independent of the molecular size. It is shown that there is a relationship between the accuracy of the predictions and the molecular structure and specific motifs that are especially challenging are identified. The results of the additivity method, combined with the transparent description of its strengths and weaknesses, ensure that this method can be used with well-defined reliability for characterization of polybenzenoid hydrocarbons. The resource-efficient and rapid nature of the method makes it a promising tool for screening and molecular design.

Peptide-Metal Frameworks with Metal Strings Guided by Dispersion Interactions.

Despite impressive advances in the construction of metal-organic frameworks (MOFs), the formation of networks from peptidic ligands is difficult, though they are sought after for their modularity and biocompatibility. Herein we present a peptide-metal framework that consists of helical oligoproline ligands and Zn/K (or Zn/Rb). The crystalline network contains pleated nanosheets with the metal ions aligned in strings. This unprecedented architecture derives from under-appreciated London dispersion interactions between the oligoproline ligands that play in concert with the metal coordination to create the network. Hence, the secondary structure of the peptidic ligand represents an additional control element for the creation of new MOF architectures. We anticipate that our results will instruct the design of further peptidic MOFs and enable the generation of versatile biocompatible materials.

Prediction of Spin Density, Baird-Antiaromaticity, and Singlet-Triplet Energy Gap in Triplet-State Polybenzenoid Systems from Simple Structural Motifs.

Triplet-state aromaticity has been recently proposed as a strategy for designing functional organic electronic compounds, many of which are polycyclic aromatic systems. However, in many cases, the aromatic nature of the triplet state cannot be easily predicted. Moreover, it is often unclear how specific structural manipulations affect the electronic properties of the excited-state compounds. Herein, the relationship between the structure of polybenzenoid hydrocarbons (PBHs) and their spin-density distribution and aromatic character in the first triplet excited state is studied. Although a direct link is not immediately visible, classifying the PBHs according to their annulation sequence reveals regularities. Based on these, a set of guidelines is defined to qualitatively predict the location of spin and paratropicity and the singlet-triplet energy gap in larger PBHs, using only their smaller tri- and tetracyclic components, and subsequently tested on larger systems.

Perturbation of Pyridinium CIVP Spectra by N2 and H2 Tags: An Experimental and BOMD Study.

In cryogenic ion vibrational predissociation (CIVP) spectroscopy, the influence of the tag on the spectrum is an important consideration. Whereas for small ions several studies have shown that the tag effects can be significant, these effects are less understood for large ions or for large numbers of tags. Nevertheless, it is commonly assumed that if the investigated molecular ion is large enough, the perturbations arising from the tag are small and can therefore be neglected in the interpretation. In addition, it is generally assumed that the more weakly bound the tag is, the less it perturbs the CIVP spectrum. Under these assumptions, CIVP spectra are claimed to be effectively IR absorption spectra of the free molecular ion. Having observed unexpected splittings in otherwise unproblematic CIVP spectra of some tagged ions, we report Born-Oppenheimer molecular dynamics (BOMD) simulations that strongly indicate that mobility among the more weakly bound tags leads to the surprising splittings. We compared the behavior of two tags commonly used in CIVP spectroscopy (H2 and N2) with a large pyridinium cation. Our experimental results surprisingly show that under the appropriate circumstances, the more weakly bound tag can perturb the CIVP spectra more than the more strongly bound tag by not just shifting but also splitting the observed bands. The more weakly bound tag had significant residence times at several spectroscopically distinct sites on the molecular ion. This indicates that the weakly bound tag is likely to sample several binding sites in the experiment, some of which involve interaction with the reporter chromophore.

Synthesis, Spectroscopic, and Structural Characterization of Organyl Disulfanides and a Tetrasulfanide.

Various room-temperature-stable monoorganylpolysulfanides of the form [X][RSn] (X = [PPh4]+, [PNP]+, [NEt4]+; R = Ph, t-Bu, n ≥ 2) were synthesized in a simple and versatile one-step process starting from sodium thiolates and elemental sulfur. The compounds were characterized by X-ray crystal structure analysis, NMR spectroscopy, microelemental analysis, and electrospray mass ionization spectrometry including collision-induced dissociation experiments. While these salts are well-defined species as crystals, they undergo complex equilibria in solution. In one case, compounds ranging from n = 1-8 have been observed in solution. Structural features, dynamics in solution, as well as thermochromic properties of one of the compounds, [PPh4][PhS2], are investigated in detail by temperature- and pressure-dependent X-ray crystal structure analysis. The experimental data are complemented by periodic boundary density functional theory calculations on the crystal structures, as well as energy decomposition analyses.

A unified view to Brønsted acidity scales: do we need solvated protons?

The most comprehensive solvent acidity scale spanning 28 orders of magnitude of acidity was measured in the low-polarity solvent 1,2-dichloroethane (DCE). Its experimental core is linked to the unified acidity scale (pHabs) in an unprecedented and generalized approach only based on experimental values. This enables future measurements of acid strengths and acidity adjustments in low polarity solvents. The scale was cross-validated computationally. The purely experimental and computational data agree very well. The DCE scale includes 87 buffer systems with values between -13.0 and +15.4, i.e. similar to water at hypothetical and extreme pH values of -13.0 to +15.4. Unusually, such high acidities in DCE are not realized via solvated protons, but rather through strongly acidic molecules able to directly donate their proton, even to weak bases dissolved in the solution. Thus, in all examined cases, not a single solvated proton is present in one liter of DCE.