A multi-descriptor analysis of substituent effects on the structure and aromaticity of benzene derivatives: π-Conjugation versus charge effects.

This work provides a detailed multi-component analysis of aromaticity in monosubstituted (X = CH3, C H 2 - , C H 2 + , NH2, NH-, NH+, OH, O-, and O+) and para-homodisubstituted (X = CH3, CH2, NH2, NH, OH, and O) benzene derivatives. We investigate the effects of substituents using single-reference (B3LYP/DFT) and multireference (CASSCF/MRCI) methods, focusing on structural (HOMA), vibrational (AI(vib)), topological (ELFπ), electronic (MCI), magnetic (NICS), and stability (S0-T1 splitting) properties. The findings reveal that appropriate π-electron-donating and π-electron-accepting substituents with suitable size and symmetry can interact with the π-system of the ring, significantly influencing π-electron delocalization. While the charge factor has a minimal impact on π-electron delocalization, the presence of a pz orbital capable of interacting with the π-electron delocalization is the primary factor leading to a deviation from the typical aromaticity characteristics observed in benzene.

Prediction Challenge: Simulating Rydberg photoexcited cyclobutanone with surface hopping dynamics based on different electronic structure methods.

This research examines the nonadiabatic dynamics of cyclobutanone after excitation into the n → 3s Rydberg S2 state. It stems from our contribution to the Special Topic of the Journal of Chemical Physics to test the predictive capability of computational chemistry against unseen experimental data. Decoherence-corrected fewest-switches surface hopping was used to simulate nonadiabatic dynamics with full and approximated nonadiabatic couplings. Several simulation sets were computed with different electronic structure methods, including a multiconfigurational wavefunction [multiconfigurational self-consistent field (MCSCF)] specially built to describe dissociative channels, multireference semiempirical approach, time-dependent density functional theory, algebraic diagrammatic construction, and coupled cluster. MCSCF dynamics predicts a slow deactivation of the S2 state (10 ps), followed by an ultrafast population transfer from S1 to S0 (<100 fs). CO elimination (C3 channel) dominates over C2H4 formation (C2 channel). These findings radically differ from the other methods, which predicted S2 lifetimes 10-250 times shorter and C2 channel predominance. These results suggest that routine electronic structure methods may hold low predictive power for the outcome of nonadiabatic dynamics.

Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony-Carbon Protonolysis.

The selective formation of antimony-carbon bonds via organic superbase catalysis under metal- and salt-free conditions is reported. This novel approach utilizes electron-deficient stibine, Sb(C6F5)3, to give upon base-catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron-deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base-catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R=C6H5, C6H4-NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base-catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first-order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ-bond metathesis transition state, where the base catalyst activates the Sb-C6F5 bond sequence through secondary bond interactions.

A comprehensive analysis of charge transfer effects on donor-pyrene (bridge)-acceptor systems using different substituents.

The alternant polycyclic aromatic hydrocarbon pyrene has photophysical properties that can be tuned with different donor and acceptor substituents. Recently, a D (donor)-Pyrene (bridge)-A (acceptor) system, DPA, with the electron donor N,N-dimethylaniline (DMA), and the electron acceptor trifluoromethylphenyl (TFM), was investigated by means of time-resolved spectroscopic measurements (J. Phys. Chem. Lett. 2021, 12, 2226-2231). DPA shows great promise for potential applications in organic electronic devices. In this work, we used the ab initio second-order algebraic diagrammatic construction method ADC(2) to investigate the excited-state properties of a series of analogous DPA systems, including the originally synthesized DPAs. The additionally investigated substituents were amino, fluorine, and methoxy as donors and nitrile and nitro groups as acceptors. The focus of this work was on characterizing the lowest excited singlet states regarding charge transfer (CT) and local excitation (LE) characters. For the DMA-pyrene-TFM system, the ADC(2) calculations show two initial electronic states relevant for interpreting the photodynamics. The bright S1 state is locally excited within the pyrene moiety, and an S2 state is localized ~0.5 eV above S1 and characterized as a donor to pyrene CT state. HOMO and LUMO energies were employed to assess the efficiency of the DPA compounds for organic photovoltaics (OPVs). HOMO-LUMO and optical gaps were used to estimate power conversion and light-harvesting efficiencies for practical applications in organic solar cells. Considering the systems using smaller D/A substituents, compounds with the strong acceptor NO2 substituent group show enhanced CT and promising properties for use in OPVs. Some of the other compounds with small substituents are also found to be competitive in this regard.

Structural stability and the low-lying singlet and triplet states of BN-n-acenes, n = 1-7.

The chemical stability and the low-lying singlet and triplet excited states of BN-n-acenes (n = 1-7) were studied using single reference and multireference methodologies. From the calculations, descriptors such as the singlet-triplet splitting, the natural orbital (NO) occupations and aromaticity indexes are used to provide structural and energetic analysis. The boron and nitrogen atoms form an isoelectronic pair of two carbon atoms, which was used for the complete substitution of these units in the acene series. The structural analysis confirms the effects originated from the insertion of a uniform pattern of electronegativity difference within the molecular systems. The covalent bonds tend to be strongly polarized which does not happen in the case of a carbon-only framework. This effect leads to a charge transfer between neighbor atoms resulting in a more strengthened structure, keeping the aromaticity roughly constant along the chain. The singlet-triplet splitting also agrees with this stability trend, maintaining a consistent gap value for all molecules. The BN-n-acenes molecules possess a ground state with monoconfigurational character indicating their electronic stability. The low-lying singlet excited states have charge transfer character, which proceeds from nitrogen to boron.

Polyradical character assessment using multireference calculations and comparison with density-functional derived fractional occupation number weighted density analysis.

The biradicaloid character of different types of polycyclic aromatic hydrocarbons (PAHs) based on small band gaps is an important descriptor to assess their opto-electronic properties. In this work, the unpaired electron densities and numbers of unpaired electrons (NU values) calculated at the high-level multireference averaged quadratic coupled-cluster (MR-AQCC) method are used to develop a test set to assess the capabilities of different biradical descriptors based on density functional theory. A benchmark collection of 29 different compounds has been selected. The DFT descriptors contain primarily the fractional occupation number weighted electron density (FOD) based on simplified thermally-assisted-occupation density functional theory (TAO-DFT) calculations, but the singlet-triplet energy difference and other descriptors denoted as y0 and nLUNO have been considered as well. After adjustment of the literature-recommended finite temperatures, a very good, detailed agreement between unpaired density and FOD analysis is observed which is also manifested in excellent statistical correlations. The other two descriptors also show good correlations even though the absolute scaling is not satisfactory. A new linear fit of FOD data to the MR-AQCC reference values leads to an improved regression relation for determining the recommended finite temperature value in dependence of the Hartree-Fock exchange. This provides the basis for fast and reliable assessment of the biradical character of many classes of PAHs without the need for performing computationally extended MR calculations.

Extremely Long C-C Bonds Predicted beyond 2.0 Å.

A number of conjugated molecules are designed with extremely long single C-C bonds beyond 2.0 Å. Some of the investigated molecules are based on analogues to the recently discovered molecule by Kubo et al. These bonds are analyzed by a variety of indices in addition to their equilibrium bond length including the Wiberg bond index, bond dissociation energy (BDE), and measures of diradicaloid character. All unrestricted DFT calculations indicate no diradical character supported by high-level multireference calculations. Finally, NFOD was computed through fractional orbital density (FOD) calculations and used to compare relative differences of diradicaloid character across twisted molecules without central C-C bonding and those with extremely elongated C-C bonds using a comparison with the C-C bond breaking in ethane. No example of direct C-C bonds beyond 2.4 Å are seen in the computational modeling; however, extremely stretched C-C bonds in the vicinity of 2.2 Å are predicted to be achievable with a BDE of 15-25 kcal mol-1.

High-Level Multireference Investigations on the Electronic States in Single-Vacancy (SV) Graphene Defects Using a Pyrene-SV Model.

The nonplanar character of graphene with a single carbon vacancy (SV) defect is investigated utilizing a pyrene-SV model system by way of complete-active-space self-consistent field theory (CASSCF) and multireference configuration interaction singles and doubles (MR-CISD) calculations. Planar structures were optimized with both methods, showing the 3B1 state to be the ground state with three energetically close states within an energy range of 1 eV. These planar structures constitute saddle points. However, following the out-of-plane imaginary frequency yields more stable (by 0.22 to 0.53 eV) but nonplanar structures of Cs symmetry. Of these, the 1A' structure is the lowest in energy and is strongly deformed into an L shape. Following a further out-of-plane imaginary frequency in the nonplanar structures leads to the most stable but most deformed singlet structure of C1 symmetry. In this structure, a bond is formed between the carbon atom with the dangling bond and a carbon of the cyclopentadienyl ring. This bond stabilizes the structure by more than 3 eV compared to the planar 3B1 structure. Higher excited states were calculated at the MR-CISD level, showing a grouping of four states low in energy and higher states starting around 3 eV.

Quantification of the Ionic Character of Multiconfigurational Wave Functions: The Qat Diagnostic.

The complete active space self-consistent field (CASSCF) method is a cornerstone in modern excited-state quantum chemistry providing the starting point for most common multireference computations. However, CASSCF, when used with a minimal active space, can produce significant errors (>2 eV) even for the excitation energies of simple hydrocarbons if the states of interest possess ionic character. After illustrating this problem in some detail, we present a diagnostic for ionic character, denoted as Q at, that is readily computed from the transition density. A set of 11 molecules is considered to study errors in vertical excitation energies. State-averaged CASSCF obtains a mean absolute error (MAE) of 0.87 eV for the 34 singlet states considered. We highlight a strong correlation between the obtained errors and the Q at diagnostic, illustrating its power to predict problematic cases. Conversely, using multireference configuration interaction with single and double excitations and Pople's size extensivity correction (MR-CISD+P), excellent results are obtained with an MAE of 0.11 eV. Furthermore, correlations with the Q at diagnostic disappear. In summary, we hope that the presented diagnostic will facilitate reliable and user-friendly multireference computations on conjugated organic molecules.

Stability and Reactivity of the Phenalene and Olympicene Isomers.

The phenalene (triangulene) and olympicene molecules belong to the polycyclic aromatic hydrocarbon class, which have attracted substantial technological interest due to their unique electronic properties. Electronic structure calculations serve as a valuable tool in investigating the stability and reactivity of these molecular systems. In the present work, the multireference calculations, namely, the complete active space second-order perturbation theory and multireference averaged quadratic coupled cluster (MR-AQCC), were employed to study the reactivity and stability of phenalene and olympicene isomers, as well as their modified structures where the sp3-carbon at the borders were removed. The harmonic oscillator model of aromaticity (HOMA) and the nucleus-independent chemical shift as geometric and magnetic indexes calculated with density functional theory were utilized to assess the aromaticity of the studied molecules. These indexes were compared with properties such as the excitation energy and natural orbitals occupation. The reactivity analyzed using the HOMA index combined with MR-AQCC revealed the radical character of certain structures as well as the weakening of their aromaticity. Moreover, the results suggest that the removal of sp3-carbon atoms and the addition of hydrogen atoms did not alter the π network and the excitation energies of the phenalene molecules.

On the Cooperative Origin of Solvent-Enhanced Symmetry-Breaking Charge Transfer in a Covalently Bound Tetracene Dimer Leading to Singlet Fission.

Singlet fission in covalently bound acene dimers in solution is driven by the interplay of excitonic and singlet correlated triplet 1(TT) states with intermediate charge-transfer states, a process which depends sensitively on the solvent environment. We use high-level electronic structure methods to explore this singlet fission process in a linked tetracene dimer, with emphasis on the symmetry-breaking mechanism for the charge-transfer (CT) states induced by low-frequency antisymmetric vibrations and polar/polarizable solvents. A combination of the second-order algebraic diagrammatic construction (ADC(2)) and density functional theory/multireference configuration interaction (DFT/MRCI) methods are employed, along with a state-specific conductor-like screening model (COSMO) solvation model in the former case. This work quantifies, for the first time, an earlier mechanistic proposal [Alvertis et al., J. Am. Chem. Soc. 2019, 141, 17558] according to which solvent-induced symmetry breaking leads to a high-energy CT state which interacts with the correlated triplet state, resulting in singlet fission. An approximate assessment of the nonadiabatic interactions between the different electronic states underscores that the CT states are essential in facilitating the transition from the bright excitonic state to the 1(TT) state leading to singlet fission. We show that several types of symmetry-breaking inter- and intra-fragment vibrations play a crucial role in a concerted mechanism with the solvent environment and with the symmetric inter-fragment torsion, which tunes the admixture of excitonic and CT states. This offers a new perspective on how solvent-induced symmetry-breaking CT can be understood and how it cooperates with intramolecular mechanisms in singlet fission.

Pathways to fluorescence via restriction of intramolecular motion in substituted tetraphenylethylenes.

The design of materials with enhanced luminescence properties is a fast-developing field due to the potential applicability of these materials as light-emitting diodes or for bioimaging. A transparent way to enhance the emission properties of interesting molecular candidates is blocking competing and unproductive non-radiative relaxation pathways by the restriction of intramolecular motions. Rationalized functionalization is an important possibility to achieve such restrictions. Using time-dependent density functional theory (TD-DFT) based on the ωB97XD functional and the semiempirical tight-binding method including long-range corrections (TD-LC-DFTB), this work investigates the effect of functionalization of the paradigmatic tetraphenylethylene (TPE) on achieving restricted access to conical intersections (RACI). Photodynamical surface hopping simulations have been performed on a larger set of compounds including TPE and ten functionalized TPE compounds. Functionalization has been achieved by means of electron-withdrawing groups, bulky groups which block the relaxation channels via steric hindrance and groups capable of forming strong hydrogen bonds, which restrict the motion via the formation of hydrogen bond channels. Most of the investigated functionalized TPE candidates show ultrafast deactivation to the ground state due to their still existing structural flexibility, but two examples, one containing -CN and -CF3 groups and a second characterized by a network of hydrogen bonds, have been identified as interesting candidates for creating efficient luminescence properties in solution.

Non-Kasha fluorescence of pyrene emerges from a dynamic equilibrium between excited states.

Pyrene fluorescence after a high-energy electronic excitation exhibits a prominent band shoulder not present after excitation at low energies. The standard assignment of this shoulder as a non-Kasha emission from the second-excited state (S2) has been recently questioned. To elucidate this issue, we simulated the fluorescence of pyrene using two different theoretical approaches based on vertical convolution and nonadiabatic dynamics with nuclear ensembles. To conduct the necessary nonadiabatic dynamics simulations with high-lying electronic states and deal with fluorescence timescales of about 100 ns of this large molecule, we developed new computational protocols. The results from both approaches confirm that the band shoulder is, in fact, due to S2 emission. We show that the non-Kasha behavior is a dynamic-equilibrium effect not caused by a metastable S2 minimum. However, it requires considerable vibrational energy, which can only be achieved in collisionless regimes after transitions into highly excited states. This strict condition explains why the S2 emission was not observed in some experiments.

Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model.

A preexisting chemisorbed defect is well-known to increase the reactivity of graphene which is normally chemically inert. Specifically, the presence of chemisorbed hydrogen atoms forming an sp3-hybridized C-H bond is known to increase the reactivity of neighboring carbon atoms toward additional hydrogenation with wide-ranging applications from materials science to astrochemistry. In this work, static DFT and DFT-based direct dynamics simulations are used to characterize the reactivity of a graphene sheet around an existing C-H bond defect. The spin density landscape shows how to guide subsequent H atom additions, always bonding most strongly to the carbon atom with greatest spin density. Molecular dynamics of an impinging H atom under thermal conditions with defect graphene was used to determine the statistics of probable reactions. The most frequent outcome is inelastic scattering (48%) and then Eley-Rideal (ER) abstraction of the chemisorbed H atom as vibrationally hot H2 (40%), while the least likely, but probably most interesting, result is formation of a novel C-H bond (12%). The C-H bonds always form in the ß sublattice. The carbon atom in the para position shows to be most reactive toward the incoming H atom, followed by the ortho carbon, in agreement with the spin density computed in the static calculations. Globally, the graphene energy surface is repulsive, but the defects create local channels into this energy surface through which reactants can move locally through and react with the activated surface without a barrier.

Molecular Dynamics Simulation of the Excited-State Proton Transfer Mechanism in 3-Hydroxyflavone Using Explicit Hydration Models.

3-Hydroxyflavon (3-HF) represents an interesting paradigmatic compound to study excited-state intramolecular proton transfer (ESIPT) and intermolecular (ESInterPT) processes to explain the experimentally observed dual fluorescence in solvents containing protic contamination (water) as opposed to single fluorescence in highly purified nonpolar solvents. In this work, adiabatic on-the-fly molecular dynamics simulations have been performed for isolated 3-HF in an aqueous solution using a polarizable continuum model and including explicit water molecules to represent adequately hydrogen bonding. For the calculation of the excited state, time-dependent density functional theory and the Becke-3-Lee-Yang-Parr (B3LYP) functional have been used. For the isolated 3-HF, ultrafast ESIPT from the enol group to the neighboring keto group has been observed. The calculated PT time of 48 fs agrees well with the experimental value of 39 fs. Addition of one water molecule quenches this ESIPT process but shows an intermolecular concerted or stepwise tautomerization process via the bridging water molecule. Adding a second or more water molecules inhibits this ESInterPT process to a large degree. Most of the trajectories do not show any PT, preserving the initial excited-state enol structure, which is the origin of the violet-blue fluorescence appearing in the solvents contaminated with protic components.

A General New Method for Calculating the Molecular Nonpolar Surface for Analysis of LC-MS Data.

The accurate determination of the nonpolar surface area of glycans is vital when utilizing liquid chromatograph/mass spectrometry (LC-MS) for structural characterization. A new approach for defining and computing nonpolar surface areas based on continuum solvation models (CS-NPSA) is presented. It is based on the classification of individual surface elements representing the solvent accessible surface used for the description of the polarized charge density elements in the CS models. Each element can be classified as polar or nonpolar according to a threshold value. The summation of the nonpolar elements then results in the NPSA resulting in a very fine resolution of this surface. The further advantage of the CS-NPSA approach is the straightforward connection to standard quantum chemical methods and program packages. The method has been analyzed in terms of the contributions of different atoms to the NPSA. The analysis showed that not only atoms normally classified as nonpolar contributed to the NPSA, but at least partially also atoms next to polar atoms or N atoms. By virtue of the construction of the solvent accessible surface, atoms in the inner regions of a molecule can be automatically identified as not contributing to the NPSA. The method has been applied to a variety of examples such as the phenylbutanehydrazide series, model dextrans consisting of glucose units and biantennary glycans. Linear correlation of the CS-NPSA values with retention times obtained from liquid chromatographic separations measurements in the mentioned cases give excellent results and promise for more extended applications on a larger variety of compounds.

Reaction mechanism for fluorination reactions with hydroxylated alumina sites: Pathways promoting aluminum combustion.

Density functional theory calculations were used to reveal the mechanism for the fluorination reaction of active Lewis acid sites on alumina structures, which is important in understanding the pyrophoric processes involving Al particles. In this reaction, hydroxyl groups of active sites are replaced by fluorine anions. Alumina structures were represented by three aluminum aqua hydroxo clusters (labeled AlOOH), in which the Al atom had different coordination spheres, particularly four, five, or six. The F-bearing molecules HF, CH3F, and CF4 were taken as reactants for the fluorination reactions. The overall reaction was represented by four reaction steps as follows: (i) formation of the reaction complex, (ii) activation of the transition state (TS), (iii) deactivation of the TS with a formation of the product complex, and (iv) its decomplexation to individual products. The active reaction center of the TS structure is four-membered, in which two bonds break heterolytically and two form. The lowest reaction barriers were observed for the HF molecule, while the two other molecules had significantly higher reaction barriers. Similarly, the largest overall reaction energies (in absolute value) were found for HF, especially for the five- and six-coordinated Al centers. While the positive charge on the Al center remained almost constant throughout the reaction steps, large charge changes were observed for carbon bearing molecules with a formation of the carbenium cations in the TS step. Realizing the important role of HF in promoting exothermic reactions will enable new molecular design strategies for transforming energy release properties of aluminum powder fuels.

Excitonic and charge transfer interactions in tetracene stacked and T-shaped dimers.

Extended quantum chemical calculations were performed for the tetracene dimer to provide benchmark results, analyze the excimer survival process, and explore the possibility of using long-range-corrected (LC) time-dependent second-order density functional tight-biding (DFTB2) for this system. Ground- and first-excited-state optimized geometries, vertical excitations at relevant minima, and intermonomer displacement potential energy curves (PECs) were calculated for these purposes. Ground-state geometries were optimized with the scaled-opposite-spin (SOS) second-order Møller-Plesset perturbation (MP2) theory and LC-DFT (density functional theory) and LC-DFTB2 levels. Excited-state geometries were optimized with SOS-ADC(2) (algebraic diagrammatic construction to second-order) and the time-dependent approaches for the latter two methods. Vertical excitations and PECs were compared to multireference configuration interaction DFT (DFT/MRCI). All methods predict the lowest-energy S0 conformer to have monomers parallel and rotated relative to each other and the lowest S1 conformer to be of a displaced-stacked type. LC-DFTB2, however, presents some relevant differences regarding other conformers for S0. Despite some state-order inversions, overall good agreement between methods was observed in the spectral shape, state character, and PECs. Nevertheless, DFT/MRCI predicts that the S1 state should acquire a doubly excited-state character relevant to the excimer survival process and, therefore, cannot be completely described by the single reference methods used in this work. PECs also revealed an interesting relation between dissociation energies and the intermonomer charge-transfer interactions for some states.

Cycloaddition of Strained Cyclic Alkenes and Ortho-Quinones: A Distortion/Interaction Analysis.

The chemistry of strained unsaturated cyclic compounds has experienced remarkable growth in recent years via the development of metal-free click reactions. Among these reactions, the cycloaddition of cyclopropenes and their analogues to ortho-quinones has been established as a highly promising click reaction. The present work investigates the mechanism involved in the cycloaddition of strained dienes to ortho-quinones and structural factors that would influence this reaction. For this purpose, we use B97D density functional theory calculations throughout, and for relevant cases, we use spin component-scaled MP2 calculations and single-point domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) calculations. The outcomes are analyzed in detail using the distortion/interaction model, and suggestions for future experimental work are made.

Interplay of Biradicaloid Character and Singlet/Triplet Energy Splitting for cis-/trans-Diindenoacenes and Related Benzothiophene-Capped Oligomers as Revealed by Extended Multireference Calculations.

The biradicaloid character of different types of polycyclic aromatic hydrocarbons is an important quality that guides the development of new materials with interesting magneto-optical properties. Diindenoacene-based systems represent such a class of promising compounds. In this work, the three types trans-diindenoacenes, cis-diindenoacenes, and trans-dicyclopentaacenobis(benzothiophenes) have been studied by means of advanced ab initio methods. The descriptors singlet/triplet splitting energy (ΔES-T), effective number of unpaired electrons (NU), unpaired electron density, and the harmonic oscillator measure of aromaticity have been used to characterize the biradicaloid properties of these species. For all trans structures, low-spin singlet ground states were found, in agreement with previous investigations. Increasing the length of the inner acene chain decreased the ΔES-T and strongly increased the NU values of the singlet state. The cis-diindenoacenes displayed a greatly increased biradicaloid character, indicating enhanced chemical instability. The thiophene rings in the trans-dicyclopentaacenobis(benzothiophenes) structures were found to simultaneously restrict the unpaired electron density from extending into the terminal six-membered rings and confine the unpaired electron density found in the core benzene rings.