Aromaticity and Magnetic Behavior in Benzenoids: Unraveling Ring Current Combinations.

Nowadays, an active research topic is the connection between Clar's rule, aromaticity, and magnetic properties of polycyclic benzenoid hydrocarbons. In the present work, we employ a meticulous magnetically induced current density analysis to define the net current flowing through any cyclic circuit, connecting it to aromaticity based on the ring current concept. Our investigation reveals that the analyzed polycyclic systems display a prominent global ring current, contrasting with subdued semi-local and local ring currents. These patterns align with Clar's aromatic π-sextets only in cases where migrating π-sextet structures are invoked. The results of this study will enrich our comprehension of aromaticity and magnetic behavior in such systems, offering significant insights into coexisting ring current circuits in these systems.

New Perspectives on Delocalization Pathways in Aromatic Molecular Chameleons.

This study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as "aromatic chameleons" since they can arrange their π-electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π-electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S0 state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T1 state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons consisting of fused 4n π-electron rings. Moreover, our study demonstrates an inverse correlation between the singlet-triplet energy difference and the antiaromatic character of the central ring in S0.

Planar tetracoordinate beryllium compounds with a partially covalent Be-Ng bond.

An analysis of the thermodynamic and kinetic stability and the nature of the chemical bond in hypercoordinated compounds with the formula BeH3Ng+ (Ng = He-Rn) through high-level calculations is presented in this work. Thermochemical calculations show that, for the heavier noble gases (Ar-Rn), these systems are thermodynamically stable at room temperature; however, this stability decreases due to a weakening of the Be-H2 interaction, while the Be-Ng bond strengthens going down the periodic table. These results are complemented by Born Oppenheimer molecular dynamics simulations, in which the increasing tendency to dissociate the Be-H2 bond is evidenced. The nature of the chemical bonding depends on the analysis performed. On the one hand, the interacting quantum atoms method indicates that the covalent contribution is around 25 to 30%. On the other hand, the electron density topology indicates a covalent nature for compounds with Kr-Rn, while Hirshfeld population analysis in conjunction with Mayer's bond order establishes polar covalent behavior. The geometrical parameters and natural energy decomposition analysis (NEDA) indicate a covalent nature, allowing us to consider that the Be-Ng bond has a partially covalent character.

Designing potentially singlet fission materials with an anti-Kasha behaviour.

Singlet fission (SF) compounds offer a promising avenue for improving the performance of solar cells. Using TD-DFT methods, anti-Kasha azulene derivatives that could carry out SF have been designed. For this purpose, substituted azulenes with a donor (-OH) and/or an acceptor group (-CN) have been systematically studied using the S2 ≥ 2T1 formula. We have found that -CN (-OH) substituents on electrophilic (nucleophilic) carbons result in improved SF properties when compared to azulene.

Exploring the Nature of Chemical Bonding between Noble Gases and Hypercoordinate Group 13 Compounds: Beyond Boron.

In this article, we systematically study the stability and chemical bond nature of EH4Ng+ compounds (E = Al-Tl; Ng = He-Rn) at the CCSD(T) and ωB97XD levels of theory. Thermochemical calculations obtained by exploring different dissociation pathways show that these compounds could be stable at low temperatures. In addition, studied compounds have a strong E-Ng bond, which has been characterized using different methodologies such as quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO) theory, and natural energy decomposition analysis (NEDA). Results indicate that the nature of the chemical bond is predominantly covalent, especially in the case those including the heavier gases (Ar-Rn), occurring through a charge transfer from the noble gas to the group 13 element. However, the electrostatic contribution is also important in the stabilization of this bond. This study extends the universe of group 13 molecules containing noble gas bonds beyond boron and other elements from the second period.

Li6 E5 Li6 : Tetrel Sandwich Complexes with 10-π-Electrons.

When (4n +2) π-electrons are located in single planar ring, it conventionally qualifies as aromatic. According Hückel's rule, systems possessing ten π-electrons should be aromatic. Herein we report a series of D5h  Li6 E5 Li6 sandwich structures, representing the first global minima featuring ten π-electrons E5 10- ring (E=Si-Pb). However, these π-electrons localize as five π-lone-pairs rather than delocalized orbitals. The high symmetry structure achieved is a direct consequence of σ-aromaticity, particularly favored in elements from Si to Pb, resulting in a pronounced diatropic ring current flow that contributes to the enhanced stability of these systems.

BH4 Ng+ (Ar-Rn): Viable Compounds with a B-Ng Covalent Bond.

In this work, we explore, using high-level calculations, the ability of BH4 + to interact with noble gases. The He system is energetically unstable, while the Ne system could only be observed at cryogenic temperatures. In the case of the Ar, Kr and Xe systems, all are energetically stable, even at room temperature. The different chemical bond descriptors reveal a covalent character between B and the noble gas from Ar to Rn. However, this interaction gradually weakens the multicentric bond between the boron atom and the H2 fragment. Thus, although BH4 Rn+ exhibits a strong covalent bond, it tends to dissociate at room temperature into BH2 Rn+ +H2 .

Strong carbon - noble gas covalent bond and fluxionality in hypercoordinate compounds.

Thermodynamic, kinetic, and chemical bonding analysis at the coupled cluster level has been carried out for a series of hypercoordinated carbon compounds with formula CH4Ng2+ (Ng = He-Rn). Results show that these compounds could be stable at room temperature and Born-Oppenheimer molecular dynamics simulations (BOMD) in conjunction with activation energies indicate high kinetic stability. In addition, all chemical bonding descriptors agree with a strong C-Ng covalent bond and a bonding pattern similar to that of CH5+. Finally, BOMD simulations showed that these compounds are fluxional, with a continuous formation/breaking of H-H and C-H bonds. To the best of the authors' knowledge, these results represent the first series of fluxional compounds possessing a covalent bond between a main group element and a noble gas atom.

Near-infrared absorption of fused core-modified expanded porphyrins for dye-sensitized solar cells.

Photophysical, photovoltaic, and charge transport properties of fused core-modified expanded porphyrins containing two pyrroles, one dithienothiophene (DTT) unit, and 1-4 thiophenes (1-4) were inspected by using density functional theory (DFT) and time-dependent DFT. Compounds 1-3 have been investigated experimentally before, but 4 is a theoretical proposal whose photophysical features match those extrapolated from 1 to 3. They exhibit absorption in the range of 700-970 nm for their Q bands and 500-645 nm for their Soret bands. The rise of thiophene rings placed in front of the DTT unit in the expanded porphyrin ring causes a bathochromic shift of the longest absorption wavelength, leading to near-infrared absorptions, which represent 49% of the solar energy. All the systems show a thermodynamically favorable process for the electron injection from the dye to TiO2 and adsorption on a finite TiO2 model. The electron regeneration of the dye is only thermodynamically feasible for the smallest expanded porphyrins 1 and 2 when I-/I3- electrolyte is used. The charge transport study shows that for voltages lower than 0.4 V, junctions featuring pentaphyrin 1 and octaphyrin 4 are more conductive than those containing hexaphyrin 2 or heptaphyrin 3. The results showed that the four fused core-modified expanded porphyrins investigated are potential dyes for applications in dye-sensitized solar cells, mainly pentaphyrin 1 and hexaphyrin 2. Moreover, increasing the number of thiophene rings in the macrocycle proved fruitful in favoring absorption in the near-infrared region, which is highly desired for dye-sensitized solar cells.

Discovery of New 2-Phenylamino-3-acyl-1,4-naphthoquinones as Inhibitors of Cancer Cells Proliferation: Searching for Intra-Cellular Targets Playing a Role in Cancer Cells Survival.

A series of 2-phenylamino-3-acyl-1,4-naphtoquinones were evaluated regarding their in vitro antiproliferative activities using DU-145, MCF-7 and T24 cancer cells. Such activities were discussed in terms of molecular descriptors such as half-wave potentials, hydrophobicity and molar refractivity. Compounds 4 and 11 displayed the highest antiproliferative activity against the three cancer cells and were therefore further investigated. The in silico prediction of drug likeness, using pkCSM and SwissADME explorer online, shows that compound 11 is a suitable lead molecule to be developed. Moreover, the expressions of key genes were studied in DU-145 cancer cells. They include genes involved in apoptosis (Bcl-2), tumor metabolism regulation (mTOR), redox homeostasis (GSR), cell cycle regulation (CDC25A), cell cycle progression (TP53), epigenetic (HDAC4), cell-cell communication (CCN2) and inflammatory pathways (TNF). Compound 11 displays an interesting profile because among these genes, mTOR was significantly less expressed as compared to control conditions. Molecular docking shows that compound 11 has good affinity with mTOR, unraveling a potential inhibitory effect on this protein. Due to the key role of mTOR on tumor metabolism, we suggest that impaired DU-145 cells proliferation by compound 11 is caused by a reduced mTOR expression (less mTOR protein) and inhibitory activity on mTOR protein.

On the stability and chemical bond of noble gas halide cations NgX+ (Ng = He - Rn; X = F - I).

Despite the belief that noble gases (Ng) are completely inert and cannot form stable molecules, a variety of Ng compounds have been reported under laboratory conditions and others were recently detected in the interstellar media, raising interest in knowing and studying their bond nature and the physicochemical properties associated with their stability. In the present work, a systematic analysis of the thermodynamic stability of noble gas halide cations (NgX+ ) at the CCSD(T)/def2-QZVP level have been performed. In addition, chemical bond was characterized through Natural Bonding Theory (NBO), Quantum Theory of Atoms in Molecules (QTAIM) and Energy Decomposition Analysis (EDA) with relativistic corrections. All methods suggest that NgX+ compounds possess a strong covalent bond. However, results show that only compounds containing Ar-Rn atoms are thermodynamic stable with a highly energetic and endergonic dissociation process. For these reasons, it is possible to suggest that several compounds that have not yet been reported could be obtained at the laboratory level or observed in the interstellar medium.

Kick-Fukui: A Fukui Function-Guided Method for Molecular Structure Prediction.

Here, we introduce a hybrid method, named Kick-Fukui, to explore the potential energy surface (PES) of clusters and molecules using the Coulombic integral between the Fukui functions in the first screening of the best individuals. In the process, small stable molecules or clusters whose combination has the stoichiometry of the explored species are used as assembly units. First, a small set of candidates has been selected from a large and stochastically generated (Kick) population according to the maximum value of the Coulombic integral between the Fukui functions of both fragments. Subsequently, these few candidates are optimized using a gradient method and density functional theory (DFT) calculations. The performance of the program has been evaluated to explore the PES of various systems, including atomic and molecular clusters. In most cases studied, the global minimum (GM) has been identified with a low computational cost. The strategy does not allow to identify the GM of some silicon clusters; however, it predicts local minima very close in energy to the GM that could be used as the initial population of evolutionary algorithms.

Boron-noble gas covalent bonds in borenium and boronium compounds.

The capability of the BH2+ parent cation to bind noble gases (Ng) has been evaluated. The results show its potential to form borenium (BH2Ng+) and boronium (BH2Ng2+) cations. Conformational search using the recently developed AUTOMATON program and Coalescence Kick method, in addition to thermochemical and Born-Oppenheimer molecular dynamics (BOMD) calculations, were performed. Results show that compounds containing Ng = Ar-Rn are thermodynamically and kinetically stable. Furthermore, it was found that the B-Ng bond has high dissociation energy values at both DFT and CCSD(T) levels suggesting a strong interaction. The nature of the chemical bond has been assessed according to the Quantum Theory of Atoms in Molecules (QTAIM), Natural Bond Orbital Theory (NBO) and Energy decomposition Analysis (EDA). Negative values of local energy density H(rc) and high values of the Wiberg bond Index (WBI) reveal its covalent nature that is confirmed by localized natural bond orbitals with 2.0 |e| occupations. Additionally, it could be observed that the orbital term (ΔEorb) is the most important component (84.6-90.1%) of the interaction energy between the parent BH2+ and Ng atoms, supporting the polar covalent nature of the B-Ng bond.

Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?

The larger stability of phenacenes compared to their acene isomers in their ground states is attributed to the larger aromaticity of the former. To our knowledge the relative stability of acenes and phenacenes in their lowest-lying triplet states (T1) has not been discussed yet. Using unrestricted density functional theory calculations, our results show that for the smallest members of the series, acenes in their T1 states are more stable than the corresponding phenacenes. However, when the number of the rings (n) involved increases, the energy difference is reduced and for n > 12, phenacenes become more stable than acenes in their T1 states. To rationalize this trend, we analyze the aromaticity of acenes and phenacenes using a set of aromaticity descriptors. We find that in the T1 states of both acenes and phenacenes, the outer rings form aromatic Clar π-sextets. In acenes, delocalization of spin density in the central rings leads to the preferred formation of the largest antiaromatic diradical. Resonant structures in the form of antiaromatic diradical Baird π-octadectets and π-tetradectets are the major contributors, while the smaller ones, such as π-doublets and π-sextets, contribute the least. In phenacenes, structures with diradical antiaromatic Baird π-sextets in some of the central rings contribute the most. These results are relevant to understand the (anti)aromaticity of larger polycyclic aromatic hydrocarbons in their triplet states.

The Relative Stability of Indole Isomers Is a Consequence of the Glidewell-Lloyd Rule.

Indole (1) is a heterocyclic aromatic compound consisting of a pyrrole ring (5MR) fused with a benzene ring (6MR). This compound is highly stable, found in several natural products, and is used as a building block for the synthesis of novel organic compounds. On the other hand, its isomers isoindole (2) and indolizine (3) are much less stable and are normally isolated when bonded to other stable compounds. The stability of these compounds has been analyzed in terms of local aromaticity using magnetic, geometric, and delocalization criteria. All criteria used indicate that there is a continuing reduction in aromaticity of the 6MR, whereas for the 5MR the aromaticity increases when going from 1 to 3. This is confirmed by Natural Resonance theory calculations indicating that the resonant structures which retain the aromaticity of the 5MR are the ones having the largest contribution. The results obtained suggest that the relative stability of indole isomers is a consequence of the Glidewell-Lloyd rule.

Assessment of New Expanded Porpholactones as UV/Vis/NIR Chromophores for Dye-Sensitized Solar Cell Applications.

Expanded porphyrins arise as an alternative for potential application as chromophores in dye-sensitized solar cells. (DSSCs). The modification of the core of these compounds provides remarkable changes in the photoelectronic behavior. In the present article, the improvement of its properties for a potential application as UV/vis/NIR chromophores in DSSCs has been studied, when an oxazolone moiety has replaced an imine ring in analogy to the porpholactones first synthesized by Crossley et al. ( J. Chem. Soc., Chem. Commun. 1984, 920-922). These expanded porpholactones present a noticeable red shift as well as an increase in the intensity of the Q-bands regarding the parent compounds. The photophysical properties of Sapphyrin have been explored through DFT calculations and vibrationally resolved absorption spectra simulations. Energetic parameters showed favorable electron injection from the chromophore to the TiO2 semiconductor. In addition, aromaticity was analyzed and rationalized using magnetic and delocalization criteria. Results showed qualitatively similar trends between aromaticity descriptors and Q bands giving a great opportunity to the use this property in the rational design of chromophores. Finally, the nonequilibrium Green's function formalism shows the ability of expanded porpholactones in electron transport.

Neither too Classic nor too Exotic: One-Electron Na⋠B Bond in NaBH3 - Cluster.

It is here reported that the NaBH3 - cluster exhibits a Na⋅B one-electron bond, a well-established type of electron-deficient bonding in the literature. The topological analysis of the electron localization function, at the correlated level, reveals that Na- , when approaching the bonding distance, fairly distributes its valence electron pair between two lobes. One of these electrons is used to bond with BH3 , which participates through its boron empty p-orbital. Furthermore, the bonding situation of LiBH3 - , KBH3 - , MgBH3 , and CaBH3 global minima structures are similar to that of NaBH3 - , extending the family of these new one-electron bond systems with biradicaloid character.

Relativistic effects on the aromaticity of E3M3H3 (E = C-Pb; M = N-Bi) benzene analogues.

The relativistic effects on the aromaticity of a set of benzene analogues, E3M3H3 (E = C-Pb; M = N-Bi) heterocycles, using magnetically induced current density (MICD) and the NICSzz component of the conventional nucleus independent chemical shift (NICS), is hereby examined. The relativistic effects were evaluated by means of four-component relativistic MICD, and two-component NMR relativistic shielding tensor methods. MICD and NICS were also computed in a non-relativistic fashion, to assess the influence of scalar-relativistic and spin-orbit effects. Most of the studied compounds exhibit a net diatropic ring current (aromatic), excluding the nitrogen-containing compounds which are non-aromatic (except for C3N3H3), in agreement with their higher E-N electronegativity difference. Only in the case of bismuth compounds, E3Bi3H3, aromaticity is substantially decreased when relativistic effects are included (mainly due to the spin-orbit contribution). The larger the mass of the system, the larger the magnitude of this change, in line with the expected relativistic effects for heavier elements. The analysis based on the NICSzz computations agrees with that of the MICD, thus supporting both the magnetic behavior and the aromatic character of these compounds.

Local and macrocyclic (anti)aromaticity of porphyrinoids revealed by the topology of the induced magnetic field.

The aromaticity in porphyrinoids results from the π conjugation through two different annular perimeters: the macrocyclic ring and the local heterocyclic rings appended to it. Analyses, based on aromatic stabilization energies (ASE), indicate that the local circuits (6π) are responsible for the significant aromatic stabilization of these systems. This local aromaticity can be coupled with the one from 4n + 2π macrocyclic circuit. It can either compensate for the destabilization due to a 4n π macrocyclic circuit, or be the only source of aromatic stabilization in porphyrinoids with macrocycles without π-conjugated bonds. This "multifaceted" aromatic character of porphyrinoids makes it challenging to analyze their aromaticity using magnetic descriptors because of the intricate interaction of local versus macro-cyclic circulation. In this contribution, we show that the analysis of the bifurcation of the induced magnetic field, Bind, allows clear identification and quantification of both local, and macrocyclic aromaticity, in a representative group of porphyrinioids. In porphyrin, bifurcation values accurately predict the local and macrocyclic contribution rate to overall aromatic stabilization determined by ASE.

The influence of antenna and anchoring moieties on the improvement of photoelectronic properties in Zn(ii)-porphyrin-TiO2 as potential dye-sensitized solar cells.

A systematic study for the rational design of porphyrins (P4 spider-shaped derivatives) with potential application in dye-sensitized solar cells is presented. Using density functional theory (DFT) (B3LYP/6-31G*) and time-dependent DFT (M06/6-31G*) we show that the UV-vis absorption properties of a spider-shaped Zn(ii) porphyrin, previously synthesized by Stangel et al., may be greatly improved by applying some push-pull strategies in meso positions. We found that the selected triphenylamine push group induces a remarkable improvement in the absorption bands of P4 spider-shaped derivatives. The pull effect reached through the π-electron-rich phenyl group and the benzodithiazole (BTD) group allowed the Q bands to be red-shifted up to 689 nm, much longer than the 593 nm reported experimentally for the original spider-shaped porphyrin. The adsorption results of the P4 spider-shaped derivatives onto a TiO2-anatase surface model [Ti16O34H4] through the carboxylic acid group showed that the adsorptions energies were favourable and very similar in all cases. Natural bond orbitals (NBO) indicated a two-center bond (BD) O(carboxyl)-Ti(TiO2) for the porphyrin with the highest adsorption energy (8.27 kcal mol-1), and donor acceptor interactions from LP O(carboxyl) to Ti(TiO2) for the other porphyrins. The natural transition orbitals (NTO) for P4-derivatives-TiO2 confirm the nature of the excited states associated with Q and Soret bands. Finally, the frontier molecular orbitals revealed charge-separated states between those occupied and unoccupied, indicating a favourable charge-transfer process between the dyes and the surface conduction bands. In conclusion, this work showed a systematic study based on the push-pull strategy that improves the performance of porphyrins with the purpose to be used in dye-sensitized solar cells.