Understanding Aromaticity in [5]Helicene-Bridged Cyclophanes: A Comprehensive Study.

This study explores the aromaticity of doubly [5]helicene-bridged (1,4)cyclophane and triply [5]helicene-bridged (1,3,5)cyclophane via calculations of the magnetic response and of electronic aromaticity indices. The primary objective is to assess the π-electron delocalization to determine whether they sustain global ring currents associated with π aromaticity. The molecules show local ring currents in the presence of an external magnetic field. The ring currents flow diatropically in the stacked six-membered rings and in the helicene arms. However, these π currents are not interconnected due to the discontinuity of the π delocalization at the C-C single bonds connecting the central six-membered rings to the helicene arms. Electronic indices suggest that the helicene-arm systems have significantly smaller electron delocalization than benzene. The reduction in the delocalization does not compromise their ability to exhibit ring currents in the presence of an external magnetic field. The analysis provides further evidence that the magnetic criteria yield a different degree of aromaticity for the helicene arms than obtained in the calculation of the electronic aromaticity indices. However, both approaches confirm that the studied molecules are not globally aromatic.

Insights into the coordination chemistry of antineoplastic doxorubicin with 3d-transition metal ions Zn2+, Cu2+, and VO2+: a study using well-calibrated thermodynamic cycles and chemical interaction quantum chemistry models.

We present a computational strategy based on thermodynamic cycles to predict and describe the chemical equilibrium between the 3d-transition metal ions Zn2+, Cu2+, and VO2+ and the widely used antineoplastic drug doxorubicin. Our method involves benchmarking a theoretical protocol to compute gas-phase quantities using DLPNO Coupled-Cluster calculations as reference, followed by estimating solvation contributions to the reaction Gibbs free energies using both explicit partial (micro)solvation steps for charged solutes and neutral coordination complexes, as well as a continuum solvation procedure for all solutes involved in the complexation process. We rationalized the stability of these doxorubicin-metal complexes by inspecting quantities obtained from the topology of their electron densities, particularly the bond critical points and non-covalent interaction index. Our approach allowed us to identify representative species in solution phase, infer the most likely complexation process for each case, and identify key intramolecular interactions involved in the stability of these compounds. To the best of our knowledge, this is the first study reporting thermodynamic constants for the complexation of doxorubicin with transition metal ions. Unlike other methods, our procedure is computationally affordable for medium-sized systems and provides valuable insights even with limited experimental data. Furthermore, it can be extended to describe the complexation process between 3d-transition metal ions and other bioactive ligands.

Benzene and Borazine, so Different, yet so Similar: Insight from Experimental Charge Density Analysis.

Although benzene and borazine are isoelectronic and isostructural, they have very different electronic structures, mainly due to the polar nature of the B-N bond. Herein, we present an experimental study of the charge density distribution obtained from the multipole model formalism and Hirshfeld atom refinement (HAR) based on high-resolution X-ray diffraction data of borazine B3N3H6 (1) and B,B',B″-trichloroborazine (2) crystals. These data are compared to those obtained from HAR for benzene (4) and 1,3,5-trichlorobenzene (5) and further compared with values obtained from density functional theory calculations in the gas phase, where N,N',N″-trichloroborazine (3) was also included. The results confirm that, unlike benzene, borazines are only weakly aromatic with an island-like electronic delocalization within the B3N3 ring involving only the nitrogen atoms. Furthermore, delocalization indices and interacting quantum atom energy for bonded and non-bonded atoms were found to be highly suitable indicators capable of describing the origin of the discrepancies observed when the degree of aromaticity in 2 and 3 is evaluated using common aromaticity indices. Additionally, analysis of intermolecular interactions in the crystals brings further evidence of a weakly aromatic character of the borazines as it reveals surprising similarities between the crystal packing of borazine and benzene and also between B,B',B″-trichloroborazine and 1,3,5-trichlorobenzene.

Reply to the Correspondence on "How Aromatic Are Molecular Nanorings? The Case of a Six-Porphyrin Nanoring".

A recent article by Anderson and co-workers challenges our conclusions on the aromaticity of the four oxidation states of a butadyine-linked six-porphyrin nanoring, based on the experimental 1 H-NMR data and some recent calculations they have performed using the BLYP35 functional. Here, we show that BLYP35 should be taken with caution and demonstrate that the indirect evidence of a ring current from experimental 1 H-NMR data is not a definite proof of aromaticity.

A refreshing approach to understanding the action on DNA of vanadium (IV) and (V) complexes derived from the anticancer VCp2Cl2.

A computational study based on derivatives of the anticancer VCp2Cl2 compound and their interaction with representative models of deoxyribonucleic acid (DNA) is presented. The derivatives were obtained by substituting the cyclopentadienes of VCp2Cl2 with H2O, NH3, OH-, Cl-, O2- and C2O42- ligands. The oxidation states IV and V of vanadium were considered, so a total of 20 derivative complexes are included. The complexes interactions with DNA were studied using two different models, the first model considers the interactions of the complexes with the pair Guanine-Cytosine (G-C) and the second involves the interaction of the complexes with adjacent pairs, that is, d(GG). This study compares methodologies based on density functional theory with coupled cluster like calculations (DLPNO-CCSD(T)), the gold standard of electronic structure methods. Furthermore, the change in the electron density of the hydrogen bonds that keep bonded the G-C pair and d(GG) pairs, due to the presence of vanadium (IV) and (V) complexes is rationalize. To this aim, quantities obtained from the topology of the electron densities are inspected, particularly the value of the electron density at the hydrogen bond critical points. The approach allowed to identify vanadium complexes that lead to significant changes in the hydrogen bonds indicated above, a key aspect in the understanding, development, and proposal of mechanisms of action between metal complexes and DNA.

Core-electron contributions to the magnetic response of molecules with heavy elements and their significance in aromaticity assessments.

This study delves into the magnetic response of core electrons and their influence on the global magnetic response of planar and three-dimensional systems containing heavy elements, employing the removing valence electron (RVE) approximation. We also explore electronic aromaticity indices to understand the potential role of core electrons on electron delocalization in the absence of an external perturbation. The study reveals that core electrons significantly contribute to the overall magnetic response, especially to the magnetic shielding, affecting the interpretation of aromaticity. In contrast, the calculation of the electronic aromaticity indices suggests a negligible participation of the core electrons on electron delocalization. Despite their widespread use, the study emphasizes caution in labeling systems as strongly aromatic based solely on shielding function computations. It is noteworthy to emphasize the limitations associated with each aromaticity criterion; particularly in the context of magnetic shielding function calculations, the core-electron effect contamination is undeniable. Hence, the integration of various criteria becomes imperative for attaining a comprehensive understanding of magnetic responses within complex systems.

All-Purpose Measure of Electron Correlation for Multireference Diagnostics.

We present an analytical relationship between two natural orbital occupancy-based indices, IND¯ and INDmax, and two established electron correlation metrics: the leading term of a configuration interaction expansion, c0, and the D2 diagnostic. Numerical validation revealed that IND¯ and INDmax can effectively substitute for c0 and D2, respectively. These indices offer three distinct advantages: (i) they are universally applicable across all electronic structure methods, (ii) their interpretation is more intuitive, and (iii) they can be readily incorporated into the development of hybrid electronic structure methods. Additionally, we draw a distinction between correlation measures and correlation diagnostics, establishing MP2 and CCSD numerical thresholds for INDmax, which are to be used as a multireference diagnostic. Our findings further demonstrate that establishing thresholds for other electronic structure methods can be easily accomplished using small data sets.

Analyzing ZnO clusters through the density-functional theory.

The potential energy surface of Zn n O n clusters (n = 2, 4, 6, 8) has been explored by using a simulated annealing method. For n = 2, 4, and 6, the CCSD(T)/TZP method was used as the reference, and from here it is shown that the M06-2X/TZP method gives the lowest deviations over PBE, PBE0, B3LYP, M06, and MP2 methods. Thus, with the M06-2X method we predict isomers of Zn n O n clusters, which coincide with some isomers reported previously. By using the atoms in molecules analysis, possible contacts between Zn and O atoms were found for all structures studied in this article. The bond paths involved in several clusters suggest that Zn n O n clusters can be obtained from the zincite (ZnO crystal), such an observation was confirmed for clusters with n = 2 - 9,18 and 20. The structure with n = 23 was obtained by the procedure presented here, from crystal information, which could be important to confirm experimental data delivered for n = 18 and 23.