In this work, we explore the applicability and limitations of the current third order density functional tight binding (DFTB3) formalism for treating transition metal ions using nickel as an example. To be consistent with recent parameterization of DFTB3 for copper, the parametrization for nickel is conducted in a spinpolarized formulation and with orbital-resolved Hubbard parameters and their charge derivatives. The performance of the current parameter set is evaluated based on structural and energetic properties of a set of nickel-containing compounds that involve biologically relevant ligands. Qualitatively similar to findings in previous studies of copper complexes, the DFTB3 results are more reliable for nickel complexes with neutral ligands than for charged ligands; nevertheless, encouraging agreement is noted in comparison to the reference method, B3LYP/aug-cc-pVTZ, especially for structural properties, including cases that exhibit Jahn-Teller distortions; the structures also compare favorably to available X-ray data in the Cambridge Crystallographic Database for a number of nickel-containing compounds. As to limitations, we find it is necessary to use different d shell Hubbard charge derivatives for Ni(I) and Ni(II), due to the distinct electronic configurations for the nickel ion in the respective complexes, and substantial errors are observed for ligand binding energies, especially for charged ligands, d orbital splitting energies and splitting between singlet and triplet spin states for Ni(II) compounds. These observations highlight that future improvement in intra-d correlation and ligand polarization is required to enable the application of the DFTB3 model to complex transition metal ions.

A detailed theoretical investigation of cyclophanes with a divergent set of methods ranging from molecular mechanics through semiempirical to ab initio is presented. Cyclophanes have attracted interest over the years due to their unusual chemistry and increasing applications. There has been previous debate over the effects contributing to the greater stability of more-crowded in isomers of certain cyclophanes, and a higher strain in the out isomer was the prevailing explanation. Application of EDA-NOCV and SAPT analysis has enabled us to distinguish between different effects controlling isomer stability and determine the significance of all effects involved. Our results show that, although strain has a large significance, orbital stabilization within the molecule from the aromatic electron density is crucial. Furthermore, we analysed halogen-substituted cyclophanes in order to further understand these subtle effects.

Chromatographic behavior and lipophilicity of 20 selected imidazoline derivatives were examined by thin-layer chromatography using CN, RP-2, RP-8 and RP-18 as the stationary phases and a mixture of methanol, water and ammonia as the mobile phase. In all examined chromatographic systems, linear relationships were established between retention parameters and the volume fraction of methanol in the mobile phase (r > 0.985, 0.978, 0.981, 0.988 for the CN, RP-2, RP-8 and RP-18, respectively). The highest correlation between the obtained [Formula: see text] values was observed for RP-2 and RP-8 stationary phases. The experimental lipophilicity indices ([Formula: see text], m and C0) obtained from the retention data were used in correlation study with the calculated logP values. Experimentally determined [Formula: see text] values for all investigated chromatographic systems exhibited the highest correlation with the calculated ClogP values (r: 0.880, 0.872, 0.897 and 0.889 for the CN, RP-2, RP-8 and RP-18 stationary phases, respectively). In addition, principal component analysis enables new information about similarity and differences between tested compounds as well as experimental lipophilicity indices and calculated logP values. Performed QSRR analysis showed that the frequency of C-C at topological distance 1 and CATS2D Lipophilic-Lipophilic at lag 01 were important descriptors with influence on the [Formula: see text] values in all the examined chromatographic systems, while the differences in the retention behavior of compounds on the examined stationary phases can be distinguished based on their specific geometrical, electronic and constitutional properties.