Molecular properties of linear amino acids in water.

Four linear amino acids of increased separation of the carboxyl and amino groups, namely glycine (aminoacetic acid), ß-alanine (3-aminopropanoic acid), GABA (4-aminobutanoic acid) and DAVA (5-aminopentanoic acid), have been studied by quantum chemical ab initio and DFT methods including the solvent effect in order to get electronic structure and molecular descriptors, such as ionisation energy, electron affinity, molecular electronegativity, chemical hardness, electrophilicity index, dipole moment, quadrupole moment and dipole polarizability. Thermodynamic functions (zero-point energy, inner energy, enthalpy, entropy, and the Gibbs energy) were evaluated after the complete vibrational analysis at the true energy minimum provided by the full geometry optimization. Reaction Gibbs energy allows evaluating the absolute redox potentials on reduction and/or oxidation. The non-local non-additive molecular descriptors were compared along the series showing which of them behave as extensive, varying in match with the molar mass and/or separation of the carboxyl and amino groups. Amino acidic forms and zwitterionic forms of the substances were studied in parallel in order to compare their relative stability and redox properties. In total, 24 species were investigated by B3LYP/def2-TZVPD method (M1) including neutral molecules, molecular cations and molecular anions. For comparison, MP2/def2-TZVPD method (M2) with full geometry optimization and vibrational analysis in water has been applied for 12 species; analogously, for 24 substances, DLPNO-CCSD(T)/aug-cc-pVTZ method (M3) has been applied in the geometry obtained by MP2 and/or B3LYP. It was found that the absolute oxidation potential correlates with the adiabatic ionisation energy; the absolute reduction potential correlates with the adiabatic electron affinity and the electrophilicity index. In order to validate the used methodology with experimental vertical ionisation energies and vibrational spectrum obtained in gas phase, calculations were done also in vacuo.

Ab initio study of the biogenic amino acids.

Ten amino acids have been subjected to the quantum chemical calculations using the ab initio MO-LCAO-SCF calculations. When the geometry optimization started form the X-ray structure confirming the zwitterionic form, the ab initio calculations in vacuo result in the amino acid (canonical) form with the hydrogen atom attached not to the amine but to the carboxylate group. At the optimum geometry, a number of properties were evaluated: dipole moment, dipole polarizability, molecular surface, molecular volume, HOMO, LUMO, ionization energy, and electron affinity using the ΔSCF approach and their values corrected for electron correlation by the 2nd order perturbation theory (MP2). Also, the Mulliken electronegativity and Pearson hardness were evaluated. These properties have been mutually correlated by employing the statistical multivariate methods: the cluster analysis, the probabilistic neural network classifier, the principal component analysis, and the Pearson pair correlation. In addition, the molecular electrostatic potential mapped on the isovalue surface of charge density has been drawn. After the full vibrational analysis, thermodynamic properties at 300 K were evaluated: internal energy, entropy, and the free energy.

Heterometallic CuIIFeIII and CuIIMnIII alkoxo-bridged complexes revealing a rare hexanuclear M6(µ-X)7(µ3-X)2 molecular core.

The novel hexanuclear complexes [Cu4Fe2(OH)(Piv)4(tBuDea)4Cl]·0.5CH3CN (1) and [Cu4Mn2(OH)(Piv)4(tBuDea)4Cl] (2) were prepared through one-pot self-assembly reactions of copper powder and iron(ii) or manganese(ii) chloride with N-tert-butyldiethanolamine (H2tBuDea) and pivalic acid (HPiv) in acetonitrile. Crystallographic studies revealed the uncommon molecular core type M6(µ-X)7(µ3-X)2 in 1 and 2, which can be viewed as a combination of two trimetallic M3(µ-X)2(µ3-X) fragments joined by three bridging atoms. The analysis and classification of the hexanuclear complexes having a M3(µ-X)2(µ3-X) moiety as a core forming fragment using data from the Cambridge Structural Database (CSD) were performed. Variable-temperature (1.8-300 K) magnetic susceptibility measurements of 1 showed a decrease of the effective magnetic moment value at low temperature, indicative of antiferromagnetic coupling between the magnetic centres (JFe-Cu/hc = -6.9 cm-1, JCu-Cu/hc = -4.1 cm-1, JFe-Fe/hc = -24.2 cm-1). Complex 1 acts as a catalyst in the reaction of mild oxidation of cyclohexane with H2O2, showing the yields of products, cyclohexanol and cyclohexanone, up to 17% using pyrazinecarboxylic acid as a promoter. In the oxidation of cis-1,2-dimethylcyclohexane with m-chloroperoxybenzoic acid (m-CPBA), 70% of retention of stereoconfiguration was observed for tertiary alcohols. Compound 1 also catalyses the amidation of cyclohexane with benzamide. In all three catalytic reactions the by-products were investigated in detail and discussed.

Details make the difference: a family of tetranuclear CuIIMnIII complexes with cube-like and double open cube-like cores.

The "direct synthesis" approach, namely one-pot reaction of metal powders and ammonium salt with a methanol solution of a polydentate Schiff base (H2L) formed in situ from salicylaldehyde and ethanolamine, has been successfully used for the preparation of the new heterometallic compounds [Cu3Mn(L)4(CH3OH)3]I3 (1), [Cu3Mn(L)4(CH3OH)3(H2O)]NCS·H2O (2), [Cu3Mn(L)4(CH3OH)(H2O)2.55]Br·0.45H2O (3) and [Cu3Mn(L)4(H2O)3.4]BF4·0.6H2O (4). Crystallographic analysis revealed that 1-4 are based on the tetranuclear core {CuMnIII(µ3-O)4} where the metal centres are joined by the oxygen bridges of Schiff base ligands forming a cube-like arrangement. The novel heterometallic compound [Cu3Mn(L)4(CH3OH)3]2[Mn(NCS)4]·2CH3OH (5) has been obtained by the "building block" approach using the reaction of [Cu(HL)2] with manganese acetate and NH4NCS in methanol. The crystal structure of 5 revealed the {CuMnIII(µ-O)2(µ3-O)2} metal core which can be viewed as a double open cube. In spite of a similar {Cu3MnO4} atom set in the cores of 1-5, the complexes show rather different molecular structures and significantly differ by the number and combinations of coordinated CH3OH/H2O solvent molecules. Variable-temperature (2-300 K) magnetic susceptibility along with variable-field magnetization measurements of 1-5 showed a decrease of the effective magnetic moment value at low temperature, indicative of the antiferromagnetic coupling of medium size (-55 to -22 cm-1). For these systems resembling a compressed prism the coupling constant in walls J4 correlates with the averaged bonding angles in walls α: J4vs. α develops approximately according to a straight line.

Field-Assisted Slow Magnetic Relaxation in a Six-Coordinate Co(II)-Co(III) Complex with Large Negative Anisotropy.

The reaction of Co(CH3COO)2·4H2O with the Schiff base ligand LH4 derived from o-vanillin and tris(hydroxymethyl)aminomethane produces the dinuclear mixed-valence complex [CoIICoIII(LH2)2(CH3COO)(H2O)](H2O)3 (1), which has been investigated using IR spectroscopy, X-ray crystallography, temperature-dependent magnetic susceptibility, magnetization, HFEPR spectroscopy, and ac susceptibility measurements at various frequencies, temperatures, and external magnetic fields. The structure of 1 consists of neutral molecules in which two cobalt ions with distorted octahedral geometries, CoIIO6 and CoIIIN2O4, are bridged by two deprotonated -CH2O- groups of the two LH22- ligands. 1 completes a series with Cl, Br, NO3, and NCS anions published before by different authors. Low-temperature HFEPR measurements reveal that the ground electronic state of the Co(II) center in 1 is a highly anisotropic Kramers doublet; the effective g values of 7.18, 2.97, and 1.96 are frequency-independent over the frequency ranges 200-630, 200-406, and 200-300 GHz for the highest, intermediate, and lowest geff values, respectively. The two lower values were not seen at higher frequencies because the magnetic field was not high enough. Temperature-dependent magnetic susceptibility and field-dependent magnetization data confirm high magnetic anisotropy of the easy axis type. Complex 1 behaves as a single-ion magnet under a small applied external field and demonstrates two relaxation modes that strongly depend on the applied static dc field. The observation of multiple relaxation pathways clearly distinguishes 1 from the Cl and Br analogues.