DFT and TD-DFT studies on copper(II) complexes with tripodal tetramine ligands

480-485Copper(II) complexes, containing aliphatic tripodal tetramine ligand, [Cu(trpn)(NH3)]2+ (1), [Cu(tren)(NH3)]2+ (2), [Cu(332)(NH3)]2+ (3) and [Cu(322)(NH3)]2+ (4) are optimized at B3LYP/ LANL2DZ and B3LYP/GEN levels of theory in gas phase (where (trpn), (tren), (332) and (322) are N(CH2CH2CH2NH2)3, N(CH2CH2NH2)3, N[(CH2CH2CH2NH2)2(CH2CH2NH2)] and N[(CH2CH2CH2NH2)(CH2CH2NH2)2], respectively). The optimization results show that the copper(II) center is trigonal bipyramidal for the studied complexes. Charge distributions on the donor and acceptor atoms are evaluated by natural population analysis. The charge distribution indicates that the ligands transfer their negative charges to copper(II) ions during formation of the complexes. Electronic excitation energies of copper(II) complexes are calculated with time dependent density functional theory in gas phase. <span style="mso-ansi-language: EN" lang="EN">It is found that the most intense bands at electronic spectra of complexes stem from <i style="mso-bidi-font-style: normal">dxz, dyz→dz2 or dx2-y2, dxy→<i style="mso-bidi-font-style: normal">dz2 transitions. </span

Indium triflate and ionic liquid-mediated Friedländer synthesis of 2-acylquinolines

<p>Friedländer synthesis of 2-acylquinolines from the reaction of symmetrical and unsymmetrical 1,2-diketones with 2-aminoarylketones in the presence of indium triflate (In(OTf)₃) and ionic liquid gives quantitative yields. Once the reaction was completed, the catalysts can be recovered and subsequently run for next cycles. Results obtained from theoretical studies have been more strengthened by FT-IR, FT-NMR chemical shifts, and structural parameters which were attained with B3LYP/6-31G(d,p) level of theory and the related results were demonstrated with the experimental interpretations.</p

Experimental and in silico studies of dichloro-tetrakis(1H-pyrazole)-cobalt(II): Structural description, photoluminescent behavior and molecular docking

A novel pyrazole-based Co(II) complex, namely dichloro-tetrakis(1H-pyrazole)-cobalt(II), was synthesized and characterized. Its X-ray crystal structure showed that it crystallizes in the monoclinic C2/c space group with discrete [CoPz4Cl2] units held together via intra- and intermolecular hydrogen bonds. The non-covalent interactions were explicitly analyzed by means of the topological and Hirshfeld surface analyses, revealing the presence of 0-periodic binodal 1,6-connected 1,6M7–1 and 14-connected uninodal bcu–x topologies built up through N—H…Cl and C—H…Cl hydrogen-bonding networks in addition to weak non-classical H…H, Nsingle bondH…C, Csingle bondH…N, N—H…π, π…lp/lp…π and lp…lp interactions. Additionally, interactions energy and energy frameworks analyses were performed in order to compute the total energies of the possible intermolecular interactions. The empty space in the crystal lattice was analyzed using void mapping which lead to the presence of small cavities. The structure was furthermore optimized showing a very good agreement with the experimental results, the molecular electrostatic potential (MEP) maps were obtained with their active regions and the non-linear optical properties estimated. Additionally, the optical properties of the title complex were investigated at room temperature using optical UV-visible absorption and photoluminescence spectroscopy, exhibiting π → π*, n → π*, d → d and ligand-field transitions which result in a large variety of emission bands predominant by a bright red photoluminescence. An in silico study was carried out and the binding ability of the title complex with Staphylococcus aureus tyrosyl-tRNA synthetase and Pyrococcus kodakaraensis aspartyl-tRNA synthetase was evaluated displaying a good inhibition activity towards the last one.Funding was provided by the General Direction of research and development technologies/Ministry of Higher Education and Research Sciences DGRSDT/MESRS, Algeria. The financial support from Abbes Laghrour University of Khenchela (Algeria), TUBITAK ULAKBIM, High Performance and Grid Computing Center (TR-Grid e-Infrastructure), Spanish MINECO (MAT2016–78155-C2–1-R), Gobierno del Principado de Asturias (GRUPIN-IDI/2018/000170) are acknowledged. This work is supported by the Scientific Research Project Fund of Sivas Cumhuriyet University under the project number RGD-020.Peer reviewe