Andrzej Kochel

Copper(I) iodide complexes containing new aliphatic aminophosphine ligands and diimines—luminescent properties and antibacterial activity

The new, water soluble, aminomethylphosphines were synthesized from P(CH2OH)3 and alkylpiperazines: P(CH2N(CH2CH2)2NCH3)3 (1) and P(CH2N(CH2CH2)2NCH2CH3)3 (2). Described already in literature P(CH2N(CH2CH2)2O)3 (3) were also obtained. The spectroscopic 1H, 31P and 13C NMR analyses and crystallographic studies of 1, 2 and 3 demonstrate that all these compounds have similar structures and spectroscopic properties, which almost do not depend on aliphatic rings in the molecules. Heteroleptic copper(I) iodide complexes with phosphines mentioned above and 2,2′-bipyridine (bpy): [CuI(bpy)P(CH2N(CH2CH2)2NCH3)3] (1B), [CuI(bpy)P(CH2N(CH2CH2)2NCH2CH3)3] (2B), [CuI(bpy)P(CH2N(CH2CH2)2O)3] (3B) or 1,10-phenanthroline (phen): [CuI(phen)P(CH2N(CH2CH2)2NCH3)3] (1P), [CuI(phen)P(CH2N(CH2CH2)NCH2CH3)3] (2P), [CuI(phen)P(CH2N(CH2CH2)2O)3] (3P) were also synthesized. All complexes were characterized by 1H, 31P and 13C NMR spectroscopy also. Molecular structures of 1P·PhCH3 and 3P·0.5Cu2I2(phen)2 were determined from single crystal X-ray diffraction studies. Upon excitation at 470 nm, all complexes in the solid state exhibit red photoluminescence due to charge transfer transition. The luminescence of phen complexes is higher than the luminescence of bpy ones. The presented phosphines and copper(I) complexes were screened for their in vitro antibacterial and antifungal activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus strains and Candida albicans. All the copper complexes exhibit significant antibacterial activity against Staphylococcus aureus strains. The activity of 1,10-phenanthroline complexes is higher than 2,2′-bipyridine complexes.

Dimethyl Sulfoxide Containing Platinum(II) and Palladium(II) Chelate Complexes of Glyoxylic and Pyruvic Acid Thiosemicarbazones. A New Class of Cytotoxic Metal Complexes

Abstract The complexes [Pt(DMSO)(GT)]·DMSO (1), [Pt(DMSO)(PT)]· 1/2 DMSO (2) and [Pd(DMSO)- (PT)] (3), where DMSO = dimethyl sulfoxide, H2GT = glyoxylic acid thiosemicarbazone and H2PT = pyruvic acid thiosemicarbazone, have been synthesized and characterized by elemental analysis, molar electric conductivity, IR, electronic and NMR (1H and 13C) spectra. The single crystal X-ray diffraction analysis has revealed for 1 (orthorhombic, Pnma, a = 12.941(3), b = 7.108(2), c = 15.148(3) Å , Z = 4) that the doubly deprotonated thiosemicarbazone molecule is coordinated to Pt(II) via the carboxylato O, azomethine N and thiolato S atoms forming two condensed fivemembered chelate rings. The fourth coordination site of Pt(II) is occupied by the S atom of DMSO. All the atoms of the complex molecule are coplanar except the methyl groups. The O atom of DMSO is in cis-position towards the thiolato-S atom (point group Cs). A system of hydrogen bonds of the type N-H· · ·O links the complex molecules between them and with the lattice DMSO molecules. Similar structures have been deduced for the remaining two complexes on the basis of spectroscopic data. The three complexes and the ligand H2GT exhibit cytotoxic activity against F4N leukemia cells, whereas the ligand H2PT is inactive.

1–D Framework l-arginine zinc(II) units bridged by oxalate: synthesis, structure, properties, and theoretical studies

Abstract We synthesized a l-arginine containing Zn2+ complex and oxalate ions. {[Zn2(l-Arg)2(ox)2]·8H2O}n (1) (l-Arg  =l-arginine, ox  =  oxalate) crystallize in the monoclinic space group P21 with a  =  8.979(2), b  =  9.840(2) (Å), c  =  18.509(3) (Å), β  =  95.58(3) (Å), V  =  1627.6(6) Å3, and Z  =  2. The zinc centers are six-coordinate via one l-arginine zwitterion and two bridging oxalates. The binuclear [Zn2(l-Arg)2(ox)2] units are linked via oxalate and form 1-D “stair-like” linear chains. The complex was characterized using FT-IR, FT-Raman, UV–vis spectroscopy, and thermal analysis techniques, as well as DFT methods. Electronic bands above 31,000 cm−1 originate in 1,3Au (n→π*) transitions within oxalate ions. Theoretical studies were performed for the model compound {[Zn(l-Arg)(Hox)2]·4H2O} using the fragment of the crystallographic structure of 1. The interaction energy (ΔE) values for l-arginine and two oxalate ions are comparable at -145 kcal mol−1. Natural bond orbital (NBO) analysis of the electronic structure and bonding is also discussed.

The conformational analysis of 2-hydroxyaryl Schiff thiosemicarbazones

X-Ray measurements and quantum-mechanical (B3LYP and MP2) calculations of 2-hydroxyaryl Schiff thiosemicarbazones were performed to describe the tautomeric and conformational equilibrium. The structures of five N-alkyl- and N-aryl-thiosemicarbazone derivatives were determined by single-crystal X-ray diffraction at 100 K. The conformational schemes for determining the various states of the compounds were calculated by the DFT (B3LYP/6-31+G(d,p)) method. The difference between the phenolic and heterocyclic derivatives with respect to the OH ⇆ HN tautomeric equilibrium is shown. The influence of the environments polarity on CS ⇆ SC conformational equilibrium was determined by DFT calculations. The potential energy curves for rotating particular fragments of the thiosemicarbazone moiety were calculated to estimate the rotational energetic barriers.

4-(4-Pyrid­yl)pyridinium triiodide

We are presently interested in the syntheses and structures of dioxorhenium(V) halide salts (Kochel, 2006). The title compound, (I) (Fig. 1), arose as an unexpected product in this system. The asymmetric unit contains a monoprotonated 4,40bipirydinium cation and an I3 triiodide anion. The geometry of the I3 species (Table 1) is normal (Wieczorrek, 2000). The closest contact beteen I atoms in different anions is 3.8880 (6) Å for I2 I3 [symmetry code: (i) x, y 1, z]; this is 0.07 Å shorter than the van der Waals contact distance of 3.96 Å for two I atoms (Bondi, 1964). The dihedral angle between the aromatic rings in the cation is 33.5 (3) .

2,2′-Bipyrimidinium hexa­chloro­rhenate(IV) dihydrate

In the title compound, (C8H8N4)[ReCl6]·2H2O, the Re atom occupies an inversion centre and is octahedrally coordinated by chloride anions. The cation also has an inversion centre. Various N—H⋯O, O—H⋯Cl and C—H⋯Cl interactions help to stabilize the crystal packing.

Why Does the 2,2′-Bipyridine-4-methyl-3,3′-Dicarboxylic Acid Not Form MOFs: Synthesis, Crystal Structure and Properties of a New Organic Ligand

Abstract2,2′-Bipyridine-4-methyl-3,3′-dicarboxylic acid monohydrate (1) is introduced as a new organic ligand. Synthesis, structure and properties (TGA, IR, NMR) are characterized. 1 includes an extensive hydrogen bonding network with formation of various graph-set motifs, such as

Impact of the Keto–Enol Tautomeric Equilibrium on the BODIPY Chromophore

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