Large Magnetic Anisotropy in Mono- and Binuclear cobalt(II) Complexes: The Role of the Distortion of the Coordination Sphere in Validity of the Spin-Hamiltonian Formalism.

To get a better insight into understanding the factors affecting the enhancement of the magnetic anisotropy in single molecule (single ion) magnets, two cobalt(II) complexes based on a tridentate ligand 2,6-di(thiazol-2-yl)pyridine substituted at the 4-position with -methyl-pyrrol-2-yl have been synthesized and studied by X-ray crystallography, AC and DC magnetic data, FIRMS and HFEPR spectra, and theoretical calculations. The change of the counteranion in starting Co(II) salts results in the formation of pentacoordinated mononuclear [Co(mpyr-dtpy)Cl]·2MeCN () complex and binuclear [Co(mpyr-dtpy)][Co(NCS)] () compound. The observed marked distortion of trigonal bipyramid geometry in and cationic octahedral and anionic tetrahedral units in brings up a question about the validity of the spin-Hamiltonian formalism and the possibility of determining the value and sign of the zero-field splitting parameter.

Insights into the binding of half-sandwich phosphino Ir(III) and Ru(II) complexes to deoxyribonucleic acid, albumin and apo-transferrin: Experimental and theoretical investigation.

A group of cytotoxic half-sandwich iridium(III) (Ir(η-Cp*)ClPPhCHOH (IrPOH)), (Ir(η-Cp*)ClP(p-OCHPh)CHOH (IrMPOH)), and ruthenium(II) (Ru(η-p-cymene)ClPPhCHOH (RuPOH), Ru(η-p-cymene)ClP(p-OCHPh)CHOH (RuMPOH)) complexes with phosphine ligands exhibit the ability to (i) slow hydrolysis which is reversed by adding a high NaCl concentration; (ii) oxidation of NADH to NAD; (iii) induction of cytotoxicity towards various cancer cell lines. Furthermore, we found that RuPOH and RuMPOH selectively inhibit the proliferation of skin cancer cells (WM266-4) while Ir(III) complexes were found to be moderate against prostate cancer cells (DU-145). Herein, to elucidate the cytotoxic effects, we investigated the interaction of these complexes with DNA and serum proteins by gel electrophoresis, fluorescence spectroscopy, and molecular docking studies.

Antibactericidal Ir(III) and Ru(II) Complexes with Phosphine-Alkaloid Conjugate and Their Interactions with Biomolecules: A Case of N-Methylphenethylamine.

The phosphine ligand (Ph PCH N(CH )(CH ) Ph, PNMPEA) obtained by the reaction of the (hydroxymethyl)diphenylphosphine with naturally occurring alkaloid N-methylphenethylamine, was used to synthesize the half-sandwich iridium(III) (Ir(η -Cp*)Cl Ph PCH N(CH )(CH ) Ph, IrPNMPEA) and ruthenium(II) (Ru(η -p-cymene)Cl Ph PCH N(CH )(CH ) Ph, RuPNMPEA) complexes. They were characterized using a vast array of methods, including 1D and 2D NMR, ESI(+)MS spectrometry, elemental analysis, cyclic voltammetry (CV), electron spectroscopy in the UV-Vis range (absorption, fluorescence) and density functional theory (DFT). The initial antimicrobial activity in vitro toward Gram-positive and Gram-negative bacterial strains was examined, indicating that both complexes are selective towards Gram-positive bacteria, e.

Liposomal Binuclear Ir(III)-Cu(II) Coordination Compounds with Phosphino-Fluoroquinolone Conjugates for Human Prostate Carcinoma Treatment.

Novel heteronuclear Ir-Cu coordination compounds ([Ir(η-Cp*)ClPcfx-Cu(phen)](NO)·1.75(CHOH)·0.75(HO) (), [Ir(η-Cp*)ClPnfx-Cu(phen)](NO)·1.

: Synthesis, Physicochemical, and Biological Properties of Phosphino Cu, Ru, Ir Complexes.

Two novel phosphine ligands, PhPCHN(CHCH) () and PhPCHN(CHCHCHCH) (), and six new metal (Cu(I), Ir(III) and Ru(II)) complexes with those ligands: iridium(III) complexes: Ir(η5-Cp*)Cl() (), Ir(η5-Cp*)Cl() () (Cp*: Pentamethylcyclopentadienyl); ruthenium(II) complexes: Ru(η6-p-cymene)Cl() (), Ru(η6-p-cymene)Cl() () and copper(I) complexes: [Cu(CHCN)()BF] (), [Cu(CHCN)()BF] () were synthesized and characterized using elemental analysis, NMR spectroscopy, and ESI-MS spectrometry. Copper(I) complexes turned out to be highly unstable in the presence of atmospheric oxygen in contrast to ruthenium(II) and iridium(III) complexes. The studied Ru(II) and Ir(III) complexes exhibited promising cytotoxicity towards cancer cells in vitro with IC values significantly lower than that of the reference drug-cisplatin.

Evaluation of anticancer activity in vitro of a stable copper(I) complex with phosphine-peptide conjugate.

[CuI(2,9-dimethyl-1,10-phenanthroline)P(p-OCH-Ph)CHSarcosineGlycine] (1-MPSG), highly stable in physiological media phosphino copper(I) complex-is proposed herein as a viable alternative to anticancer platinum-based drugs. It is noteworthy that, 1-MPSG significantly and selectively reduced cell viability in a 3D spheroidal model of human lung adenocarcinoma (A549), in comparison with non-cancerous HaCaT cells. Confocal microscopy and an ICP-MS analysis showed that 1-MPSG effectively accumulates inside A549 cells with colocalization in mitochondria and nuclei.

Interaction between DNA, Albumin and Apo-Transferrin and Iridium(III) Complexes with Phosphines Derived from Fluoroquinolones as a Potent Anticancer Drug.

A group of cytotoxic half-sandwich iridium(III) complexes with aminomethyl(diphenyl)phosphine derived from fluoroquinolone antibiotics exhibit the ability to (i) accumulate in the nucleus, (ii) induce apoptosis, (iii) activate caspase-3/7 activity, (iv) induce the changes in cell cycle leading to G2/M phase arrest, and (v) radicals generation. Herein, to elucidate the cytotoxic effects, we investigated the interaction of these complexes with DNA and serum proteins by gel electrophoresis, fluorescence spectroscopy, circular dichroism, and molecular docking studies. DNA binding experiments established that the complexes interact with DNA by moderate intercalation and predominance of minor groove binding without the capability to cause a double-strand cleavage.