A series of neutral ruthenium(II) arene complexes [(arene)Ru(Q)Cl] (arene = p-cymene (cym) or hexamethylbenzene (hmb)) containing 4-acyl-5-pyrazolonate Q ligands with different electronic and steric substituents (R = 4-cyclohexyl, 4-stearoyl, or 4-adamantyl) and related ionic complexes [(arene)Ru(Q)(PTA)][PF] (PTA = 1,3,5-triaza-7-phosphaadamantane) were synthesized and characterized by spectroscopy (IR, UV-vis, ESI-MS, and H andC NMR), elemental analysis, X-ray crystallography, and density functional theory studies. The cytotoxicity of the proligands and metal complexes was evaluated in vitro against human ovarian carcinoma cells (A2780 and A2780cisR), as well as against nontumorous human embryonic kidney (HEK293) cells. In general the cationic PTA-containing complexes are more cytotoxic than their neutral precursors with a chloride ligand in place of the PTA. Moreover, the complexes do not show cross-resistance and are essentially equally cytotoxic to both the A2780 and A2780cisR cell lines, although they only show limited selectivity toward the cancer cell lines.

New silver(I) acylpyrazolonato derivatives displaying a mononuclear, polynuclear, or ionic nature, as a function of the ancillary azole ligands used in the synthesis, have been fully characterized by thermal analysis, solution NMR spectroscopy, solid-state IR and NMR spectroscopies, and X-ray diffraction techniques. These derivatives have been embedded in polyethylene (PE) matrix, and the antimicrobial activity of the composite materials has been tested against three bacterial strains (E. coli, P. aeruginosa, and S. aureus): Most of the composites show antimicrobial action comparable to PE embedded with AgNO3 . Tests by contact and release tests for specific migration of silver from PE composites clearly indicate that, at least in the case of the PE, for composites containing polynuclear silver(I) additives, the antimicrobial action is exerted by contact, without release of silver ions. Moreover, PE composites can be re-used several times, displaying the same antimicrobial activity. Membrane permeabilization studies and induced reactive oxygen species (ROS) generation tests confirm the disorganization of bacterial cell membranes. The cytotoxic effect, evaluated in CD34(+) cells by MTT (3-(4,5-dimethylthiazole-2-yl)-2,5-diphenyltetrazoliumbromide) and CFU (colony forming units) assays, indicates that the PE composites do not induce cytotoxicity in human cells. Studies of ecotoxicity, based on the test of Daphnia magna, confirm tolerability of the PE composites by higher organisms and exclude the release of Ag(+) ions in sufficient amounts to affect water environment.

Novel silver(I) acylpyrazolonato coordination polymers of formula [Ag(Q(R))]n (1-3) have been synthesized by interaction of silver nitrate with HQ(R) in methanol in the presence of an equivalent quantity of KOH (in general HQ(R) = 1-phenyl-3-methyl-4-RC(═O)-5-pyrazolone, in detail HQ(fb), R = -CF2CF2CF3; HQ(cy), R = -cyclo-C6H11; HQ(be), R = -C(H)═C(CH3)2). [Ag(Q(R))]n react with 2-ethylimidazole (2EtimH), 1-methylimidazole (Meim), and triphenylphosphine (PPh3), affording the mononuclear Ag(Q(fb))(EtimH) (4), Ag(Q(cy))(Meim)2 (5), Ag(Q(be))(Meim) (6), and Ag(Q(R))(PPh3)2 (7-9). All complexes have been analytically and spectroscopically characterized, and for some of them the X-ray crystal structure has been resolved. In particular, the single crystal molecular structure determination of Ag(Q(fb))(EtimH) and Ag(Q(be))(PPh3)2 has confirmed the different coordination modes of the HQ(fb) and HQ(be) acylpyrazolone ligands, the former being bound to the silver(I) ion in a monodentate fashion while the latter in the O2-chelating mode. Density functional theory computations suggest new insights about metal-ligand interactions and the observed linkage isomerism. While phosphine-containing complexes Ag(Q(R))(PPh3)2 (7-9) seem not to be able to efficiently inhibit the growth of Escherichia coli and Staphylococcus aureus, the polynuclear complexes [Ag(Q(R))]n (1-3) and the mononuclear Ag(Q(fb))(EtimH) (4), Ag(Q(cy))(Meim)2 (5), and Ag(Q(be))(Meim) (6) show a high and almost steady in time antibacterial activity, comparable to that of AgNO3. This activity is likely related to the degree of saturation of the silver center and to the presence of different ancillary ligands in the diverse typologies of complexes.

A series of neutral ruthenium(ii)-arene complexes, [(arene)Ru(Q)Cl] (arene = p-cymene or hexamethylbenzene), containing 4-acyl-5-pyrazolonate (Q) ligands with aromatic substituents in the acyl moiety (a phenyl in Q and a 1-naphthyl in Q) and related ionic complexes [(arene)Ru(Q)(PTA)][PF] (PTA = 1,3,5-triaza-7-phosphaadamantane) have been synthesized and characterized by IR, H,C and P NMR spectroscopy, elemental analysis and ESI mass spectrometry. The structures of five of these compounds were also determined by X-ray crystallography. DFT studies have been performed on all complexes and, in the case of two cationic [(arene)Ru(Q)(PTA)][PF], the existence of two conformers with a different relative orientation of the naphthyl group in the Q ligand has been assessed, showing that they possess similar energies, in agreement with the experimentally observed NMR spectra in solution. The cytotoxicity of the 4-acyl-5-pyrazolonate proligands (HQ) and complexes was evaluated in vitro against human ovarian carcinoma cells (A2780 and A2780cisR) and non-tumorous human embryonic kidney (HEK293) cells. In general, each complex is about equally cytotoxic to all three cell lines and the PTA derivatives with the naphthyl-modified Q ligands are the most active of the series.

Novel composite materials PEn (n = 1-9) have been prepared by an easily up-scalable embedding procedure of three different families of Ag(I) acylpyrazolonato complexes in polyethylene (PE) matrix. In details, PE1-PE3 composites contain polynuclear [Ag(Q)] complexes, PE4-PE6 contain mononuclear [Ag(Q)(L)] complexes and PE7-PE9 are loaded with mononuclear [Ag(Q) (PPh)] complexes, respectively (where L = 1-methylimidazole or 2-ethylimidazole, m = 1 or 2, and HQ = 1-phenyl-3-methyl-4-RC(═O)-5-pyrazolone, where in detail HQ, R = -CFCFCF; HQ, R = -cyclo-CH; HQ, R = -C(H)═C(CH)). The PEn composites, prepared by using a 1:1000 w/w silver additive/polyethylene ratio, have been characterized in bulk by IR spectroscopy and TGA analyses, which confirmed that the properties of polyethylene matrix are essentially unchanged. AFM, SEM, and EDX surface techniques show that silver additives form agglomerates with dimensions 10-100 μm on the polyethylene surface, with a slight increment of surface roughness of pristine plastic within 50 nm. However, the elastic properties of the composites are essentially the same of PE. The antibacterial activity of all composites has been tested against three bacterial strains (E. coli, P. aeruginosa and S. aureus) and results show that two classes of composites, PE1-PE3 and PE4-PE6, display high and persistent bactericidal and bacteriostatic activity, comparable to PE embedded with AgNO. By contrast, composites PE7-PE9 exhibit a reduced antibacterial action. Contact and release tests in several conditions for specific migration of Ag from plastics, indicate a very limited but time persistent release of silver ions from PE1-PE6 composites, thus suggesting that they are potential antibacterial materials for future applications. Instead, PE7-PE9 almost do not release silver, only trace levels of silver ions being detected, in accordance with their reduced antibacterial action. None of the composites is toxic against higher organisms, as confirmed by D. magna test of ecotoxicity.

Novel arylhydrazones of barbituric acid were synthesized and their water soluble AgI, CoII, CoII/III and CuII complexes obtained. The AgI compound shows remarkable cytotoxic and antibacterial activity.

Graphical abstractArylhydrazones of barbituric acid are valuable ligands for Co II , Co II/III and Cu II leading to mononuclear complexes which effectively catalyse the oxidation of cyclohexane. AbstractNew ortho-substituted arylhydrazones of barbituric acid, 5-(2-(2-hydroxyphenyl)hydrazono) pyrimidine-2,4,6(1H,3H,5H)-trione (H 4 L 1 ) and the sodium salt of 2-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazinyl)benzenesulfonic acid (H 4 L 6 ][H 3 L 2 ] 2 ·8H 2 O (6). The complexes are water soluble and the mono-or dideprotonated ligands display different coordination modes, depending on the synthetic conditions. The electrochemical behaviour of all compounds was investigated by cyclic voltammetry and controlled potential electrolysis, revealing that also the ligands are redox active. All compounds were evaluated as catalysts for the peroxidative (with H 2 O 2 ) oxidation of cyclohexane at room temperature. The compounds 2 and 3 are the most active ones (yields up to 21 % and TON up to 213 are achieved, in the presence of 3).

Six scorpionate complexes of group 10-12 metal elements (Cu I , Cu II , Zn II , and Cd II ) containing the anionic hydrotris[3-(2Ј-thienyl)pyrazol-1-yl]borate (Tp Tn ) ligand were prepared from the reaction of the thallium(I) salt of Tp Tn with the corresponding metal acceptors in chloroform solution. The air-and heat-stable complexes were characterized by analytical and spectroscopic methods (IR, conductivity, ESI-MS, 1 H NMR and 13 C NMR solution data) and structurally characterized by single-crystal X-ray studies. The Zn II complexes [Zn-(Tp Tn )X] (X = Cl or Br) contain a tripodal tridentate Tp Tn ligand, in which the tetrahedral metal environment is completed by a halide; in [Cd(Tp Tn ) 2 ], cadmium is found in an octahedral environment coordinated by two Tp Tn ligands. In [Cu(Tp Tn )(PPh 3 )]·CHCl 3 and [Cu(Tp Tn )(OC(O)CH 3 )], Tp Tn is also coordinated in the tripodal fashion, in which the copper environment is completed by a triphenylphosphine ligand in the former complex and by a symmetrically coordinated bi-[a]