Ruthenium nitrosyl complexes of the general formulas (cation)+[cis-RuCl4(NO)(Hazole)]−, where (cation)+ = (H2ind)+, Hazole = 1H-indazole (Hind) (1c), (cation)+ = (H2pz)+, Hazole = 1H-pyrazole (Hpz) (2c), (cation)+ = (H2bzim)+, Hazole = 1H-benzimidazole (Hbzim) (3c), (cation)+ = (H2im)+, Hazole = 1H-imidazole (Him) (4c) and (cation)+[trans-RuCl4(NO)(Hazole)]−, where (cation)+ = (H2ind)+, Hazole = 1H-indazole (1t), (cation)+ = (H2pz)+, Hazole = 1H-pyrazole (2t), as well as osmium analogues of the general formulas (cation)+[cis-OsCl4(NO)(Hazole)]−, where (cation)+ = (n-Bu4N)+, Hazole =1H-indazole (5c), 1H-pyrazole (6c), 1H-benzimidazole (7c), 1H-imidazole (8c), (cation)+ = Na+; Hazole =1H-indazole (9c), 1H-benzimidazole (10c), (cation)+ = (H2ind)+, Hazole = 1H-indazole (11c), (cation)+ = H2pz+, Hazole = 1H-pyrazole (12c), (cation)+ = (H2im)+, Hazole = 1H-imidazole (13c), and (cation)+[trans-OsCl4(NO)(Hazole)]−, where (cation)+ = n-Bu4N+, Hazole = 1H-indazole (5t), 1H-pyrazole (6t), (cation)+ = Na+, Hazole = 1H-indazole (9t), (cation)+ = (H2ind)+, Hazole = 1H-indazole (11t), (cation)+ = (H2pz)+, Hazole = 1H-pyrazole (12t), have been synthesized. The compounds have been comprehensively characterized by elemental analysis, ESI mass spectrometry, spectroscopic techniques (IR, UV–vis, 1D and 2D NMR) and X-ray crystallography (1c·CHCl3, 1t·CHCl3, 2t, 3c, 6c, 6t, 8c). The antiproliferative activity of water-soluble compounds (1c, 1t, 3c, 4c and 9c, 9t, 10c, 11c, 11t, 12c, 12t, 13c) in the human cancer cell lines A549 (nonsmall cell lung carcinoma), CH1 (ovarian carcinoma), and SW480 (colon adenocarcinoma) has been assayed. The effects of metal (Ru vs Os), cis/trans isomerism, and azole heterocycle identity on cytotoxic potency and cell line selectivity have been elucidated. Ruthenium complexes (1c, 1t, 3c, and 4c) yielded IC50 values in the low micromolar concentration range. In contrast to most pairs of analogous ruthenium and osmium complexes known, they turned out to be considerably more cytotoxic than chemically related osmium complexes (9c, 9t, 10c, 11c, 11t, 12c, 12t, 13c). The IC50 values of Os/Ru homologs differ by factors (Os/Ru) of up to ∼110 and ∼410 in CH1 and SW480 cells, respectively. ESI-MS studies revealed that ascorbic acid may activate the ruthenium complexes leading to hydrolysis of one M–Cl bond, whereas the osmium analogues tend to be inert. The interaction with myoglobin suggests nonselective adduct formation; i.e., proteins may act as carriers for these compounds.
New europium(III) β-diketonate based complexes with the general formula [Eu(β-Dik)3(NL)x], where β-Dik = 2thenoyltrifluoroacetonate, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, NL = diphenyl sulfoxide (x = 2), bis[2-(diphenylphosphino)phenyl] ether oxide (x = 1), triphenylphosphine oxide (x = 2), 5,6epoxy-5,6-dihydro-[1,10]phenanthroline (x = 1), are designed and synthesized. The coordination complexes are comprehensively characterized by elemental analysis, infrared and 1 H, 13 C, 19 F NMR spectroscopy. The complexes are embedded into poly(ethylene-co-vinyl acetate) (EVA), poly(methyl methacrylate) (PMMA) or poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (PVB) matrices. Photoluminescence behavior is investigated in detail and exhibits the characteristic 5 D0→ 7 F0-4 emission bands with quantum yields of 55-83 % in the solid state and 34-86 % in the polymers. Encapsulation of CIGS solar cells with luminescent downshifting (LDS) layer results in an important improvement of external quantum efficiency (EQE) in the UV region, from 14 % and up to 58 % at 360 nm for the best compound. The short circuit current density (Jsc) in the range of 300-400 nm increases up to 0.77 mA/cm 2 for the best LDS which corresponds to 71 % of the Jsc enhancement of an ideal downshifter. I-V measurements follow the spectral response data with an absolute increase in conversion efficiency of up to 0.8 %.emission bands, whose 5 D 0 → 7 F 2 transition at ca 613 nm transition reaches up to 80-90 % of all emission light and milliseconds photoluminescence (PL) lifetime. 23 The long term stability upon light irradiation and high thermal decomposition
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