New first-row transition-metal compounds with the ligand norharmane (9H-Pyrido[3,4-b]indole; Hnor) are reported. The compounds have the general formula [M(LL)(Hnor)(NO3)(2)](MeOH)(0-1) (M = Co, Ni,... Show moreNew first-row transition-metal compounds with the ligand norharmane (9H-Pyrido[3,4-b]indole; Hnor) are reported. The compounds have the general formula [M(LL)(Hnor)(NO3)(2)](MeOH)(0-1) (M = Co, Ni, Cu, Zn; LL 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen)) and have been characterized by physical and analytical methods. X-ray structural analysis revealed that the compound of formula [Cu(phen)(Hnor)(NO3)(2)], (1) has a distorted 6-coordinated octahedrally-based geometry, with a planar-based [CuN3O] core, where Cu-L varies between 1.99 and 2.04 angstrom and two weak axial Cu-O contacts (2.209 and 2.644 angstrom) from two different nitrates. Based on spectroscopic similarities, the other compounds appear to have the same or very similar coordination geometries. The compounds showed clear cell growth inhibitory effects in two different cancer cell lines in vitro, with the copper and zinc complexes being the most toxic and in fact almost comparable to cisplatin. Flow-cytometry analysis confirmed induction of apoptosis in cancer cells treated with the compounds. Interestingly, co-incubation of the cells with metal complexes and CuCl2 induced an increase in the cytotoxic effects, most likely due to the conversion of the metal compounds in the corresponding, and most active, copper analogues. (C) 2016 Elsevier Inc. All rights reserved. Show less
Khan, R.A.; Dielmann, F.; Liu, X.; Hahn FE, Al-Farhan, K.; Alsalme, A.; Reedijk, J. 2016
Three isomorphous compounds have been prepared, i.e. [Cu-I(PPh3)(2)(Hnor)(I)], [Cu-I(PPh3)(2)(Hnor)Cl] and [Cu-I(PPh3)(2)(Hnor)Br]. The compounds are tetrahedrally coordinated, as deduced from the... Show moreThree isomorphous compounds have been prepared, i.e. [Cu-I(PPh3)(2)(Hnor)(I)], [Cu-I(PPh3)(2)(Hnor)Cl] and [Cu-I(PPh3)(2)(Hnor)Br]. The compounds are tetrahedrally coordinated, as deduced from the single-crystal X-ray diffraction analysis of the iodide compound. The chloride and bromide compounds were found to be isomorphous. Significant twinning hampered a detailed X-ray diffraction study of the bromide derivative. All three compounds are highly luminescent in the solid state at room temperature and at 100 K. In addition, in acetonitrile (solution) at room temperature the compounds are luminescent. (C) 2016 Elsevier Ltd. All rights reserved. Show less
Jaafar, M.; Liu, X.; Dielmann, F.; Hahn, F.E.; Al-Farhan, K.; Alsalme, A.; Reedijk, J. 2016
Four new compounds containing the (chlorido)((2-x))(cyanido)(x)argentate(I) anion (x = 2, 1.63, 1 and 0.5) are reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane... Show moreFour new compounds containing the (chlorido)((2-x))(cyanido)(x)argentate(I) anion (x = 2, 1.63, 1 and 0.5) are reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane) iminium, are described; in a few cases the products also contain solvent molecules. The compounds have the formula (PPN)(2)[Ag2Cl3(CN)], (PPN)[Ag(CN)Cl](CH2Cl2) and (PPN)[Ag(CN)(1.63)Cl-0.37](hexane)(0.5) and (PPN)[Ag(CN)(2)] (CH2Cl2). Apart from the molecular structures and the synthetic process, also the solid-state luminescence has been studied.In the case of (PPN)(2)[Ag2Cl3(CN)], the silver ions are pseudo-trigonally coordinated, with 2 chloride bridges between the Ag+ ions. The terminal Cl and terminal CN ligands are disordered over two positions, but only a single C-13 NMR signal is observed for the cyanide ligands of this compound. The compound (PPN)[Ag(CN)(2)] serves as a reference compound and contains the linear [Ag(CN)(2)] unit.The compound with CN/Cl = 1.0 shows disorder of the [AgCl(CN)] unit, and also in the compounds with other CN/Cl ratios, disorder among the Cl - and CN - ligands is seen. The Ag+ ion is linearly coordinated by two ligands in these two cases, and for cyanides normal Ag-C bond lengths are observed in both cases (1.97-1.99 angstrom). The [Ag(CN)(2)] anion is linear and uneventful. The PPN cation has normal bond lengths in all 4 compounds and no short contacts with other atoms in the lattice are observed. The luminescence properties of the new compounds were explored as solid powders. Only one of the compounds (compound 2, with x = 1) shows luminescence under excitation. The other three compounds do not show emission when irradiated at 320 nm, 350 nm or 380 nm. (C) 2015 Elsevier B. V. All rights reserved. Show less
Folda, A.; Scalcon, V.; Ghazzali, M.; Jaafar, M.H.; Khan, R.A.; Casini, A.; ... ; Reedijk, J. 2015
