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A series of heteroleptic square-planar Pt and Pd complexes with bis(diisopropylphenyl) iminoacenaphtene (dpp-Bian) and Cl, 1,3-dithia-2-thione-4,5-dithiolate (dmit), or 1,3-dithia-2-thione-4,5-diselenolate (dsit) ligands have been prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis, and cyclic voltammetry (CV). The intermolecular noncovalent interactions in the crystal structures were assessed by density functional theory (DFT) calculations. The anticancer activity of Pd complexes in breast cancer cell lines was limited by their solubility. Pd(dpp-Bian) complexes with dmit and dsit ligands as well as an uncoordinated dpp-Bian ligand were devoid of cytotoxicity, while the [Pd(dpp-Bian)Cl] complex was cytotoxic. On the contrary, all Pt(dpp-Bian) complexes demonstrated anticancer activity in a low micromolar concentration range, which was 8-20 times higher than the activity of cisplatin, and up to 2.5-fold selectivity toward cancer cells over healthy fibroblasts. The presence of a redox-active dpp-Bian ligand in Pt and Pd complexes resulted in the induction of reactive oxygen species (ROS) in cancer cells. In addition, these complexes were able to intercalate into DNA, indicating the dual mechanism of action.
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http://dx.doi.org/10.1021/acs.inorgchem.1c03314 | DOI Listing |
Inorg Chem
March 2023
Institut des Sciences Chimiques de Rennes, Université de Rennes, CNRS, UMR 6226, F-35000 Rennes, France.
Highly conducting, mixed-valence, multi-component nickel bis() salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)] (Me-thiazds: -methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (EtN and BuN PhP, respectively). This behavior strongly differs from that of the corresponding monoanionic complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands.
View Article and Find Full Text PDFInorg Chem
January 2022
Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Acad. Lavrentiev Ave., Novosibirsk 630090, Russia.
A series of heteroleptic square-planar Pt and Pd complexes with bis(diisopropylphenyl) iminoacenaphtene (dpp-Bian) and Cl, 1,3-dithia-2-thione-4,5-dithiolate (dmit), or 1,3-dithia-2-thione-4,5-diselenolate (dsit) ligands have been prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis, and cyclic voltammetry (CV). The intermolecular noncovalent interactions in the crystal structures were assessed by density functional theory (DFT) calculations. The anticancer activity of Pd complexes in breast cancer cell lines was limited by their solubility.
View Article and Find Full Text PDFDalton Trans
December 2014
Institute of Applied Physics, University of Bern, Sidlerstrasse 5, CH-3012 Bern, Switzerland.
Ultrafast excited-state dynamics of planar Pt, Pd, and Ni dithione-dithiolato complexes were investigated by transient absorption spectroscopy on the femtosecond-picosecond timescale. All studied complexes show a common photobehaviour, although individual kinetics parameters and quantum yields vary with the metal, the dithione ligand and, namely the solvent (DMF, MeCN). Laser pulse irradiation at 800 nm populates the lowest singlet excited state of a dithiolato → dithione charge transfer character, (1)LL'CT.
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October 2012
Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, Unità di Ricerca dell'INSTM, S.S. 554-Bivio per Sestu, I09042 Monserrato-Cagliari, Italy.
The donor-acceptor type mixed-ligand complexes [M(Bz(2)pipdt)(dsit)]; dsit = 2-thioxo-1,3-dithiole-4,5-diselenolato (donor); Bz(2)pipdt = 1,4-dibenzyl-piperazine-2,3-dithione (acceptor); M(II) = Ni (1), Pd (2), and Pt (3) were prepared and characterized to investigate the variation of the properties by substituting selenium for sulfur in the donor ligand dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato of the corresponding known complexes. Both these classes of complexes exhibit large negative second-order polarizabilities, amongst the highest values determined so far for metal-complexes, and are potential candidates for redox switchability of the molecular first hyperpolarizability due to the bleaching/restoring of the solvatochromic peak for mono-reduction/oxidation. DFT and TD-DFT calculations on 1-3 allow one to correlate geometries and electronic structures and are in agreement with the observed minor changes following the substitution of selenium for sulfur atoms in the dichalcogenolato ligand.
View Article and Find Full Text PDFInorg Chem
October 2008
Departament de Quimica Fisica i Analitica, Universitat Jaume I, Campus de Riu Sec, Avda. Sos Baynat s/n, E- 12071 Castello, Spain.
A general route for the preparation of a series of dianionic Mo3S7 cluster complexes bearing dithiolate or diselenolate ligands, namely, [Mo3S7L3](2-) (where L = tfd (bis(trifluoromethyl)-1,2-dithiolate) (4(2-)), bdt (1,2-benzenedithiolate) (5(2-)), dmid (1,3-dithia-2-one-4,5-dithiolate) (6(2-)), and dsit (1,3-dithia-2-thione-4,5-diselenolate) (7(2-))) is reported by direct reaction of [Mo3S7Br6](2-) and (n-Bu)2Sn(dithiolate). The redox properties, molecular structure, and electronic structure (BP86/VTZP) of the 4(2-) to 7(2-) clusters have also been investigated. The HOMO orbital in all complexes is delocalized over the ligand and the Mo3S7 cluster core.
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