New C,N,S-cyclometalated palladium(II) and platinum(II) complexes have been synthesized and their structural, electrochemical, and photochemical properties examined. The blue color of these complexes in solution changed to yellow under visible-light irradiation. By measurement of the absorption spectra for quantifying changes in color, isosbestic points for each complex clearly indicated the presence of only two species responsible for the change of color. X-ray analysis revealed that the visible-light-induced yellow species were S-oxygenated sulfinato complexes. Photosensitized generation of singlet oxygen (O) was confirmed by the direct detection of singlet oxygen luminescence at 1275 nm. The present cyclometalated palladium(II) and platinum(II) complexes are efficient photosensitizers of singlet oxygen, which rapidly reacts with coordinating sulfur atoms.
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http://dx.doi.org/10.1021/acs.inorgchem.9b01492 | DOI Listing |
Molecules
December 2024
Institute of Chemistry, Faculty of Science and Technology, Jan Dlugosz University in Czestochowa, Armii Krajowej 13/15, 42-200 Czestochowa, Poland.
This study investigates the structural, vibrational, and biological properties of novel palladium(II) and platinum(II) complexes with 5-chloro-7-azaindole-3-carbaldehyde (5ClL) and 4-chloro-7-azaindole-3-carbaldehyde (4ClL) ligands. Infrared and Raman spectroscopy, combined with DFT (ωB97X-D) calculations, provided valuable information about metal-ligand interactions, the or conformation of the aldehyde group in the ligands, and the presence of isomers in the metal complexes obtained in the solid state. tests were used to evaluate the antiproliferative activity of the novel complexes against several cancer cell lines, including ovarian cancer (A2780), cisplatin-resistant ovarian cancer (A2780cis), colon cancer (HT-29), and triple-negative breast cancer (MDA-MB-231), as well as normal mouse fibroblasts (BALB/3T3).
View Article and Find Full Text PDFChemphyschem
November 2024
University of Belgrade: Univerzitet u Beogradu, Faculty of Physical Chemistry, SERBIA.
The stepwise, one-pot synthesis of heterobimetallic carbene gold(i) platinum(ii) complexes from readily available starting materials is presented. The protecting group free methodology is based on the graduated nucleophilicities of aliphatic and aromatic amines as linkers between both metal centers. This enables the selective, sequential installation of the metal fragments.
View Article and Find Full Text PDFJ Phys Chem A
September 2024
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States.
Metalloporphyrins are ubiquitous in their applications as triplet photosensitizers, particularly for promoting sensitized photochemical upconversion processes. In this study, bimolecular excited state triplet-triplet quenching kinetics, termed homomolecular triplet-triplet annihilation (HTTA), exhibited by the traditional triplet photosensitizers-zinc(II) tetraphenylporphyrin (ZnTPP), palladium(II) octaethylporphyrin (PdOEP), platinum(II) octaethylporphyrin (PtOEP), and platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP)─were revealed using conventional transient absorption spectroscopy. Nickel(II) tetraphenylporphyrin was used as a control sample as it is known to be rapidly quenched intramolecularly through ligand-field state deactivation and, therefore, cannot result in triplet-triplet annihilation (TTA).
View Article and Find Full Text PDFMolecules
July 2024
Department of Inorganic Chemistry, Faculty of Pharmacy, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain.
This work describes the synthesis of eight new Pd(II) and Pt(II) complexes with the general formula [M(TSC)Cl], where TSC represents the 4N-monosubstituted thiosemicarbazone derived from 2-acetylpyridine N-oxide with the substituents CH (H4MLO), CH (H4ELO), phenyl (H4PLO) and (CH) (H4DMLO). These complexes have been characterized by elemental analysis, molar conductivity, IR spectroscopy, H, C, Pt and ESI-MS. The complexes exhibit a square planar geometry around the metallic center coordinated by a thiosemicarbazone molecule acting as a donor ONS-type pincer ligand and by a chloride, as confirmed by the molecular structures of the complexes, [Pd(4ELO)Cl] () and [Pd(4PLO)Cl] (), determined by single-crystal X-ray diffraction.
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