A supramolecule, 6, based on an electron-donor zinc phthalocyanine (ZnPc) and an electron-acceptor perylene diimide (PDI) has been synthesized and characterized by elemental analysis, UV/Vis, IR, (1)H NMR and solid state (13)C CPMAS NMR and also MALDI-TOF and ICP mass spectrometry. The PDI appended ZnPc core brings about a geometrical constraint in the molecule with intriguing spectroscopic, electrochemical and photovoltaic properties. The first reduction process of 6 occurs on the PDI core while the first oxidation takes place on the Pc ring. These processes reflect a considerably small HOMO-LUMO gap of 1.50 eV, which has vital importance for optoelectronic applications. In addition, the PDI-based first and second reduction processes of 6 are accompanied by an electrochromic behaviour with colour changes from dark purple to blue and blue to turquoise, respectively. A photovoltaic cell involving 6 as the donor and [6,6]-phenyl C61 butyric acid methyl ester as the acceptor has been fabricated. The measurements of the effect of annealing temperature on its performance indicated that the annealing process gives rise to a significant increase in the open circuit voltage, the fill factor and the photoconversion efficiency.
The mononuclear coordination compounds, [Zn(L)Cl2] (1), [Pd(L)Cl]Cl (2), and [Pt(L)Cl]Cl (3) (L) is a tridentate‐coordinated of 4‐(6‐hydroxyphenyl)‐2,6‐di(thiazol‐2‐yl)pyridine) were synthesized and characterized by different spectroscopic methods (FTIR, MALDI‐TOF‐MS, 1H NMR, 13C NMR, and UV/Vis). By using density functional theory (DFT) and time‐dependent DFT (TD‐DFT) methods, the geometrical parameters, UV/Vis absorption spectra, and infrared vibrational frequencies for the investigated compounds were explored. Anticancer activities of these compounds were determined by SRB viability assay in human lung (A549 and H1299), prostate (LNCAP), colorectal (HT‐29), breast cancer (MDA‐MB‐231) and healthy bronchial (BEAS‐2B), breast (MCF‐10A), colon (CCD‐18Co), and prostate (WPMY‐1) epithelial cells. Caspase 3/7 activity, cleaved cytokeratin‐18, and PARP levels were measured to determine apoptosis in the metal compounds found to be effective. Among the compounds, 1 showed a selective inhibiting effect and induced apoptosis on the cancer cells, thus further analyses are needed to evaluate its antitumor/anticancer activity.
Two complex compounds [Cu(L)Cl2] (Cu-L) and [Pt(L)Cl]Cl (Pt-L) containing tridentate ligand (L= 2,6-bis(benzimidazol-2-yl)-4-hydroxypyridine) were prepared. After the successful immobilization of Cu-L and Pt-L on graphene oxide (GO), the electrochemical deposition of Pt nanoparticles was carried out on the modified surface. The resulting electrodes were demonstrated to possess exceptional electrocatalytic features towards the detection of H2O2, and glucose as indicated by the improvement in the cathodic peak response and a favourable shift in the reduction potential of each two reagents. The sensing devices exhibited promising electrochemical performance for the non-enzymatic measurement of H2O2, ranging from 0.01 mmol L-1 to 5 mmol L-1, and a considerably low limit of detection (LOD) of 0.063 and 0.113 µmol L-1 for Cu-L and Pt-L modified-GO decorated with Pt nanoparticles, respectively. Both sensors also showed exceptional sensitivity in the detection of glucose, with LOD of 0.054 and 0.065 µmol L-1 in the concentration range of 0.01 to 2 mmol L-1. The fabricated sensors also demonstrated decent sensitivity, long-term durability, and minimal interference capability. They were also tested for their ability to identify H2O2 and glucose in the actual biological fluid, demonstrating their practical use in routine H2O2 and glucose detection.
A new unsymmetrically substituted 2,2'-bipyridine ligand, 5-methyl-5'-carbomethoxy-2,2'-bipyridine (L) was isolated from the dry distillation of the copper(II) complex, monoaqua-bis(trans-5-methyl-pyridine-2-carboxylato-N,O)copper(II). The ligand was fully characterized. The spectroscopic and single-crystal X-ray diffraction (SCXRD) studies of the coordination compounds of the ligand with platinum(II) and silver(I); cis-Pt(L)Cl2 (1) and [Ag(L)2]PF6 (2), respectively are reported. In 1, the Pt centre coordinates to tertiary N atoms of the ligand and two chloride ions to form a neutral square-planar coordination sphere, while in 2, the Ag(I) centre is coordinated by two ligands through N atoms to generate a cationic flattened tetrahedron geometry in which two mean planes intersect each other at 50.93°. The pyridine rings are nearly coplanar as revealed by the torsion angle [N1-C5-C6-N3] of 0.32°. In both complexes, L acts as a chelating ligand through pyridyl N atoms. In 1, the molecular units are stacked in a head-to-tail fashion with a Pt•••Pt separation of 3.5 Å. Supramolecular self-assembly of the molecular units by extensive intermolecular contacts through C-H•••Cl and C-H•••O between the adjacent units results in an infinite two-dimensional flattened-out herringbone structure in the crystalline state. In 2, the molecular units are interconnected with each other by C-H•••O contacts between the adjacent units running parallel to each other. Both complexes are fluorescent in solution and have emission maxima in the UV-Vis regions, which is a very important property for optoelectronic applications. DFT (density functional theory) and TD-DFT (time-dependent-DFT) calculations were performed at B3LYP/6-311+G(d,p)/LANL2DZ level to explore structural, electronic, and spectroscopic properties to compare with the experimental results. The molecular orbitals (MOs) were carried out with DFT at the same level.
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