To examine the influence of both the important π-acceptor character of the 4-cyanopyridine ligand and the nature of the -substituted phenyls of -porphyrins on the electronic, electrochemical and structural properties of cobaltous metalloporphyrins, we prepared and fully characterized two coordination compounds: the (4-cyanopyridine)[-tetra(-methoxyphenyl)porphyrinato]cobalt(ii) and the (4-cyanopyridine)[-tetra(-chlorophenyl)porphyrinato]cobalt(ii) with the [Co(TMPP)(4-CNpy)] and [Co(TClPP)(4-CNpy)] formulas (complexes 1-2). The solution structures of compounds 1-2 were confirmed by H NMR spectroscopy and mass spectrometry methods. They were further characterized by cyclic voltammetry and photoluminescence studies. The X-ray molecular structure data show that the Co-TClPP-4-NCpy derivative (2) exhibits high ruffling deformation compared to that of the Co-TMPP-4-CNpy species (1). Notably, the crystal packing of complex 1 shows the formation of Co⋯Co supramolecular dimers with a distance of 5.663 Å. As an application of our two cobaltous compounds, an investigation involving complexes 1-2 in the degradation of the methylene blue dye in the presence and absence of HO in aqueous solutions was carried out. These promising results show that 1-2 can be used as catalysts in the degradation processes of dyes.
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http://dx.doi.org/10.1039/c9ra08504a | DOI Listing |
J Org Chem
August 2024
Key Laboratory of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Shenzhen Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, Guangdong 518055, PR China.
Although the concerted [3 + 2] mechanism of osmium-catalyzed asymmetric dihydroxylation has been generally accepted, the unusual nonlinear Hammett relationship induced by amine-type ligands remains unexplained. To understand this, we carried out a density functional theory (DFT) study for the osmylation of substituted styrenes by the following: OsO, OsO-pyridine, OsO-4-cyanopyridine, OsO-4-pyrrolidinopyridine, and OsO-quinuclidine. Calculations using the M06 functional successfully reproduce the experimentally observed nonlinear relationships.
View Article and Find Full Text PDFACS Omega
August 2022
Radioisotope Research Center, Institute for Radiation Sciences, Osaka University, Suita 565-0871, Japan.
The present study reports that the ground- and excited-state Re(23e)/Re(24e) redox potentials of an octahedral hexanuclear rhenium(III) complex can be controlled by systematically changing the number and type of the -heteroaromatic ligand (L) and the number of chloride ions at the six terminal positions. Photoirradiation of [Re(μ-S)Cl] with an excess amount of L afforded a mono-L-substituted hexanuclear rhenium(III) complex, [Re(μ-S)Cl(L)] (L = 4-dimethylaminopyridine (dmap), 3,5-lutidine (lut), 4-methylpyridine (mpy), pyridine (py), 4,4'-bipyridine (bpy), 4-cyanopyridine (cpy), and pyrazine (pz)). The bis- and tris-lut-substituted complexes, - and -[Re(μ-S)Cl(lut)] and -[Re(μ-S)Cl(lut)], were synthesized by the reaction of [Re(μ-S)Cl] with an excess amount of lut in refluxed ,-dimethylformamide.
View Article and Find Full Text PDFInorg Chem
April 2022
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
A series of new mixed-ligand lanthanide trifluoroacetates of formula Ln(4-cpno)(tfa)(HO)·HO (Ln = Sm, Eu, Gd, Tb, Dy; 4-cpno = 4-cyanopyridine -oxide; tfa = trifluoroacetate) is reported. Trifluoroacetates were synthesized as chemically pure polycrystalline solids and their crystal structures were probed using single-crystal and powder X-ray diffraction. Ln(4-cpno)(tfa)(HO)·HO solids make up an isostructural series in which LnO polyhedra are bridged by 4-cpno to form edge-sharing dimers.
View Article and Find Full Text PDFInorg Chem
December 2021
Institut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany.
The sterically demanding carbene ITr ('-bis(triphenylmethyl)imidazolylidene) was used as a ligand for the preparation of luminescent copper(I) complexes of the type [(ITr)Cu(R-pyridine/R'-quinoline)]BF (R = H, 4-CN, 4-CHO, 2,6-NH, and R' = 8-Cl, 6-Me). The selective formation of linear, bis(coordinated) complexes was observed for a series of pyridine and quinoline derivatives. Only in the case of 4-cyanopyridine a one-dimensional coordination polymer was formed, in which the cyano group of the cyanopyridine ligand additionally binds to another Cu atom in a bridging manner, thus leading to a trigonal planar coordination environment.
View Article and Find Full Text PDFRSC Adv
February 2020
University of Monastir, Laboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir Avenue de l'environnement 5019 Monastir Tunisia.
To examine the influence of both the important π-acceptor character of the 4-cyanopyridine ligand and the nature of the -substituted phenyls of -porphyrins on the electronic, electrochemical and structural properties of cobaltous metalloporphyrins, we prepared and fully characterized two coordination compounds: the (4-cyanopyridine)[-tetra(-methoxyphenyl)porphyrinato]cobalt(ii) and the (4-cyanopyridine)[-tetra(-chlorophenyl)porphyrinato]cobalt(ii) with the [Co(TMPP)(4-CNpy)] and [Co(TClPP)(4-CNpy)] formulas (complexes 1-2). The solution structures of compounds 1-2 were confirmed by H NMR spectroscopy and mass spectrometry methods. They were further characterized by cyclic voltammetry and photoluminescence studies.
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