14090-76-7Relevant academic research and scientific papers
Oximato-Based Ligands in 3 d/4 f-Metal Cluster Chemistry: A Family of {Cu3Ln} Complexes with a "propeller"-like Topology and Single-Molecule Magnetic Behavior
Worrell, Anne,Sun, Di,Mayans, Julia,Lampropoulos, Christos,Escuer, Albert,Stamatatos, Theocharis C.
, p. 13944 - 13952 (2018)
The organic chelating and bridging ligands 9,10-phenanthrenedione-9-oxime (phenoxH) and 9,10-phenanthrenedione-9,10-dioxime (phendoxH2) were synthesized and subsequently employed for the first time in heterometallic 3d/4f-metal cluster chemistry. The general reaction between CuCl2·2H2O, LnCl3·6H2O, phenoxH, and NEt3 in a 1:2:2:4 molar ratio, in a solvent mixture comprising MeCN and MeOH, afforded brown crystals of a new family of [Cu3LnCl3(phenox)6(MeOH)3] clusters (Ln = Gd (1), Tb (2), Dy (3)) that possess an unprecedented [Cu3Ln(μ-NO)6]3+ "propeller"-like core. Complexes 1-3 are the first {Cu3Ln} clusters in which the outer CuII and the central LnIII atoms are solely bridged by diatomic oximato bridges. The {Cu-N-O-Ln} bridging units are very distorted with torsion angles spanning the range 35.5-48.9° and 25.2-55.6° in 1 and 2, respectively. As a result, complexes 1-3 are antiferromagnetically coupled, in agreement with previously reported magnetostructural criteria for oximato-bridged Cu/Ln complexes. The magnetic susceptibility data for all complexes were nicely fit to an isotropic spin Hamiltonian (for 1) or a Hamiltonian that accounts for the spin of the CuII atoms, the spin component of the LnIII, the spin-orbit coupling (λ), an axial ligand-field component around the LnIII atoms (Δ), and the Zeeman effect (for the anisotropic 2 and 3). The resulting fit parameters were J = -1.34 cm-1 and g = 2.10 (1), J = -1.42 cm-1, gCu = 2.10, and Δ = -26.3 cm-1 (2), and J = -1.70 cm-1, gCu = 2.05, and Δ = -38.1 cm-1 (3). The reported fitting procedure, implemented in the PHI program, is here used for the first time. Even if this method is only valid in high-symmetry Ln environments, when it is properly used allows a very simple and efficient method to obtain the exchange parameters. In light of the negative anisotropy, compounds 2 and 3 were found to exhibit frequency-dependent tails of out-of-phase signals in the presence of a small external dc field, characteristic of the slow magnetization relaxation of a single-molecule magnet. By using the Kramers-Kronig equations, the effective energy barriers (Ueff) were derived and reported as Ueff = 10.1 and 5.4 cm-1 for 2 and 3, respectively.
Novel tin complexes containing an oximato ligand: Synthesis, characterization, and computational investigation
Thomas, Raji,Nelson, Joseph P.,Pardasani, Ramchand T.,Pardasani, Pushpa,Mukherjee, Tulsi
, p. 1740 - 1749 (2013)
Organotin complexes 1-6 of the general formula [SnR2L] and [(SnR3)2L] (L=phenanthrenequinone dioximato - a bidentate ligand, R=Me, Bu, and Ph) were synthesized by the reaction of the sodium salt of the ligand H2L (prepared in situ with MeONa) and SnR2Cl2/SnR3Cl in 1: 1 and 1: 2 molar ratios. The physical and spectral properties of the newly synthesized complexes 1-6 are described. DFT and HF Calculations were performed to confirm the proposed structures. Copyright
Effect of the planar center moiety for a donor-acceptor polymeric electrochrome
Doyranl?, Ceylan,?olak, Betül,Lacinel, G?zde,Can, Mustafa,Koyuncu, Fatma Baycan,Koyuncu, Sermet
, p. 423 - 431 (2017)
In this work, phenanthrene centered donor-acceptor monomer; 5,10-bis(4-hexyl-2-thienyl)phenantro[9,10-c][1,2,5]thiodiazole; MES16 was synthesized and then its electrochromic application of corresponding polymer was carried out. 4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole (TST) was also synthesized as a standard molecule to determine the effect of the planar phenanthrene center on electrochromic performance. Electrochemical properties were elucidated by cyclic voltammetry and then HOMO-LUMO band gaps were calculated by using their oxidation and reduction onset potentials. Finally, electrochromic properties of poly-(MES16) and poly-(TST) were investigated via spectro-electrochemical measurements. DFT calculations exhibit that poly-(MES16) has a high planarity and an intramolecular charge transfer from the polymer backbone-donor to thiadiazole-acceptor subunit. Because of high solid state π?π interactions of the poly-(MES16), a good quality film was obtained corresponding to self-assembly property planar phenantrene center. Owing to this property, electrochromic performance of poly-(MES16) such as response time, stability and ΔT% were better than the standard poly-(TST).
High-Throughput Screening of Earth-Abundant Water Reduction Catalysts toward Photocatalytic Hydrogen Evolution
Motz, Rachel N.,Lopato, Eric M.,Connell, Timothy U.,Bernhard, Stefan
, p. 774 - 781 (2021)
Noble-metal photosensitizers and water reduction co-catalysts (WRCs) still present the highest activity in homogeneous photocatalytic hydrogen production. The search for earth-abundant alternatives is usually limited by the time required to screen new catalyst combinations; however, here, we utilize newly designed and developed high-throughput photoreactors for the parallel synthesis of novel WRCs and colorimetric screening of hydrogen evolution. This unique approach allowed rapid optimization of photocatalytic water reduction using the organic photosensitizer Eosin Y and the archetypal cobaloxime WRC [Co(GL1)2pyCl], where GL1 is dimethylglyoxime and py is pyridine. Subsequent combinatorial synthesis generated 646 unique cobalt complexes of the type [Co(LL)2pyCl], where LL is a bidentate ligand, that identified promising new WRC candidates for hydrogen production. Density functional theory (DFT) calculations performed on such cobaloxime derivative complexes demonstrated that reactivity depends on hydride affinity. Alkyl-substituted glyoximes were necessary for hydrogen production and showed increased activity when paired with ligands containing strong hydrogen-bond donors.
Electrochromic properties of phenantrene centered EDOT polymers
Colak, Betül,Büyükkoyuncu, Ahmet,Baycan Koyuncu, Fatma,Koyuncu, Sermet
, p. 366 - 375 (2017)
A series of phenantrene centered donor-acceptor type electroactive 3,4-ethlenedioxythiophene (EDOT) monomers (EP-X) containing N, S and Se heteroatom on the bezophenantra-X-diazole acceptor unit have been synthesized by Stille coupling reaction. These monomers were electrochemically polymerized by potentiodynamic method to obtain electrochromic polymer films. Spectro-electrochemical properties were also investigated by UV-vis absorption connected with the cyclic voltammetry measurements. The polymer films exhibited a remarkable trend of visible color (yellow, orange, red) at the neutral state due to changing the central acceptor moiety. These polymer films have multielectrochromic properties by means of moderately changing the absorbance/transmittance at the visible regime upon applied positive potentials. The donor-acceptor interaction at the neutral state correlated by DFT calculations was also supported by the interesting trend in the colors of these polymers. Finally, the electrochromic performance of EP-X polymer films represented a high redox stability, reasonable contrast ratio, coloration efficiency and response times.
MOLECULARLY TUNABLE HETEROGENEOUS CATALYSTS BY EDGE FUNCTIONALIZATION OF GRAPHITIC CARBONS
-
, (2017/03/21)
Disclosed are surface immobilized (electro)catalysts that may be prepared by a condensation reaction that generates an aromatic unit that is robust to acid and base and elevated temperatures. Among their many desirable characteristics, the catalysts are far less prone to the bimolecular deactivation pathways commonly observed for homogeneous catalysts, and may be used in solvents with a range of polarities and dielectric strengths. The catalysts are suitable for a wide array of thermal catalytic reactions (polymerization, oxidation, hydrogenation, cross- coupling etc. ) and as anodes and or cathodes in fuel cells, electrolyzers, and in batteries and supercapacitors.
ELECTROLUMINESCENT IMIDAZO-QUINOXALINE CARBENE METAL COMPLEXES
-
Page/Page column 219, (2016/04/04)
Metal carbene complexes comprising at least one imidazo-quinoxaline ligand, organic electronic devices, especially OLEDs (Organic Light- Emitting Diodes) which comprise such complexes, a light-emitting layer comprising at least one inventive metal carbene complex, an apparatus selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, the use of such a metal carbene complex for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices and a process for preparing such metal carbene complexes.
Synthesis and properties of the alkyl/aryl germanium dioximates containing Ge-O bond: Stability factors-A theoretical approach
Thomas, Raji,Joseph P., Nelson,Pardasani, Pushpa,Mukherjee
, p. 545 - 550 (2013/01/15)
The reactions of R2GeCl2 and R3GeCl with 9,10-phenanthrenequinone dioxime in 1:1 and 1:2 molar ratios to form a series of organogermanium complexes of the general formula R2GeL and (R 3Ge)2
A new class of phenazines with activity against a chloroquine resistant plasmodium falciparum strain and antimicrobial activity
Hussain, Hidayat,Specht, Sabine,Sarite, Salem R.,Saeftel, Michael,Hoerauf, Achim,Schulz, Barbara,Krohn, Karsten
supporting information; experimental part, p. 4913 - 4917 (2011/09/15)
New phenazines were synthesized by oxygenation of 1- and 2-naphthol with transition metal peroxo complexes and in situ reaction with 1,2-diamines. The title compounds were evaluated for in vitro antimalarial activity against Plasmodium falciparum and chloroquine-resistant strains. Phenazines 12, 27, and 28 were most prominent in growth inhibition. In vivo protection against cerebral malaria was observed with the phenazines 11, 12, 20, and 27, whereas partial protection was provided by 19.
