- Syntheses, crystal structure, and magnetic properties of a self-assembling dicopper(II) helicate with novel bipyridine ligand
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Anovel double helical dicopper(II) complex was synthesized by reaction of a polydentate ligand L = 2,2'- bipyridyl-6,6'-bis(2-acetylpyrazinohydrazone) with copper(II) perchlorate in CH3CN. The self-assembling process was studied by UV-Vis spectrometric titration experiments which revealed the formation of dinuclear complexes [Cu2L2](ClO 4)4. The structure of dicopper double-helicate was confirmed by X-ray diffractometry. Each copper(II) center occupies a distorted octahedral environment. Variable-temperature magnetic measurements reveal weak antiferromagnetic interactions between Cu(II) ion centers with J = -0.63 cm -1.
- Kao, Hsien-Chang,Wang, Yi-Chun,Wang, Wen-Jwu
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- A Bridge-bond Isomerism. X-Ray Crystal Structure, Spectral and Magnetic Properties of Two Dinuclear Isomeric Complexes (bipyo = 2,2'-bipyridine N,N'-dioxide)
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Copper(II) chloride reacts with 2,2'-bipyridine N,N'-dioxide (bipyo), in methanolic solution, in a manner depending on the reaction conditions (temperature, ligand: metal ion ratio, concentration, etc.) to form different products.Two of them, a green and a yellow-orange isomer of , have been characterized by elemental microanalysis, electronic, IR and ESR spectra and magnetic susceptibility measurements.The crystal and molecular structures of both isomers have been determined from X-ray diffractometer data by the heavy-atom method and refined by full-matrix least-squares.The structures of the green and yellow-orange isomers, respectively, have been refined to R=0.054 (for 1366 reflections) and 0.063 (for 1283 reflections): green isomer, triclinic, space group P, a= 8.664(2), b=8.732(2), c=9.099(3) Angstroem, α=95.62(2), β=107.04(2), γ=114.05(2) deg, and Z=1; yellow-orange isomer, monoclinic, space group P21/c, a=7.912(2), b=9.878(2), c=15.086(3) Angstroem, β=99.86(2) deg and Z=2.Both crystal structures comprise centrosymmetric dimeric molecules.The copper(II) atoms of the green isomer are bridged by two chlorine atoms, those of the orange-yellow isomer by the oxygen atoms of two bipyo ligands.
- Baran, Peter,Koman, Marian,Valigura, Dusan,Mrozinski, Jerzy
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- Models of molecular photocatalysts for water oxidation: Strategies for conjugating the Ru(bda) fragment (bda = 2,2′-bipyridine-6,6′-dicarboxylate) to porphyrin photosensitizers
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Model dyads, in which the Ru(bda) water oxidation catalyst (WOC) is connected to a porphyrin, were prepared following two different modular strategies: i) the direct linkage approach, in which porphyrins bearing peripheral pyridyl rings are bound to the {
- Adamo, F.,Alessio, E.,Iengo, E.,Vidal, A.
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supporting information
(2020/12/09)
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- Bis-(1,2,4-triazin-3-yl) ligand structure driven selectivity reversal between Am3+and Cm3+: solvent extraction and DFT studies
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Selectivity between Am3+and Cm3+was investigated after their aqueous complexation with three structurally tailored hydrophilic bis-(1,2,4-triazin-3-yl) ligands followed by their extraction withN,N,N′N′-tetraoctyl diglycolamide (TODGA) dissolved in an ionic liquid (C4mim·Tf2N). The three hydrophilic ligands used were SO3PhBTP, SO3PhBTBP, and SO3PhBTPhen. It was evident from the solvent extraction studies that SO3PhBTP formed a stronger complex with Cm3+than with Am3+, but SO3PhBTPhen showed better complexation ability for Am3+than for Cm3+, and SO3PhBTBP showed no selectivity for the two actinide ions. DFT calculations indicated that the coordinating ‘N’atoms in BTP were more co-planar in the complex and this co-planarity was higher in the Cm3+complex as compared to that in Am3+. In the case of BTBP and BTPhen ligands, on the other hand, the co-planarity was more pronounced in the Am3+complexes. Mayer's bond order calculations of M-N bonds in the complexes also indicated a reversal of the complexation ability of the BTP and BTPhen ligands for Am3+and Cm3+. Calculations of the complexation energies further supported the higher selectivity of the BTP ligand for Am3+by ?52.0 kJ mol?1, and better selectivity of the BTPhen ligand for Cm3+by ?24.7 kJ mol?1
- Ansari, S. A.,Bhattacharyya, Arunasis,Karthikeyan, N. S.,Mohapatra, P. K.,Rao, T. S.,Ravichandran, C.,Seshadri, H.,Venkatachalapathy, B.
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supporting information
p. 7783 - 7790
(2021/06/16)
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- The M?CPbA?NH3(G) system: A safe and scalable alternative for the manufacture of (substituted) pyridine and quinoline N?oxides?
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An improved, safe, and scalable isolation process for (substituted) pyridine and quinoline N-oxides in quantitative yields along with high purities using the m-CPBA?NH3(g) system is described. The safety was assessed by reaction calorimetry and differential scanning calorimetry studies for possible hazards during the conversion and isolation steps. Careful interpretation of the data substantiated the safety and scalability. The process flow is simplified to meet the industrial requirements of safety, cost-effectiveness, and utility minimization. The reaction was safely demonstrated at a 2.5 kg scale.
- Palav, Amey,Misal, Balu,Ernolla, Anilkumar,Parab, Vinod,Waske, Prashant,Khandekar, Dileep,Chaudhary, Vinay,Chaturbhuj, Ganesh
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supporting information
p. 244 - 251
(2019/03/17)
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- Electrochemistry and spectroscopy of substituted [Ru(phen)3]2+ and [Ru(bpy)3]2+ complexes
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The metal-to-ligand charge transfer property of nitrogen-based ruthenium complexes earns it a central place in dye-sensitized solar cell and photo-catalytic H2O and CO2 reduction research and applications. Electronic and spectral tuning are conveniently done by altering substituents and ligands. Cyclic voltammograms and UV–visible spectra of a synthesized series of electronically altered phenanthroline and bipyridyl ruthenium complexes (ΔE°' > 1.4 V for RuII-III) were obtained and, amongst others, correlated with DFT computed HOMO energies and ionization potentials. A good linear relationship with R2 = 0.97 were found for the combined bipyridyl and phenanthrolinato ruthenium series, thereby providing a convenient computational tool for the theoretical prediction of associated redox potentials. TDDFT closely simulates spectral properties of these complexes, where λmax varies from 420 to 520 nm. The former wavelength is representative of the dione-phenanthroline and the latter of the dinitro-bipyridyl ruthenium complex.
- van der Westhuizen, Deidré,von Eschwege, Karel G.,Conradie, Jeanet
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- The synthesis of diethyl 2-(2,2 ′ -bipyridin-4-ylmethylene)malonate and diethyl 3,3 ′ -(2,2 ′ -bipyridine-4,4 ′ -diyl)diacrylate
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Abstract: The new acrylic acid derivatives diethyl 2-(2,2′-bipyridin-4-ylmethylene)malonate and diethyl 3,3′-(2,2′-bipyridine-4,4′-diyl)diacrylate which may be used for the introduction of metal coordination sites in polyacrylates were synthesized and characterized. Intermediates of the syntheses were prepared by improved synthetic protocols working under microwave conditions whenever it was advantageous for the resulting product in terms of reaction time and/or chemical yield. In addition, the crystal structure of one of the intermediates, 4,4′-dibromo-2,2′-bipyridine (6), is reported, in which molecules are arranged into infinite chains by C-H—Br interactions. Graphical Abstract: SYNOPSIS Synthesis and characterization of new 2,2’-bipyridine ligands with substituents related to acrylic acid esters are reported. These compounds offer the possibility to incorporate 2,2’-bipyridine ligands or coordination compounds derived from them into polyacrylate materials. [Figure not available: see fulltext.].
- Heintz, Katharina,G?rls, Helmar,Imhof, Wolfgang
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- Synthesis and in vitro evaluation of diverse heterocyclic diphenolic compounds as inhibitors of DYRK1A
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Dual-specificity tyrosine phosphorylation-related kinase 1A (DYRK1A) is a dual-specificity protein kinase that catalyses phosphorylation and autophosphorylation. Higher DYRK1A expression correlates with cancer, in particular glioblastoma present within the brain. We report here the synthesis and biological evaluation of new heterocyclic diphenolic derivatives designed as novel DYRK1A inhibitors. The generation of these heterocycles such as benzimidazole, imidazole, naphthyridine, pyrazole-pyridines, bipyridine, and triazolopyrazines was made based on the structural modification of the lead DANDY and tested for their ability to inhibit DYRK1A. None of these derivatives showed significant DYRK1A inhibition but provide valuable knowledge around the importance of the 7-azaindole moiety. These data will be of use for developing further structure-activity relationship studies to improve the selective inhibition of DYRK1A.
- Zhou, Qingqing,Reekie, Tristan A.,Abbassi, Ramzi H.,Indurthi Venkata, Dinesh,Font, Josep S.,Ryan, Renae M.,Munoz, Lenka,Kassiou, Michael
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p. 5852 - 5869
(2018/11/10)
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- A mild and efficient H2O2 oxygenation of N-heteroaromatic compounds to the amine N-oxides and KI deoxygenation back to the tertiary amine with hexaphenyloxodiphosphonium triflate
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A mild and efficient method for the oxidation of N-heteroaromatic compounds to the corresponding N-oxides using H2O2 in the presence of hexaphenyloxodiphosphnium triflate (Hendrickson reagent) in EtOH at room temperature was reported. This methodology presented relatively fast and selective reactions to afford the N-oxides in good yields. The reverse reactions, deoxygenation reactions, were also carried out under the same reaction conditions by KI to produce the tertiary amines.
- Khodaei, Mohammad Mehdi,Alizadeh, Abdolhamid,Hezarkhani, Hadis Afshar
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p. 1843 - 1849
(2018/07/06)
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- Uranyl Complexes with Aroylbis(N, N-dialkylthioureas)
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The reaction of isophthaloylbis(N,N-diethylthiourea), H2L1, with UO2(CH3COO)2·2H2O and NEt3 as a supporting base gives a tetranuclear, anionic complex of the composition [{UO2(L1)}4(OAc)2]2-, in which the uranyl ions are S,O-chelate bonded. Each two of them are additionally linked by an acetato ligand. Similar reactions of various uranyl starting materials (uranyl acetate, uranyl nitrate, (NBu4)2[UO2Cl4]) with corresponding pyridine-centered ligands (pyridine-2,6-dicarbonylbis(N,N-dialkylthioureas), H2L2) yield mononuclear, neutral compounds, in which the thiourea derivatives are coordinated as S,N,N,N,S-five-dentate chelators. The equatorial coordination spheres of the formed hexagonal bipyramidal complexes [UO2(L2)(solv)] are completed by solvent ligands (H2O, MeOH, or DMF). Attempted reactions without a supporting base result in decomposition of the organic ligands and the formation of hexanuclear uranyl complexes with pyridine-2,6-dicarboxylato ligands, while the use of an excess of base results in condensation and the formation of dinuclear [{UO2(L2)(μ-OMe)}2]2- complexes. A stable complex of the composition [UO2(L3)] results from reactions of common uranyl starting materials with 2,2′-bipyridine-6,6′-dicarbonylbis(N,N-diethylthiourea) (H2L3). The equatorial coordination sphere of the neutral, hexagonal bipyramidal complex is occupied by an SN4S donor atom set, which is provided by the hexadentate organic ligand. While the uranium complexes with {L1}2- and {L2}2- are labile and rapidly decompose in acidic solutions, [UO2(L3)] is stable over a wide pH range, and the ligand readily extracts uranyl ions from aqueous solutions into organic solvents.
- Noufele, Christelle Njiki,Pham, Chien Thang,Hagenbach, Adelheid,Abram, Ulrich
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p. 12255 - 12269
(2018/09/27)
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- Ruthenium(II)–Pyridylimidazole Complexes as Photoreductants and PCET Reagents
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Complexes of the type [Ru(bpy)2pyimH]2+[bpy = 2,2′-bipyridine; pyimH = 2-(2-pyridyl)imidazole] with various substituents on the bpy ligands can act as photoreductants. Their reducing power in the ground state and in the long-lived3MLCT excited state is increased significantly upon deprotonation, and they can undergo proton-coupled electron transfer (PCET) in the ground and excited state. PCET with both the proton and electron originating from a single donor resembles hydrogen atom transfer (HAT) and can be described thermodynamically by formal bond dissociation free energies (BDFEs). Whereas the class of complexes studied herein has long been known, their N–H BDFEs have not been determined even though this is important in view of assessing their reactivity. Our study demonstrates that the N–H BDFEs in the3MLCT excited states are between 34 and 52 kcal mol–1depending on the chemical substituents at the bpy spectator ligands. Specifically, we report on the electrochemistry and PCET thermochemistry of three heteroleptic complexes in 1:1 (v/v) CH3CN/H2O with CF3, tBu, and NMe2substituents on the bpy ligands.
- Pannwitz, Andrea,Prescimone, Alessandro,Wenger, Oliver S.
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supporting information
p. 609 - 615
(2017/02/05)
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- Hard-and-soft phosphinoxide receptors for f-element binding: structure and photophysical properties of europium(iii) complexes
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New phosphinoyl-containing tetradentate heterocycles preorganised for metal ion binding were designed and prepared in high yields. The X-ray structures of two allied phosphinoyl-bearing 2,2′-bipyridyl and phenanthroline ligands, as well as closely related structures of 2,6-bis(diphenylphosphinoyl)pyridine and 9-(diphenylphosphinoyl)-1,10-phenanthroline-2-one, are reported. Complexes of nitrates of several lanthanides and trifluoroacetate of Eu(iii) with two phosphinoyl-bearing 2,2′-bipyridyl and phenanthroline ligands were isolated and characterised. The first structures of lanthanide complexes with phosphinoyl-bearing 2,2′-bipyridyl and phenanthroline ligands are reported. The nature of the counter-ion is crucial for the coordination environment of the metal ion. The photophysical properties of the complexes differring in both the nature of the ligand and counter-ion were investigated. The photophysical properties of the complexes are strongly ligand- and counter-ion-dependent. Absorbance and luminescence excitation spectra of complexes showed main peaks in the UV range which correspond to the absorption of light by the ligand and these are ligand-dependent. Luminescence spectra of complexes show typical europium emission in the red region with a high quantum yield, which orresponds to the transitions5D0→7FJ (J = 0-6). The value of deviation of the components of5D0 →7F2 and5D0 →7F1 transitions from the inversion centre shows a larger dependence on the counter-ion than on the nature of the ligand. The value of the luminescence quantum yield is larger for europium complexes with 2,2′-bipyridyl-based ligands and NO3 counter-ions than for complexes with phenanthroline-based ligands and NO3 counter-ions. A low dependence of the luminescence lifetime of Eu complexes on the nature of the ligand has been demonstrated: values in the solid state were in the range 1.1-2.0 ms.
- Borisova, Nataliya E.,Kharcheva, Anastasia V.,Patsaeva, Svetlana V.,Korotkov, Leonid A.,Bakaev, Sergey,Reshetova, Marina D.,Lyssenko, Konstantin A.,Belova, Elena V.,Myasoedov, Boris F.
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p. 2238 - 2248
(2017/02/26)
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- Syntheses and crystal structures of two self-assembled dizinc(II) helicates with novel hydrazone linked polypyridyl ligands
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The rationally designed polydentate ligands, L1 and L2, based on the pyridinyl moiety and the hydrazone fragment have been synthesized to coordinate zinc(II) ions. We utilize pyridine as a rigid core connecting two bipyridines as ligand building blocks with a hydrozone linker for the L1. The L2 has a reversed design in which a bipyridine was used as a hinging-available building block of the ligand core, connecting two pyridazine arms with a hydrazone linker. Two novel helical dizinc(II) complexes were obtained by the reaction of L1 and L2 with zinc(II) perchlorate in acetonitrile. The structures of both helicates were confirmed by X-ray diffractometry. Single-stranded helicate Zn2L1 contains two zinc ions bridged by an oxygen atom. Except for the L2 ligand, no other bridging species were found between the two zinc ions in the double-stranded helicate Zn2L2 2. The self-assembling process of helicate Zn2L1 in solution state was studied by UV–Vis spectrometric titration experiments. The stepwise formation constants imply a slightly positive cooperative behavior for the formation of helicates.
- Kao, Hsien-Chang,Wang, Yi-Chun,Wang, Wen-Jwu
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p. 3539 - 3552
(2017/05/19)
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- In order to BipySi for preparation of the prismatic body cage oligomeric silsesquioxane and its rare earth luminescent material
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The invention relates to a cage type oligomeric silsesquioxane prepared by taking BipySi as supplement bodies and a rare earth luminescent material prepared from cage type oligomeric silsesquioxane. By taking 1,3,5,7,9,11,14-heptaisobutyl tricyclic[7,3.3.15,11] heptatrisiloxane-intra-3,7,14-triol as a matrix, alpha-thenoyl trifluoroacetone silanized derivative, a dipyridine silanized derivative and a terpyridyl silanized derivative as supplement bodies, the supplement bodies react with the matrix in form of supplements to form integrated novel cage type oligomeric silsesquioxane. The cage type oligomeric silsesquioxane is combined with rare earth elements to form a POSS/rare earth ion luminescent material. The obtained rare earth ion luminescent material/POSS is rich in luminescent color, high in color purity, long in fluorescent lifetime (0.5-1.5ms), high in quantum efficiency (20) and strong in thermal stability (350 DEG C) and light stability, is a valuable optical material and can be applied to the field of display and development, light source, X-ray intensifying screen and the like.
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Paragraph 0069; 0070
(2017/08/25)
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- Catalyst-free and selective oxidation of pyridine derivatives and tertiary amines to corresponding N-oxides with 1,2-diphenyl-1,1,2,2-tetrahydroperoxyethane
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The catalyst-free oxidation of various pyridine derivatives and tertiary amines to their corresponding N-oxides with 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as an efficient oxidant has been developed. The methodology proved to tolerate a number of functional groups. The reactions proceeded smoothly under solvent-free and mild conditions at room temperature. All the products were easily extracted from the reaction mixtures in excellent yields. Graphical abstract: The catalyst-free oxidation of various pyridine derivatives and tertiary amines to their corresponding N-oxides with 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as an efficient oxidant has been developed. The methodology proved to tolerate a number of functional groups. The reactions proceeded smoothly under solvent-free and mild conditions at room temperature. All the products were easily extracted from the reaction mixtures in excellent yields.
- Azarifar, Davood,Mahmoudi, Boshra
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p. 645 - 651
(2016/02/19)
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- Design and synthesis of new Ru-complexes as potential photo-sensitizers: Experimental and TD-DFT insights
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We report density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations on a novel organic ligand and a novel class of ruthenium complexes; cis-RuL2X2 with L = 2,2′-bipyridine-6,6′-bis ethyl ester phosphonate and phosphonic acid, X = Cl, CN or NCS. The calculations show that cis-configurations are more stable than the trans-counterparts. The DFT results have been used to help design such novel complexes for potential use as sensitizers. We demonstrate the opportunity to synthesize such complexes with high purity. The synthesis of these complexes relies on the preparation of the key intermediates cis-Ru(2,2′-bipyridine-6,6′-bisdiethyl ester phosphonate)Cl2. These complexes were characterized by 1H, 13C, and 31P NMR, elemental analysis and FTIR spectroscopy. The NCS complex shows the smallest optical band gap followed by the Cl and CN complexes, respectively, with the highest performance upon use as a sensitizer in dye-sensitized solar cells.
- Sharmoukh,Hassan, Walid M. I.,Gros, Philippe C.,Allam, Nageh K.
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p. 69647 - 69657
(2016/08/05)
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- Separation and complexation of palladium(II) with a new soft N-donor ligand 6,6′-bis(5,6-dinonyl-1,2,4-triazin-3-yl)-2,2′-bipyridine (C9-BTBP) in nitric acid medium
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Soft N-donor bis-triazine ligands developed for the separation of minor actinides (MAs) from lanthanides have been intensively studied for the past two decades. However, the investigation on the recovery and complexation of fission products Pd(ii) with these ligands has rarely been reported to date. Herein, the synthesis, and solvent extraction of Pd(ii) and some typical metals from HNO3 solutions as well as Pd(ii) complexation with a new soft N-donor ligand C9-BTBP were presented. The C9-BTBP ligand exhibited high extraction capability and high selectivity for Pd(ii) in HNO3 solution. Both 1:1 and 2:1 Pd(ii)-C9-BTBP complexes were found in solution by a combination of ESI-MS and 1H NMR titration experiments. A solid binuclear Pd(ii) complex [Pd2(NO3)4·(C9-BTBP)]·2.5H2O was synthesized and characterized by elemental analysis, DSC-TGA and 1H NMR. This is the first example that a binuclear Pd(ii) complex with any N-donor bis-triazine ligand has been confirmed both in solution and in the solid state.
- Zhang, Anyun,Xu, Lei,Lei, Gaoming
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p. 6374 - 6383
(2016/07/16)
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- Long-Lived, Emissive Excited States in Direct and Amide-Linked Thienyl-Substituted RuII Complexes
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The excited state behavior of a new series of homoleptic and heteroleptic RuII complexes bearing thienyl groups appended to a 2,2′-bipyridine chelating ligand via direct, secondary and tertiary amide linkages is examined. The results of nanosecond transient absorption spectroscopy, emission lifetime measurements and bimolecular quenching experiments are correlated to determine that although the amide linkage does not act as a conjugated bridge to the peripheral substituents, it does not preclude possible electron transfer processes. Complexes bearing directly bound thienyl and bithienyl substituents exhibit long excited state and emission lifetimes (τem = 2 and 15 μs), with high emission quantum yields in solution (Φ = 0.35) and slow rates of non-radiative decay.
- Majewski, Marek B.,Smith, Jeremy G.,Wolf, Michael O.,Patrick, Brian O.
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supporting information
p. 1470 - 1479
(2016/04/26)
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- Palladium-catalyzed highly regioselective oxidative homocoupling of 1,2,3-triazole N-oxides
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A convenient and highly regioselective palladium-catalyzed direct C–H homocoupling of 1,2,3-triazole N-oxides was developed in the presence of silver carbonate and 1,10-phenanthroline. This protocol provides a straightforward and operationally simple rout
- Peng, Xiangjun,Huang, Panpan,Jiang, Lili,Zhu, Jiayi,Liu, Liangxian
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p. 5223 - 5226
(2016/11/11)
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- Exchange of pyridine and bipyridine ligands in trimethylplatinum(iv) iodide complexes: Substituent and solvent effects
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A series of mononuclear trimethylplatinum(iv) complexes of bipyridine ligands, [PtMe3(L-L)I] (L-L = bipy, 4-Mebipy, 4-MeObipy and 4-Me2Nbipy) has been synthesized by the reaction of trimethylplatinum(iv) iodide with bipyridine ligands L-L in an equimolar ratio. Also, treatment of mononuclear trimethylplatinum(iv) iodide complexes of pyridine ligands, [PtMe3L2I] (L = py, 4-Mepy, 4-MeOpy and 4-Me2Npy) with the corresponding bipyridine ligands leads to the exchange of the pyridines by the bipyridine ligands, thereby resulting in the formation of the more stable chelate bipyridine complexes. The ligand-exchange reactions have been studied by 1H NMR spectroscopy. The 1H NMR spectra of a 1: 1 mixture of mononuclear pyridine complexes [PtMe3L2I] and corresponding bipyridine ligands L-L reveal the formation of two chelate bipyridine complexes, [PtMe3(L-L)I] and [PtMe3(L-L)L]I, in solution. Speciation of the pyridine and bipyridine complexes in solution was found to be dependent on the substituent as well as on the nature of the solvent. Furthermore, crystal structures of three bipyridine complexes [PtMe3(L-L)I] (L-L = 4-Mebipy, 4-MeObipy and 4-Me2Nbipy) have also been investigated here.
- Ghosh, Biswa Nath,Schlecht, Sabine
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p. 101900 - 101909
(2015/12/08)
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- Hydroxyl and amino functionalized cyclometalated Ir(III) complexes: Synthesis, characterization and cytotoxicity studies
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A series of Ir(III) complexes (?N)2Ir(N N) (N N are 4,4′-dihydroxy-2,2′-bipyridine and 4,4′-diamino-2,2′-bipyridine, and ?N are phenylpyridine, benzo[h]quinolone, and 2-phenylquinoline) were synthesized and characterized. Two of the complexes were structurally characterized via X-ray crystallography. The photophysical and photochemical properties of these complexes were studied. Preliminary studies of their applications on pH sensing, and cell imaging were also performed.
- Wu, Zhaozhen,Mu, Juanjuan,Wang, Qiong,Chen, Xing,Jensen, Lasse,Yi, Changqing,Li, Mei-Jin
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supporting information
p. 175 - 182
(2015/06/22)
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- Catalytic N-oxidation of tertiary amines on RuO2NPs anchored graphene nanoplatelets
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Ultrafine ruthenium oxide nanoparticles (RuO2NPs) with an average diameter of 1.3 nm were anchored on graphene nanoplatelets (GNPs) using a Ru(acac)3 precursor by a very simple dry synthesis method. The resultant material (GNPs-RuO2NPs) was used as a heterogeneous catalyst for the N-oxidation of tertiary amines for the first time. The transmission electron microscopy (TEM) images of the GNPs-RuO2NPs showed the excellent attachment of RuO2NPs on GNPs. The loading of Ru in GNPs-RuO2NPs was 2.68 wt%, as confirmed by scanning electron microscope-energy dispersive spectroscopy (SEM-EDS). The X-ray photoelectron spectrum (XPS) and the X-ray diffraction pattern (XRD) of GNPs-RuO 2NPs revealed that the chemical state of Ru on GNPs was +4. After the optimization of reaction conditions for N-oxidation of triethylamine, the scope of the reaction was extended to various aliphatic, alicyclic and aromatic tertiary amines. The GNPs-RuO2NPs showed excellent catalytic activity in terms of yields even at a very low amount of Ru catalyst (0.13 mol%). The GNPs-RuO2NPs was heterogeneous in nature, chemically as well as physically, very stable and could be reused up to 5 times. The Royal Society of Chemistry 2014.
- Gopiraman, Mayakrishnan,Bang, Hyunsik,Babu, Sundaram Ganesh,Wei, Kai,Karvembu, Ramasamy,Kim, Ick Soo
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p. 2099 - 2106
(2014/06/24)
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- 2,2,2-Trifluoroacetophenone as an organocatalyst for the oxidation of tertiary amines and azines to N-oxides
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A cheap, mild and environmentally friendly oxidation of tertiary amines and azines to the corresponding Noxides is reported by using polyfluoroalkyl ketones as efficient organocatalysts. 2,2,2-Trifluoroacetophenone was identified as the optimum catalyst for the oxidation of aliphatic tertiary amines and azines. This oxidation is chemoselective and proceeds in high-to-quantitative yields utilizing 10 mol% of the catalyst and H2O2 as the oxidant.
- Limnios, Dimitris,Kokotos, Christoforos G.
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supporting information
p. 559 - 563
(2014/04/03)
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- Na2(smbipy) - A bipyridine-derived ligand with chelating sulfonate tags and its 3d metal complexes
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The sulfonated bipyridine derivative disodium 6,6′-bis(sulfonatomethyl)-2,2′-bipyridine [Na2(smbipy)] was synthesized, and its complexation behaviour towards divalent 3d metals in aqueous solution was explored. The complexes of late 3d metals [M(smbipy)(H2O)2]·H2O (M = Co, Ni, Zn) and [Cu(smbipy)(H2O)] are sparingly soluble in water, and their crystal structures show fourfold equatorial coordination (κ4N,N',O,O') of the smbipy ligand. Ammonia-rich solutions of the NiII and CuII aqua complexes yield the decomplexation products [Ni(NH3)6](smbipy), [Ni(NH3)5(H2O)](smbipy) and [Cu(NH3)4](smbipy)·2H2O. Buffered solutions with a reduced ammonia content lead to [Ni(smbipy)(NH3)2] and [Cu(smbipy)(NH3)3]·2H2O, and the latter shows twofold coordination of the smbipy ligand through the nitrogen atoms only (κ2N,N'). When nearly quantitative amounts of ammonia are applied, two closely related complexes with the core motif [(smbipy)Cu(μ-OH)2Cu] form. Crystal structures of all complexes were obtained, and their features are discussed.
- Oelkers, Benjamin
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p. 5838 - 5848
(2015/02/02)
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- Strongly blue luminescent cationic iridium(III) complexes with an electron-rich ancillary ligand: Evaluation of their optoelectronic and electrochemiluminescence properties
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Two strongly blue luminescent cationic heteroleptic iridium complexes 1b and 2b bearing a 4,4′-bis(dimethylamino)-2,2′-bipyridine (dmabpy) ancillary ligand and either 1-benzyl-4-(2,4-difluorophenyl)-1H-1,2,3-triazole (dFphtl) or 2-(2,4-difluorophenyl)-5-methylpyridine (dFMeppyH), respectively, have been synthesized and fully characterized. In comparison with other analogues, the interplay of the triazole unit with the dmabpy unit and methylation of the pyridine ring are discussed with respect to the photophysical, electrochemical, and electrochemiluminescent (ECL) properties of the complexes. The two complexes, 1b and 2b, are blue emitters with λmax = 495 and 494 nm, respectively. The nature of the excited states was established by various photophysical and photochemical experiments as well as DFT calculations. Both complexes emit from a ligand-centered state, however, the emission of 1b possesses significant charge-transfer character, which is absent in 2b. The presence of the methyl group on the cyclometalating ligand leads only to a modest increase in the radiative rate constant, k r, but otherwise does not appreciably influence the optoelectronic properties of the complex compared with the non-methylated analogue. In contrast, the efficacy of the ECL emission when scanning to 2.50 V is strongly influenced by the presence of the methyl group. ECL emission is also enhanced in complexes bearing dmabpy ancillary ligands compared with those containing dtBubpy ligands. The two complexes exhibit similar electrochemical behavior. Incorporation of the dmabpy ligand shifts both the oxidation and reduction cathodically. The combination of the dmabpy and dFphtl groups increases the redox potential difference and thus the HOMO-LUMO gap but the emission is not further blueshifted. Thus, the structural modification of the cyclometalating ligand, although only modestly tuning the emission energy, modulates the nature of the excited state and the efficiency of the ECL process. The synthesis, photophysical, electrochemical, and electrochemiluminescent properties of two highly emissive cationic blue-emitting Ir complexes are reported. Variation of the ligand results in a change in the nature of the emission. The decoration on both the cyclometalating and ancillary ligands strongly influences the ECL efficiencies. A detailed DFT/TDDFT study corroborates experiment. Copyright
- Ladouceur, Sebastien,Swanick, Kalen N.,Gallagher-Duval, Shawn,Ding, Zhifeng,Zysman-Colman, Eli
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supporting information
p. 5329 - 5343
(2013/11/06)
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- Synthesis and spectral properties of ruthenium(II) complexes based on 2,2′-bipyridines modified by a perylene chromophore
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Five new 2,2′-bipyridines functionalized with a perylene or a perylenediimide moiety were synthesized and the corresponding heteroleptic ruthenium(II) complexes ([Ru(bpy)2(L)](PF6)2; bpy = 2,2′-bipyridyl, L = perylene-substituted bpy ligand) were prepared. The UV-vis spectra of the ruthenium(II) complexes showed red-shifted and intense absorption bands derived from the conjugated structure of the new ligands.
- Kodama, Koichi,Kobayashi, Akinori,Hirose, Takuji
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supporting information
p. 5514 - 5517
(2013/09/23)
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- ORGANIC METAL DYE, AND PHOTOELECTRIC ELEMENT AND DYE-SENSITIZED SOLAR CELL USING THE ORGANIC METAL DYE
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The present invention relates to an organic metal dye comprising fused heterocyclic derivatives, and to a photoelectric element and to a dye-sensitized solar cell using the organic metal dye.
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Page/Page column 34-35
(2012/10/08)
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- A modular 'click' approach to substituted 2,2′-bipyridines
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The CuAAC reaction was used for the development of a click approach to a series of triazole-substituted bipyridinyl derivatives. 4,4′-Diethinyl 2,2′-bipyridine and 4,4′-diazido 2,2′-bipyridine were synthesized and tested in the cycloaddition reactions. While 4,4′-diazido 2,2′-bipyridine revealed unreactive in CuAAC reactions, its corresponding N,N′-dioxide afforded the expected cycloaddition product. Georg Thieme Verlag Stuttgart.
- Fabbrizzi, Pierangelo,Cecconi, Bianca,Cicchi, Stefano
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scheme or table
p. 223 - 226
(2011/03/22)
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- Electronic optimization of heteroleptic Ru(II) bipyridine complexes by remote substituents: Synthesis, characterization, and application to dye-sensitized solar cells
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We prepared a series of new heteroleptic ruthenium(II) complexes, Ru(NCS)2LL0 (3a-3e), where L is 4,40-di(hydroxycarbonyl)-2,20-bipyridine and L0 is 4,40-di(p-Xphenyl)- 2,20-pyridine (X = CN (a), F (b), H (c), OMe (d), and NMe2 (e)), in an attempt to explore the structure-activity relationships in their photophysical and electrochemical behavior and in their performance in dye-sensitized solar cells (DSSCs). When substituent X is changed from electron-donating NMe2 to electron-withdrawing CN, the absorption and emission maxima reveal systematic bathochromic shifts. The redox potentials of these dyes are also significantly influenced by X. The electronic properties of the dyes were theoretically analyzed using density functional theory calculations; the results show good correlations with the experimental results. The solar-cell performance of DSSCs based on dye-grafted nanocrystalline TiO2 using 3a-3e and standard N3 (bis[(4,40-carboxy-2,20-bipyridine)(thiocyanato)]ruthenium(II)) were compared, revealing substantial dependences on the dye structures, particularly on the remote substituent X. The 3d-based device showed the best performance: η = 8.30%, JSC = 16.0 mA 3 cm-2, VOC = 717 mV, and ff = 0.72. These values are better than N3-based device. 2011 American Chemical Society. 2011 American Chemical Society.
- Han, Won-Sik,Han, Jung-Kyu,Kim, Hyun-Young,Choi, Mi Jin,Kang, Yong-Soo,Pac, Chyongjin,Kang, Sang Ook
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scheme or table
p. 3271 - 3280
(2011/06/22)
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- Structural studies of complex compounds of 6,6'-diacetyl-2,2'-bipyridine dioxime with copper(I/II), platinum(II), and palladium(II) metal ions
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The tetradentate ligand 6,6'-diacetyl-2,2'-bipyridine dioxime (L) was obtained in high yield by the condensation reaction of 6,6'-diacetyl-2,2'- bipyridine with hydroxyl amine in alkaline solution. Density functional calculations and 3D modeling of the structure at the B3LYP/6-31G(d) level of theory for L revealed that the energy difference between the global trans conformer (trans-L), which possesses the C2h point group, and the distorted cis conformer (cis-L) was 5.214 kcal/mol. Synthesis and characterization of the metal complexes with Cu(I), Cu(II), Pt(II), and Pd(II) metal ions were reported. L acted as a N4- donor ligand to coordinate to the metal centers via N atoms of the 2,2'-bipyridine and the imine moieties to afford tetrahedral complex [CuI L]PF6 (1), distorted octahedral complex [CuII L(OH2)2](NO 3)2 (2), and square-planar complexes [PtII L]Cl2 (3) and [PdII L]Cl (4), respectively. The CHN analysis for 1 implies that L coordinated to 2 copper(I) ions as a bridging ligand to form a dinuclear metal complex, [Cu2L2] 2+, due to the twisting of the coordinated bonds exposed by the tetrahedral geometry preference for the metal ion. The ligand formed intramolecular hydrogen bonds between the oxime groups in 4, as revealed by the spectroscopic studies. The most stable conformations of the compounds were obtained by using the molecular mechanics optimization feature in CAChe software with an augmented MM2 force field. 1.
- Sengul, Abdurrahman,Agac, Hakan,Coban, Burak,Eroglu, Erol
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scheme or table
p. 25 - 36
(2011/12/22)
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- Conversion of solar energy to chemical energy
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The rate of evolution of hydrogen from water by photochemical process using solar energy has been investigated employing fourteen metal complexes as catalysts, ten electron relays, three electron donors and two co-catalysts in different permutation and combinations. The effect of varying reaction conditions like temperature, concentration and pH have also been investigated for the optimum production of hydrogen by the photochemical cleavage of water molecules.
- Ranganayakulu,Murthy
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scheme or table
p. 309 - 316
(2011/08/09)
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- Towards allosteric receptors - Synthesis of Resorcinarene-Functionalized 2,2′-Bipyridines and their metal complexes
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Based on a first: example of an allosteric hemicarcerand (1) we prepared four new 2,2′bipyridines that carry resorcinarene moieties in a highly convergent manner. Upon coordination to suitable transition metal ions or their complexes these compounds undergo conformational changes in a way that: they switch between "open" and. "closed" forms (2, 3, and 4) or vice versa (5), thus, bringing together or separating the two functional, moieties on the central, bipyridine, Among the transition metal complexes that act: as effectors for the conformational switching, [Re(CO)5Cl] and monomeric copper(I) complexes of sterically hindered 2,9-arylated 1,10-phenanthrolines proved, to be very effective.
- Staats, Holger,Eggers, Friederike,Hass, Oliver,Fahrenkrug, Frank,Matthey, Jens,Luening, Ulrich,Luetzen, Arne
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body text
p. 4777 - 4792
(2009/12/25)
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- Remarkable tuning of the coordination and photophysical properties of lanthanide ions in a series of tetrazole-based complexes
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A series of seven new tetrazole-based ligands (Ll, L3-L8) containing terpyridine or bipyridine chromophores suited to the formation of luminescent complexes of lanthanides have been synthesized. All ligands were prepared from the respective carbonitriles by thermal cycloaddition of sodium azide. The crystal structures of the homoleptic terpyridine-tetrazolate complexes [Ln(Li)2]NHEt3 (Ln = Nd, Eu, Tb for i = 1, 2; Ln = Eu for i = 3, 4) and of the monoaquo bypyridine-tetrazolate complex [Eu(H 2O)(L7)2]NHEt3 were determined. The tetradentate bipyridine-tetrazolate ligand forms nonhelical complexes that can contain a water molecule coordinated to the metal. Conversely, the pentadentate terpyridine-tetrazolate ligands wrap around the metal, thereby preventing solvent coordination and forming chiral double-helical complexes similarly to the analogue terpyridine-carboxylate. Proton NMR spectroscopy studies show that the solid-state structures of these complexes are retained in solution and indicate the kinetic stability of the hydrophobic complexes of terpyridine-tetrazolates. UV spectroscopy results suggest that terpyridine-tetrazolate complexes have a similar stability to their carboxylate analogues, which is sufficient for their isolation in aerobic conditions. The replacement of the carboxylate group with tetrazolate extends the absorption window of the corresponding terpyridine- (≈ 20nm) and bipyridine-based (25 nm) complexes to-wards the visible region (up to 440 nm). Moreover, the substitution of the terpyridine-tetrazolate system with different groups in the ligand series L3-L6 has a very important effect on both absorption spectra and luminescence efficiency of their lanthanide complexes. The tetrazole-based ligands Ll and L3-L8 sensitize efficiently the luminescent emission of lanthanide ions in the visible and near-IR regions with quantum yields ranging from 5 to 53 % for Eu III complexes, 6 to 35 % for Tb1" complexes, and 0.1 to 0.3% for NdIII complexes, which is among the highest reported for a neodymium complex. The luminescence efficiency could be related to the energy of the ligand triplet states, which are strongly correlated to the ligand structures.
- Andreiadis, Eugen S.,Demadrille, Renaud,Imbert, Daniel,Pecaut, Jacques,Mazzanti, Marinella
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scheme or table
p. 9458 - 9476
(2010/04/05)
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- Syntheses, characterizations, and properties of electronically perturbed 1,1′-dimethyl-2,2′-bipyridinium tetrafluoroborates
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The syntheses of three new 2,2′-bipyridinium tetrafluoroborate sensitizers are reported. Their preliminary electrochemical and photophysical properties are compared to the properties of the more widely used pyrylium cation sensitizers. In addition, the first examples of triplet-triplet absorption spectra of 2,2′-bipyridinium ions are presented.
- Zhang, Dong,Dufek, Eric J.,Clennan, Edward L.
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p. 315 - 319
(2007/10/03)
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- Silica-supported vanadium-catalyzed N-oxidation of tertiary amines with aqueous hydrogen peroxide
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A recyclable silica supported vanadium 1 catalyzes the oxidation of tertiray amines to the corresponding N-oxides with 30% H2O 2 in high yield.
- Rout, Laxmidhar,Punniyamurthy, Tharmalingam
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p. 1958 - 1960
(2007/10/03)
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- Catalytic Conversions in Water. Part 22: Electronic Effects in the (Diimine)palladium(II)-Catalysed Aerobic Oxidation of Alcohols
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The electronic effects in the (diimine)Pd-(II)-catalysed aerobic oxidation of alcohols were investigated from the viewpoint of both the catalyst and the alcohol. A 'push-pull' mechanism is operative, where both electron-donating substituents on the benzyl alcohol (ρ = -0.58) and electron-withdrawing groups on the 4,4′-disubstituted-2,2′-bipyridine ligand (ρ = +0.18) increase the reaction rate. The results indicate partial reduction of the palladium centre in the transition state of the rate-limiting step.
- Ten Brink, Gerd-Jan,Arends, Isabel W. C. E.,Hoogenraad, Marcel,Verspui, Goeran,Sheldon, Roger A.
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p. 497 - 505
(2007/10/03)
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- Divalent osmium complexes: Synthesis, characterization, strong red phosphorescence, and electrophosphorescence
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We report new divalent osmium complexes that feature strong red metal-to-ligand-charge-transfer (MLCT) phosphorescence and electrophosphorescence. The general formula of the complexes is Os(II)(N-N)2L-L, where N-N is either a bipyridine or a phenanthroline and L-L is either a phosphine or an arsine. New polypyridyl ligands synthesized are 4,4′-di(biphenyl)-2,2′-bipyridine (15) and 4,4′-di(diphenyl ether)-2,2′-bipyridine (16), and the 1,10-phenanthroline derivatives synthesized are 4,7-bis(p-methoxyphen-yl)-1,10-phenanthroline (17), 4,7-bis(p-bromophenyl)-1,10-phenanthroline (18), 4,7-bis(4′-phenoxybiphen-4-yl)-1,10-phenanthroline (19), and 4,7-bis(4-naphth-2-ylphenyl)-1,10-phenanthroline (20). 4,4′-Diphenyl-2,2′-bipyridine (21) and 4,7-diphenyl-1,10-phenanthroline (22) were also used in these studies. Strong π-acid ligands used were 1,2-bis(diphenylarseno) ethane (23), cis- 1,2-bis(diphenylphosphino)ethylene (24), and cis-1,2-vinylenebis(diphenylarsine) (25). Ligand 25 is used for the first time in these types of luminescent osmium complexes. These compounds feature strong MLCT absorption bands in the visible region and strong red phosphorescent emission ranging from 611 to 651 nm, with quantum efficiency up to 45% in ethanol solution at room temperature. Red organic light-emitting diodes (OLEDs) were successfully fabricated by doping the Os(II) complexes into blend of poly(N-vinylcarbazole) (PVK) and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD). Brightness over 1400 cd/m2 for a double-layer device has been reached, with a turn-on voltage of 8 V. The maximum external quantum efficiency was 0.64%. Commission Internationale de I'Eclairage (CIE) chromaticity coordinates (x, y) of the red electrophosphorescence from the complexes are (0.65, 0.34), which indicates pure red emission.
- Carlson, Brenden,Phelan, Gregory D.,Kaminsky, Werner,Dalton, Larry,Jiang, Xuezhong,Liu, Sen,Jen, Alex K.-Y.
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p. 14162 - 14172
(2007/10/03)
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- Tertiary amine oxidation using HOF-CH3CN: A novel synthesis of N-oxides
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HOF·CH3CN, probably the best oxygen transfer agent organic chemistry has to offer, is easily made by bubbling diluted fluorine (10-15%) through aqueous acetonitrile solution. Used as formed without any isolation or purification, it reacts with various tertiary amines such as pyridine derivatives, polyaromatic nitrogen containing compounds and aliphatic and alicyclic ones to form the corresponding N-oxides. When two nitrogen atoms are present it is possible to make both the N-monoxides and the N,N-dioxides. The reaction times are short (a few minutes), conditions are very mild (0-25 °C) and the yields range from good to excellent (70-95%).
- Dayan, Sharon,Moshe, Kol,Rozen, Shlomo
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p. 1427 - 1430
(2007/10/03)
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- 52. Influence of Chelating Groups on the Luminescence Properties of Europium(III) and Terbium(III) Chelates in the 2,2'-Bipyridine Series
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Eight different 2,2'-bipyridine derivatives, i.e. 2, 5, 8, 10, 12, 13, 15, and 19 (Schemes 1 and 2), were prepared to study the influence of the chelating groups on the luminescence properties of their EuIII and TbIII chelates.According to our luminescence results, 2,2'-(methylenenitrilo)bis(acetic acid) as well as (methylenenitrilo)bis(methylphosphonic acid) in 6- and 6'-position of 2,2'-bipyridine is a suitable group when developing luminescent markers for bioaffinity assays based on time-resolved luminescence measurement.
- Mukkala, Veli-Matti,Kwiatkowski, Marek,Kankare, Jouko,Takalo, Harri
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p. 893 - 899
(2007/10/02)
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- An Excellent Method for the Mild and Safe Oxidation of N-Heteroaromatic Compounds and Tertiary Amines
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Selective, mild and safe N-oxidation of N-heteroaromatic compounds and tertiary amines affording high product yields was achieved by using the H2O2-urea/phthalic anhydride system. Key Words: N-Oxidation / Hydrogen peroxide / Urea / Phthalic anhydride
- Kaczmarek, Lukasz,Balicki, Roman,Nantka-Namirski, Pawel
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p. 1965 - 1966
(2007/10/02)
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- Nature of the Reactive Intermediates from the Iron-Induced Activation of Hydrogen Peroxide: Agents for the Ketonization of Methylenic Carbons, the Monooxygenation of Hydrocarbons, and the Dioxygenation of Arylolefins
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The reaction efficiencies and product selectivities for a group of ML/HOOH/substrate/solvent systems have been evaluated.The catalysts include Fe(II)(PA)2, Fe(II)(DPA)22-, Fe(III)Cl3, (ClO4)2, Fe(II)(MeCN)
- Tung, Hui-Chan,Kang, Chan,Sawyer, Donald T.
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p. 3445 - 3455
(2007/10/02)
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- Preparation and Characterisation of 2,2'-Bipyridine-4,4'-disulphonic and -5-sulphonic Acids and their Ruthenium(II) Complexes. Excited-state Properties and Excited-state Electron-transfer Reactions of Ruthenium(II) Complexes containing 2,2'-Bipyridine-4,4'-disulphonic Acid or 2,2'-Bipy..
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We report the syntheses of 2,2'-bipyridine-4,4'-disulphonic acid (H2bp-4,4'-ds) and 2,2'-bipyridine-5-sulphonic acid (Hbp-5-s), and several ruthenium(II) complexes derived therefrom, including 4-, 2- (bipy=2,2'-bipyridine), , and - and their 2,2'-bipyridine-4,4'-dicarboxylic acid (H2bpdc) analogues, viz. 4-, 2-, and .Some novel thioalkyl derivatives of 2,2'-bipyridine, including 4,4'-di(methylthio)-2,2'-bipyridine, 4,4'-di(ethylthio)-2,2'-bipyridine, and 4,4',6,6'-tetra(methylthio)-2,2'-bipyridine, were also prepared and characterised during the course of this investigation.The luminescent states of the complexes 4-, 2-, 4-, 2-, and were studied using variable-temperature lifetime measurements.Studies of the quenching of 2+>*, >*, 2->*, and 4->* by 1,1'-dimethyl-4,4'-bipyridinium bromide (methyl viologen) in aqueous solution as a function of ionic strength have demonstrated that the effects of charge in these electron-transfer reactions can be understood in terms of conventional theories of ionic reactions whilst, at the same time, confirming the effective charges of the ruthenium(II) complex ions.The rate constants for the quenching of 4->* and 2->* by copper(II) ions in neutral aqueous solution show unusual (non-Arrhenius) temperature dependences.A novel kinetic scheme involving parallel inner- and outer-sphere quenching mechanisms has been proposed to account for the observed behaviour.The luminescence decay of >* in the presence of aqueous copper(II) ions at pH 3.5 is non-exponential.This is interpreted in terms of a combination of static and dynamic quenching effects.
- Anderson, Susan,Constable, Edwin C.,Seddon, Kenneth R.,Turp, Janet E.,Baggott, James E.,Pilling, Michael J.
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p. 2247 - 2262
(2007/10/02)
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