21907-47-1Relevant articles and documents
Synthesis, and crystal and molecular structures of the triflato and trifluoroacetato complexes of zinc, Zn(O3SCF3)2(DME)2 and [Zn(O2CCF3)2(DME)]n
Dell'Amico, Daniela Belli,Boschi, Daniele,Calderazzo, Fausto,Labella, Luca,Marchetti, Fabio
, p. 149 - 154 (2002)
Anhydrous Zn(O3SCF3)2 and Zn(O2CCX3)2, X=F, Cl, Br were obtained in substantially quantitative yields from ZnO (or ZnEt2 in the case of the bromide derivative) and a mixture of the corresponding acid and anhydride in heptane as medium. The reactions are rapid and moderately exothermic. Recrystallization of the triflate and trifluoroacetate complexes from dimethoxyethane (DME) produced single crystals of Zn(O3SCF3)2(DME)2 (1) and [Zn(O2CCF3)2(DME)]n (2) suitable for X-ray diffraction studies. In both compounds zinc is hexacoordinated with a pseudo-octahedral geometry. Compound 1 is constituted by mononuclear molecules with terminal monodentate O3SCF3 ligands in trans position. A polynuclear chain structure was found for 2 with zinc atoms joined alternatively by triple and single carboxylato bridges, and with bidentate terminal DME.
Syntheses, structures, and fluxionality of blue luminescent Zinc(II) complexes: Zn(2,2',2-tpa)Cl2, Zn(2,2',2-tpa)2(O2CCF3)2, and Zn(2,2',3-tpa)4(O2CCF3)2 (tpa = tripyridylamine)
Yang, Wenyu,Schmider, Hartmut,Wu, Qingguo,Zhang, You-Sheng,Wang, Suning
, p. 2397 - 2404 (2000)
Three novel Zn(II) complexes containing either 2,2',2-tripyridylamine (2,2',2-tpa) or 2,2',3-tripyridylamine (2,2',3-tpa) have been synthesized and structurally characterized. Compound 1, Zn(2,2',2-tpa)Cl2, has a tetrahedral geometry while compounds 2, Zn(2,2',2-tpa)2(O2CCF3)2, and 3, Zn(2,2',3-tpa)4(O2CCF3)2, have an octahedral geometry. The 2,2',2-tpa ligand in 1 and 2 functions as a bidentate ligand, chelating to the zinc center, while the 2,2,3-tpa ligand in 3 functions as a terminal ligand, binding to the zinc center through the 3-pyridyl nitrogen atom. All three compounds emit a blue color in solution and in the solid state. The emission maxima for the three compounds in solution are at λ = 422, 426, and 432 nm, respectively. The blue luminescence of the complexes is due to a π* → π transition of the tpa ligand as established by an ab initio calculation on the free ligand 2,2',2-tpa and complex 1. Compounds 1 and 2 are fluxional in solution owing to an exchange process between the coordinate and noncoordinate 2-pyridyl rings of the 2,2',2-tpa ligand. Compound 2 is also fluxional owing to a cis-trans isomerization process, as determined by variable-temperature 1H NMR spectroscopic analysis.
Formation of ionic liquids of divalent metal complexes comprising N?alkylethylenediamines and the solvation of the nickel(II) complexes
Yasuda, Haruka,Nakayama, Chisayo,Iida, Masayasu
, p. 169 - 177 (2018/08/21)
A series of divalent N?alkylethylenediamine (alkyl?en) metal(II) (alkyl = hexyl, 2?ethylhexyl, octyl, dodecyl; metal = Ni, Cu, and Zn) complexes was prepared and their phase behavior was studied using differential scanning calorimetry. This kind of metal complexes is very useful for systematically investigating the relationship between phase behavior and molecular structures. It was found that several of the zinc(II) and nickel(II) complexes form room-temperature ionic liquids (RTILs), despite the divalent cation. Although the solid-to-liquid transition temperatures of metal(II) complex-based ILs are typically higher than those of the more common monovalent ionic liquids (ILs), they are dependent on the nature and combination of the metal(II) ions, alkyl chains, and counter anions. The zinc(II) complexes coupled with weakly coordinating bis(fluorosulfonyl)amide (FSA) or bis(trifluoromethanesulfonyl)amide (Tf2N) anions have significantly lower melting points, which is attributable to the longer distance between the zinc(II) ions and the counter anions upon the formation of tetrahedral bis(alkyl?en)zinc(II) complexes as compared to the corresponding distances in NO3 and trifluoroacetate (TFA) complexes. The correlation of melting points with the molecular structures of the zinc(II) complexes is similar to that for the silver(I) alkyl?en complexes. The tris(alkyl?en)nickel(II) complexes coupled with Tf2N counter ions do not readily solidify and have glass transition temperatures below 0 °C, whereas the corresponding bis complexes have much higher melting points despite the counter-ions residing in the outer-spheres of the nickel(II) ions. The interactions of NO3, TFA, FSA, and Tf2N anions with the nickel(II) ions of the bis(alkyl?en) complexes and their solvation behaviors were also studied in organic solvents using visible absorption spectroscopy based on the structures of the neat states. The characteristic solvation behaviors of the nickel(II) complexes were rationalized in terms of the counter anions and solvents.
ORGANIC ELECTRONIC COMPONENT HAVING A CHARGE CARRIER GENERATION LAYER AND THE USE OF A ZINC COMPLEX AS A P-TYPE DOPANT IN CHARGE CARRIER GENERATION LAYERS
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Paragraph 0316-0317, (2018/10/19)
The invention relates to an organic electronic component (100) comprising at least one charge generation layer (5) which has an organically p-doped region (5a) that contains a zinc complex as a p-dopant, said zinc complex in turn containing at least one ligand L of the following structure: formula (I) wherein R1 and R2 can be oxygen, sulphur, selenium, NH or NR4 independently from one another, wherein R4 is selected from the group containing alkyl or aryl and which can be bonded to R3; and wherein R3 is selected from the group containing alkyl, long-chain alkyl, cycloalkyl, halogen alkyl, at least partially halogenated long-chain alkyl, halogen cycloalkyl, aryl, arylene, halogen aryl, heteroaryl, heteroarylene, heterocyclic alkylene, heterocycloalkyl, halogen heteroaryl, alkenyl, halogen alkenyl, alkynyl, halogen alkynyl, ketoaryl, halogen ketoaryl, ketoheteroaryl, ketoalkyl, halogen ketoalkyl, ketoalkenyl, halogen ketoalkenyl, halogen alkyl aryl, and halogen alkyl heteroaryl, wherein, for suitable groups, one or a number of non-adjacent CH2 groups can be replaced by —O—, —S—, —NH—, —NR°°°—, —SiR°R°°—, —CO—, —COO—, —COR°OR°°—, —OCO—, —OCO—O—, —SO2-, —S—CO—, —CO—S—, —O—CS—, —CS—O—, —CY1=CY2 or —C≡C— independently from one another, and in such a way that O and/or S atoms are not directly bonded to one another, and are replaced optionally with aryl- or heteroaryl preferably containing between 1 and 30 C atoms (terminal CH3 groups are understood to be CH2 groups in the sense of CH2-H). The invention further relates to the use of a zinc complex as a p-dopant in charge generation layers.
Series of dicyanamide-interlaced assembly of zinc-schiff-base complexes: Crystal structure and photophysical and thermal studies
Maiti, Monami,Sadhukhan, Dipali,Thakurta, Santarupa,Roy, Syamantak,Pilet, Guillaume,Butcher, Ray J.,Nonat, Aline,Charbonniere, Loic J.,Mitra, Samiran
, p. 12176 - 12187 (2013/01/15)
Four new dicyanamide (dca) bridged multinuclear ZnII-Schiff-base complexes, {[Zn2L1(μ1,5-dca)dca] ·CH3OH}2 (1), [Zn2L2(μ 1,5-dca)dca]n (2), [Zn3L3 2(μ1,5-dca)2]n (3), and [(ZnL4)2Zn(μ1,5-dca)dca]n (4), have been synthesized using four different Schiff bases L1H 2 = N,N/-bis(3-methoxysalicylidenimino)-1,3- diaminopentane, L2H2 = N,N'-bis(5-bromo-3- methoxysalicylidenimino)-1,3-diaminopropane, L3H2 = N,N'-bis(5-bromosalicylidenimino)-1,3-diaminopropane, and L4H 2 = N,N'-bis(5-chlorosalicylidenimino)-1,3-diaminopropane and NaN(CN)2 in order to extend the metal-ligand assembly. The directional properties of linear end-to-end bridging dca ligands have resulted in different metal ion connectivities leading to unique variety of templates in each of the complexes. All the ligands and complexes have been characterized by microanalytical and spectroscopic techniques. The structures of the complexes have been conclusively determined by single crystal X-ray diffraction studies. Thermogravimetric analyses have been performed to investigate the thermal stability of the metal-organic frameworks. Finally, the photoluminescence properties of the complexes as well as their respective ligands have been investigated with a comparative approach.
Large kinetic isotope effects for the protonolysis of metal-methyl complexes are not reliable mechanistic indicators
Scott, Valerie J.,Labinger, Jay A.,Bercaw, John E.
, p. 4374 - 4378 (2011/10/10)
Earlier work on protonolyses of several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal-methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension of these measurements to a wider set of complexes, we find no support for the proposed correlation.
(II), Copper(II), and Nickel(II) Complexes of Bis(tripodal) Diamide Ligands - Reversible Switching of the Amide Coordination Mode upon Deprotonation
Hahn, F.Ekkehardt,Schroeder, Henning,Pape, Tania,Hupka, Florian
, p. 909 - 917 (2010/06/18)
A series of dinuclear Zn(II), Cu(II) and Ni(II) complexes of two new bis-tripodal ligands with aromatic (H2-4a) and aliphatic (H 2-4b) diamide spacers has been synthesized and structurally characterized. Each of the two tripodal entities of the neutral dinucleating ligands coordinates to one metal ion via three amine functions and a carbonyl oxygen atom of the amide groups. Either trifluoroacetate counterions or solvent molecules complete the trigonal-bipyramidal (Zn, Sa), square-pyramidal (Cu, 6a and 6b), and octahedral (Ni, 7a and 7b) coordination environment at the metal centers. Complexes 5a, 6a, and 7a with the phenylene-bridged diamide ligand are readily deprotonated by potassium tert-butoxide effecting a rearrangement of the dinuclear complexes. In the resulting zinc and copper complexes 8 and 9, one of the metal centers is coordinated by three amine functions of a tripodal subunit and the two amidate nitrogen atoms of the deprotonated ligand 4a2- while the coordination geometry of the second metal atom remains unchanged. The analogous nickel compound crystallizes as neutral tetranuclear complex (10) 2 with intermolecular coordination of two amide carbonyl oxygen atoms to the nickel atoms of an adjacent dinuclear complex. The resulting coordination mode with binding of all four donor functions of the diamide spacer to three discrete metal centers is to date unprecedented for ortho-phenylene-bridged acetamides. The rearrangement upon deprotonation has been shown to be fully reversible and the starting complexes can be retrieved upon protonation of the two amidate functions. Synthesis of the trinuclear zinc complex 11 with coordination of the two amidate nitrogen atoms to a third metal center was achieved via deprotonation of (H6-4a)-(CF 3CO2)4 by three equivalents of diethylzinc. In protic solvents 11 rapidly rearranges to give the entropically favored dinuclear complex 8 with elimination of one equivalent of zinc trifluoroacetate.
Salts of zinc and aliphatic haloid carboxylic acids for therapy of skin neoplasms and visible mucous coats
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Page/Page column 4, (2008/06/13)
The invention relates to medicine, and more particularly to dermatology, namely to new salts of zinc and aliphatic haloid carboxylic acids which can be used to treat benign skin lesions and visible mucous coats. The following chemical formula of salts of zinc and aliphatic haloid carboxylic acids is proposed wherein in formulae Fluorine (F), Chlorine (Cl), Bromine (Br) or Iodine (J) can be a halogen atom. The obtained technical result is the creation of a unique preparation to treat benign skin lesions and visible mucous coats. The preparation is low-toxic, fast acting with a pronounced therapeutic effect and a good tolerance. It causes no complications during therapy, and ensures healing without scar tissue formation. The created preparation allows to extend the assortment of drugs for therapy of similar diseases.
Rational syntheses, structure, and properties of the first bismuth(II) carboxylate
Dikarev, Evgeny V.,Li, Bo
, p. 3461 - 3466 (2008/10/09)
Bismuth(II) trifluoroacetate (1), the first inorganic salt of bismuth in oxidation state +2, has been obtained in its pure, unstabilized form. Several synthetic routes suggested for the isolation of the new compound include (i) mild oxidation of elemental bismuth with some metal trifluoroacetates, e.g., AgI and HgII; (ii) mild reduction of bismuth-(III) trifluoroacetate with metals, such as Zn; (iii) comproportionation reaction between Bi and Bi(O2CCF3)3. The last approach gives the title compound 1 in quantitative yield as a sole product. Bismuth(II) trifluoroacetate has been characterized by NMR, IR, and UV-vis spectroscopy as well as by single-crystal X-ray diffraction. Crystallographic study reveals the dinuclear paddle-wheel structure for diamagnetic molecules Bi2(O 2CCF3)4. The Bi-Bi bond distances in dimetal units of 1 are averaged to 2.9462(3) A, and there are no axial intermolecular contacts between these units in the solid state. The compound is volatile and exists in vapor phase up to 220 °C when it disproportionates back to Bi0 and BiIII species, i.e., by the reverse of the synthetic route iii. In contrast, the solution chemistry is quite limited: the bismuth(II) trifluoroacetate is decomposed by the majority of common solvents, but it can be stabilized by aromatic systems. The dibismuth unit has been shown to be preserved in the latter solvents and can be crystallized out in a form of π-adducts with arenes. Two such adducts, Bi2(O 2CCF3)4·(C6H5Me) (2) and Bi2(O2CCF3)4· (1,4-C6H4Me2)2 (3), have been isolated as single crystals and characterized by X-ray diffraction techniques. In the structures of both 2 and 3, the bismuth(II) centers exhibit weak η6-coordination to aromatic rings.
