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1.
Synthesis and electrochemical properties of a chiral silyl-substituted tetrathiafulvalene derivative
A new chiral tetrathiafulvalene(TTF) derivative and related silyl-substituted 1,3-dithiole-2-(thi)one compounds were synthesized and characterized by ~1H NMR,~(13)C NMR,MS and IR spectra.Single crystal structure of the silyl-substituted 1,3-dithiole-2-one revealed the high degree of conjugation of the fivemembered ring moiety in the compound.The electrochemical properties of the new TTF derivative were studied by cyclic voltammetry and the results indicated that the electron-donating ability of the chiral TTF derivative was similar to that of BEDT-TTF.The △E value for the new TTF derivative was smaller than those for TTF and BEDT-TTF,indicative of decreased Coulombic repulsion in the dicationic redox state.Formation of charge-transfer(CT) complex between the new donor and electron acceptor 2,3-dichloro-5,6-dicyano-l,4-benzoquinone(DDQ) was demonstrated. 相似文献
2.
Ying-Fen Ran Martin Steinmann Marc Sigrist Shi-Xia Liu Jürg Hauser Silvio Decurtins 《Comptes Rendus Chimie》2012,15(10):838-844
The explorative lanthanide coordination chemistry of 4′,5′-bis-(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2′,3′-c]phenazine (TTF-dppz) is described. Thereby, four new Ln(III) complexes, [Ln(NO3)3(TTF-dppz)2] with Ln(III) = Nd (1), Eu (2), Gd (3), Tb (4), have been prepared and characterized. An X-ray crystallographic study of [Gd(NO3)3(TTF-dppz)2] (3) shows that the Gd(III) ion is coordinated to six oxygen atoms from three bidentate nitrate ligands and four nitrogen atoms from two bidentate TTF-dppz molecules forming a distorted bicapped square antiprism coordination geometry. The UV-vis spectra of the four Ln(III) complexes show very strong absorption bands in the UV region consistent with ligand centred electronic π-π* transitions and an intense broad absorption band in the visible region corresponding to a spin-allowed electronic π-π* 1ILCT transition from the TTF-dppz ligand. Upon coordination, the 1ILCT band of the free TTF-dppz ligand is bathochromically shifted. The electrochemical studies reveal that all complexes undergo two reversible oxidation and one (quasi)reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the dppz unit, respectively. Moreover, the magnetic properties of complexes 3 and 4 are discussed. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(6):965-972
A silver(I) complex with nitronyl nitroxide, [Ag2(NIT-R)4(NO3)2]?·?CH3OH [NIT-R?=?2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl-3-oxide], has been prepared and characterized by magnetic and single-crystal X-ray diffraction studies. In the complex, the silver(I) ion is coordinated with two monodentate nitronyl nitroxide radicals by the nitrogen of the imizadole ring. The silver(I) ion is two-coordinate and forms a dimer through Ag?···?Ag weak metal bonding interactions. The magnetic properties for the title complex have been investigated in the temperature range 2?~?300?K showing ferromagnetic interactions between the coordinated nitronyl nitroxides (J?=?3.64?cm?1) and intermolecular antiferromagnetic interactions. 相似文献
4.
《Journal of Coordination Chemistry》2012,65(15):2506-2514
The mononuclear cobalt(III) complex [Co(L)2]Cl ·?H2O (1) (where L is H2N(CH2)2N=CC6H3(OMe)(O?)) has been prepared and characterized by IR, UV-Vis spectroscopy, conductivity measurements, elemental analysis, TGA, cyclic voltammetry and an X-ray structure determination. The cobalt(III) coordination sphere in [Co(L)2] is cis-CoN4O2 with the NNO ligands. Electrochemical studies of 1 using cyclic voltammetry indicate an irreversible cathodic peak (E pc, ca ?0.60 V) corresponding to reduction of cobalt(III) to cobalt(II). 相似文献
5.
Gang Wu Xiao-Feng Wang Min Chen Norikazu Ueyama 《Journal of solid state chemistry》2010,183(9):2174-2182
Five new silver(I) complexes [Ag2(L2)2](BF4)2·CH3CN·CH3OH (1), [Ag(L2)(CF3SO3)] (2), [Ag(L3)]ClO4·CH3OH (3), [Ag2(L3)2](CF3SO3)2·CH3CN·CH3OH·H2O (4) and [Ag(L3)]PF6·2CH3CN (5) [L2=1,3,5-tris(2-pyridylmethoxyl)benzene, L3=1,3,5-tris(3-pyridylmethoxyl)benzene] were synthesized and characterized by single crystal X-ray diffraction analyses. In complexes 1-5, ligands L2 and L3 show different conformations and act as three-connectors, while the Ag(I) atom serves as three-connecting node to result in the formation of 2D and 3D frameworks. Complexes 1 and 2 with different counteranions have similar 2D network structure with the same (4,82) topology. Complex 3 has a 3D structure with (10,3)-a topology while complexes 4 and 5 have the same 2D (6,3) topological structure. The results showed that the structure of organic ligands and counteranions play subtle but important role in determining the structure of the complexes. In addition, the photoluminescence and anion-exchange properties of the complexes were investigated in the solid state at room temperature. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(5):835-847
Two ligands, bis(benzimidazol-2-ylmethyl) aniline (bba) and bis(N-methyl-benzimidazol-2-ylmethyl) aniline (Mebba), and their transition metal complexes [Zn(bba)(Br)2]·2DMF (1) and [Cu(Mebba)(Br)2]·2DMF (2) have been synthesized and characterized by elemental analyses, molar conductivities, UV–vis spectra, IR spectra, NMR spectroscopy, and X-ray crystallography. The structure around Zn(II) can be described as distorted tetrahedral. Complex 2 can be described as distorted trigonal bipyramidal. Cyclic voltammograms of 2 indicate a quasireversible Cu2+/Cu+ couple. Additionally, the antioxidant activities of the free ligands and their complexes were determined by the superoxide and hydroxyl radical scavenging methods in vitro. Complexes 1 and 2 possess potent hydroxyl radical scavenging activity and better than standard antioxidants such as vitamin C and mannitol. Complex 2 possesses excellent superoxide radical activity. 相似文献
7.
G. Attilio Ardizzoia Stefano Brenna Fulvio Castelli Simona Galli Girolamo LaMonica Norberto Masciocchi Angelo Maspero 《Polyhedron》2004,23(18):3063-3068
When the polymeric complex [Ag(im)]n (Him = imidazole) is reacted with PPh3 (PPh3 = triphenylphosphine), it yields the [Ag2(μ2-im)2(PPh3)3]n and [Ag(μ2-im)(PPh3)2]n species, shown to contain wavy chains of metal ions, singly bridged by N,N′-exo-bidentate imidazolate ligands. The former, crystallised as the CH2Cl2 solvate, contains two non-equivalent silver(I) ions, differing in the number of coordinated phosphines (one, in trigonal planar stereochemistry, or two, having tetrahedral geometry). The latter has a unique independent silver(I) ion in a tetrahedral environment, with two coordinated PPh3 ligands. The reactivity of known silver(I) azolates with PPh3, as well as the solution behaviour and (when available) the crystal structures of the corresponding derivatives are taken into consideration for a due comparison. 相似文献
8.
《Journal of Coordination Chemistry》2012,65(24):3905-3912
A new coordination polymer [Zn(PMP)2Cl] n (PMP = 1-phenyl-3-methyl-5-pyrazolone) has been prepared by the reaction of zinc chloride and PMP, and characterized by elemental analysis, IR, UV, and fluorescence spectra, TG/DTA, and electrochemical analysis. Single crystal X-ray diffraction revealed that the complex is monoclinic, space group P 2(1)/n, with a = 10.850(17), b = 17.578(2), c = 10.997(18) Å, β = 104.999(3)°, V = 2025.8(5) Å3, Z = 4, Dc = 1.470 mg m?3, F(000) = 920, goodness-of-fit = 0.905, and R 1 = 0.0441. The complex is a 1-D coordination polymer, and the coordination geometry of Zn(II) is a distorted tetrahedron. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(23):4098-4107
A macrocyclic hexanuclear iron(III) 18-metallacrown-6 complex, [Fe6(C9H6BrN2O3)6(CH3OH)4(H2O)2]?·?7CH3OH?·?4H2O, has been prepared using a trianionic pentadentate ligand N-acetyl-5-bromosalicylhydrazidate, abshz3–, and characterized by X-ray diffraction. The crystal structure contains a neutral 18-membered metallacrown ring consisting of six Fe(III) and six abshz3– ligands. The 18-membered metallacrown ring is formed by combination of six structural moieties, [Fe(III)–N–N]. Due to meridional coordination of ligand to Fe3+, the ligand enforces the stereochemistry of the Fe3+ ions as a propeller configuration with alternating Δ/Λ forms. Methanol and water are linked with Fe1, Fe1A, Fe,3 and Fe3A. The ratios of methanol to water are 0.76?:?0.24 for Fe1 and Fe1A, and 0.30?:?0.70 for Fe3 and Fe3A, which results in four component crystals of metallacrown rings with ratio of 0.168?:?0.072?:?0.532?:?0.228. Antibacterial screening data showed that the iron metallacrown has moderate antimicrobial activity against Bacillus subtilis. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(16):2935-2944
Self-assembly of anthraquinone-2,6-disulfonic acid disodium salt (Na2a-2,6-dad) and AgNO3 under hydrothermal conditions resulted in an unprecedented coordination complex, which was characterized by single-crystal X-ray analyses, elemental analyses, IR spectra, TG analyses, and fluorescence investigations. Complex 1 is a 3-D coordination polymer, where a-2,6-dad and Ag–Ag bonds play vital roles. Two sulfonate groups of a-2,6-dad are μ 4- and μ 5-bridges. The unique packing environments of the Ag ions and Ag–Ag bonds lead to 1-D chains consisting of eight- and four-membered rings for Ag1 and Ag1, Ag2 and Ag2 connection, respectively. 相似文献
11.
Michael JaggiBelinda Schmid Shi-Xia Liu Sheshanath V. Bhosale Shadi RivadehiSteven J. Langford Silvio Decurtins 《Tetrahedron》2011,67(38):7231-7235
A tetrathiafulvalene donor has been attached to the naphthalene diimide core via a rigid bridge affording a new planar molecular dyad. Its electronic properties have been studied experimentally by the combination of electrochemistry and UV-vis-NIR spectroscopy. Various electronic excited charge-transfer states are generated in different oxidation states, leading to almost full absorption in the visible to near-IR region with high extinction coefficients. The observed electronic properties are explained on the basis of density-functional-theory. In particular, the oxidized radical species show a strong tendency to undergo aggregation, in which the long-distance attractive interactions overcome the electrostatic repulsions. 相似文献
12.
《Journal of Coordination Chemistry》2012,65(13):2312-2320
A uranium coordination compound with pyridine-2,6-dicarboxylic acid in deionized water has been synthesized and characterized by IR, UV, XPS, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group C2/c with a?=?1.8427(4)?nm, b?=?0.6886(16)?nm, c?=?1.5442(4)?nm, α?=?90°, β?=?94.082(2)°, γ?=?90°, Z?=?4, and V?=?1.9544(8)?nm3. The structure shows an eight-coordinate uranium forming a hexagonal bi-pyramidal 3-D geometry with pyridine-2,6-dicarboxylate as building units. Fluorescent studies show several strong emissions. Cyclic voltammetric measurement of the compound reveals that uranium(VI) is reduced irreversibly at E 1/2?=?927?mV with ΔE p?=?77?mV, E 1/2?=??289?mV with ΔE p?=?113?mV. The electron transfer number (n) involved in reduction processes could be calculated to be approximately two and one, which corresponded to the unusual U(VI)/U(IV) and U(IV)/U(III) couples. 相似文献
13.
Ying-Fen RanCarmen Blum Shi-Xia Liu Lionel Sanguinet Eric LevillainSilvio Decurtins 《Tetrahedron》2011,67(9):1623-1627
Highly selective formation of 2+2 macrocycle 1 from 2,5-bis(3-formyl-2-hydroxyphenyl)-1,3,4-oxadiazole and a diamine-functionalized tetrathiafulvalene derivative is reported. Its electronic properties have been studied experimentally by the combination of electrochemistry and UV-vis-NIR spectroscopy. Particularly, its largely extended π-conjugation renders this novel macrocycle simultaneously a good multielectron donor and a strong chromophore, which is rationalized on the basis of density functional theory. 相似文献
14.
《Journal of Coordination Chemistry》2012,65(9):1518-1524
A manganese(II) coordination polymer [Mn(TMB)2?·?H2O] n (1) (HTMB?=?3,4,5-trimethoxybenzoic acid) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, powder X-ray diffraction analysis, spectroscopic (IR, solid state UV-Vis), and thermal methods. The crystal belongs to orthorhombic system, space group P212121, with cell parameters a?=?7.3001(8), b?=?11.4146(13), c?=?27.053(3)?Å, α?=?β?=?γ?=?90°, V?=?2254.3(4)?Å3, Z?=?4. In 1, TMB in two different coordination modes bridges six-coordinate manganese(II) centers forming a 1-D infinite chain coordination framework. The spectral and thermal properties of the complexes have also been studied. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(24):2747-2754
A mixed-valence cyano-bridged CuII/CuI complex, 1, has been prepared. Complex 1 was fully characterized spectroscopically (UV-Vis and IR), and its structure was determined by X-ray crystallography. The magnetic property was measured in the temperature range 2–300?K. Electrochemical studies of 1 reveal a one-electron oxidation-reduction process associated with the Cu(II)/Cu(I) couple. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(14):2529-2540
A new ion-pair complex, [TTF][Pd(mnt)2] (1), where TTF+ =?tetrathiafulvalene and mnt2??=?maleonitriledithiolate, was synthesized and characterized structurally. Compound 1 crystallizes in triclinic space group P-1, with a?=?8.008(5)?Å, b?=?11.333(8)?Å, c?=?11.373(6)?Å, α?=?108.112(7)°, β?=?91.550(5)°, γ?=?95.232(5)°, and V?=?975.2(11)?Å3. The [TTF]+ cations (C) and [Pd(mnt)2]? anions (A) form mixed stacks in …AACCAACC… fashion, and the neighboring mixed stacks are held together via van der Waals forces in the crystal. Compound 1 shows weak Curie/Weiss-type magnetic behavior from 2 to 370?K; theoretical investigation disclosed the existence of strongly antiferromagnetic coupling in both [Pd(mnt)2]2 2? and [TTF]2 2+ dimer pairs via frontier orbitals overlap mechanism and weakly ferromagnetic coupling between the face-to-face overlapped [TTF]+ and [Pd(mnt)2]? via spin polarization mechanism within a mixed stack. The powdered pellet electrical conductivity measurement indicated that 1 shows semiconductor character with activation energy of 1.1(3)?eV. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(9):1412-1422
Three symmetrical macrocyclic dinuclear complexes [M2L(H2O) n ](ClO4)2 (M2+ = Cu2+, Ni2+, Mn2+ and n = 0, 2) have been synthesized by cyclocondensation between 2,6-diformyl-4-fluorophenol and 1,4-diaminobutane in the presence of M2+ cations. The crystal structure of [Cu2L](ClO4)2 was determined by X-ray diffraction techniques. The electronic and magnetic properties of the complexes were studied by cyclic voltammetry and magnetic susceptibility. The results confirm that the complexes obtain electrons easily and there are very strong antiferromagnetic couplings between two copper(II) ions in [Cu2L](ClO4)2. The strong electron-drawing groups of fluorine attached to the phenyl ring of a macrocyclic complex enhances the antiferromagnetic exchange of the complex and makes it more easily reduced than its analogs. 相似文献
18.
Four new silver(I) coordination polymers, namely [Ag(NH2pyz)(ox)0.5]n (1), [Ag(NH2pyz)(adp)0.5·2H2O]n (2), [Ag2(NH2pyz)2(bdc)·H2O]n (3) and [Ag2(NH2pyz)2.5(ndc)]n (4) [NH2pyz = 2-aminopyrazine, ox = oxalate anion, adp = adipate anion, bdc = 1,4-benzenedicarboxylate anion, ndc = 1,4-naphthalenedicarboxylate anion] have been synthesized by solution phase ultrasonic reactions of Ag2O with heterocyclic NH2pyz and various dicarboxylates under ammoniacal conditions. The complexes were characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Complex 1 is a three-dimensional (3D) framework with an α-ThSi2 topology. Complex 2 features a 2D 44-sql net involving infinite 1D double Ag-NH2pyz chains and flexible adp anion spacers. Complex 3 is a 3D framework in which 1D single Ag-NH2pyz chains are pillared by bdc anions to form a 2D 63-hcb network, adjacent 2D networks are packed into a 3D framework through bridging O atoms of dbc anions. Complex 4 is a 2D structure built from infinite 1D stair-like chains containing finite Ag4(NH2pyz)5 subunits. The results show that the structural diversity of the complexes result from the nature of the dicarboxylate ligands. The photoluminescence properties of the complexes were also investigated in the solid state at room temperature. 相似文献
19.
Lamia L. G. Al-Mahamad William Clegg 《Acta Crystallographica. Section C, Structural Chemistry》2024,80(3):80-84
Silver nitrate reacts with 6-methylmercaptopurine riboside (6-MMPR) in aqueous solution containing methanol and dimethyl sulfoxide at room temperature to give a colourless crystalline complex, namely, bis(6-methylmercaptopurine riboside-κN7)(nitrato-κ2O,O′)silver(I) 2.32-hydrate, [Ag(NO3)(C11H14N4O4S)2]·2.32H2O. The crystal structure, determined from synchrotron diffraction data, shows a central AgI ion on a crystallographic twofold rotation axis, coordinated in an almost linear fashion by two 6-MMPR ligands via atom N7 (purine numbering), with the nitrate counter-ion loosely coordinated as a bidentate ligand, forming a discrete molecular complex as an approximate dihydrate. The complex and water molecules are connected in a three-dimensional network by hydrogen bonding. 相似文献