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1.
The reactions of [RuCl2(PPh3)3] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid was examined, and a novel ruthenium(II) complex—[Ru(PPh3)2(C5H8NO)2]—was obtained. The compound was studied by IR, UV–vis spectroscopy, and X-ray crystallography. The molecular orbital diagram
of the complex was calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic
transitions of the compound were calculated using the time-dependent DFT method, and the UV–vis spectrum of the compound was
discussed, on this basis. The luminescence property of the [Ru(PPh3)2(C5H8NO)2]was examined. 相似文献
2.
Sofia Nikolaou Daniela M. Tomazela Marcos N. Eberlin Henrique E. Toma 《Transition Metal Chemistry》2008,33(8):1059-1065
The polymetallic [Ru3O(CH3COO)6(py)2(BPE)Ru(bpy)2Cl](PF6)2 complex (bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru3O] moiety with a [Ru(bpy)2(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS)
spectrometry. The [Ru3O(CH3COO)6(py)2(BPE)Ru(bpy)2Cl]2+ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic
of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)2(BPE)] charge-transfer bands and to the [Ru3O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at −1.07 V, 0.13 V, 1.17 V, 2.91 V and
−1.29 V (vs SHE) assigned to the [Ru3O]−1/0/+1/+2/+3 and to the bpy0/−1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru+2/+3 pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling
through the π-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation. 相似文献
3.
L. S. Cavalcante J. C. Sczancoski F. S. De Vicente M. T. Frabbro M. Siu Li J. A. Varela E. Longo 《Journal of Sol-Gel Science and Technology》2009,49(1):35-46
Ba[Zr0.25Ti0.75]O3 (BZT) thin films were synthesized by the complex polymerization method and heat treated at 400 °C for different times and
at 700 °C for 2 h. These thin films were analyzed by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy,
field emission gun-scanning electron microscopy (FEG-SEM) and atomic force microscopy (AFM), Ultraviolet–visible (UV–vis)
absorption spectroscopy, electrical and photoluminescence (PL) measurements. FEG-SEM and AFM micrographs showed that the microstructure
and thickness of BZT thin films can be influenced by the processing times. Dielectric constant and dielectric loss of BZT
thin films heat treated at 700 °C were approximately 148 and 0.08 at 1 MHz, respectively. UV–vis absorption spectra suggested
the presence of intermediary energy levels (shallow and deep holes) within the band gap of BZT thin films. PL behavior was
explained through the optical band gap values associated to the visible light emission components. 相似文献
4.
Zhen-Qian Zhang Hong Li Juan Xu Su Yao Zheng-He Xu Jin-Gang Liu Liang-Nian Ji 《Transition Metal Chemistry》2007,32(6):776-780
The effects of copper ion on the interaction of [Ru(bpy)2HPIP]2+(bpy = 2,2′-bipyridine, HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f] [1, 10] phenanthroline) with DNA have been investigated
by electronic absorption spectroscopy and fluorescence spectroscopy. HPIP ligand of the complex with an intramolecular hydrogen
bond can bind Cu2+ in the absence of DNA, as revealed by the absorbance and fluorescence decrease for [Ru(bpy)2HPIP]2+. The resultant heterometallic complex binds to DNA via intercalation of HPIP into the DNA base pairs and its DNA-binding ability is stronger than [Ru(bpy)2HPIP]2+ itself. The DNA bound [Ru(bpy)2HPIP]2+ cannot bind Cu2+ at low Cu2+ concentration and the intramolecular hydrogen bond in HPIP is located inside the DNA helix. While the Cu2+ concentration is relative high, Cu2+ can quench the fluorescence of DNA bound [Ru(bpy)2HPIP]2+. The quenching reason is proposed. 相似文献
5.
XueQin Chang Shun Wang DaJie Lin WeiPeng Guan Huan Zhou ShaoMing Huang 《中国科学B辑(英文版)》2009,52(3):318-324
An indium tin oxide (ITO) electrode modified with monolayer clay/[Ru(phen)2(dC18bpy)]2+ (phen=1,10-phenanthroline, dC18bpy = 4,4′-dioctadecyl-2,2′ bipyridyl) hybrid film has been fabricated by the Langmuir-Blodgett
(LB) method. Atomic force microscopy revealed that the single-layered hybrid film of clay/[Ru(phen)2(dC18bpy)]2+ (denoted as Clay-Ru) was closely packed at a surface pressure of 25 mN·m−1 and had a thickness of 3.4±0.5 nm. Cyclic voltammograms showed that the redox current of Ru(II) complex decreased when incorporated
into the clay film, suggesting that the clay layer acts as a barrier against electron transfer. When applied to oxidizing
the mononucleotide of guanosine 5′-monophosphate (GMP), a large catalytic oxidative current was achieved on the Clay-Ru(II)
modified ITO electrode at the external potential above 900 mV (vs. Ag|AgCl|KCl) and, more significantly, this response was
further enhanced by light irradiation (λ>360 nm), in which the photocurrent is increased about 11 times in comparison with
that of a bare ITO. Mechanism of the photoelectrocatalytic effect was proposed in terms of the reduction of the photoelectrochemically
generated Ru(III) complex in the Clay-Ru film by GMP.
Supported by the National Natural Science Foundation of China (Grant Nos. 20471043 and 20843007), Zhejiang Provincial Natural
Science Foundation (Grant Nos. Y404118 and Y408177), the “151” Distinguished Person Foundation of Zheji-ang Province of China,
Zhejiang Technology Project Foundation (Grant No. 2007C21134) and Wenzhou Technology Project Foundation (Grant No. N2004B040) 相似文献
6.
The ethylenediaminetetraacetate complex Li(H2O)3[Ga(Edta)] was synthesized and its crystal structure composed of octahedral (Ga(Edta)− anions connected to the Li(H2O)3+ ion through the oxygen atom was studied. Five of the six hydrogen atoms of water molecules are involved in weak hydrogen
bonds with the oxygen atoms of four Ga(Edta)− complexes, the complex anion is hydrogen-bonded to five water molecules. In addition, shortened contacts C(221)–H(22A)…O(112) between the Ga(Edta)− anions were found. As a result, the molecular packing in the crystal is determined by the three-dimensional lace of hydrogen
bonds. The results are compared with published data for the lithium salts of Bi(III), Sb(III), Fe(III), Ni(II), and Hg(II)
ethylenediaminetetraacetates. 相似文献
7.
Hui Li Jinshu Wang Hongyi Li Shu Yin Tsugio Sato 《Research on Chemical Intermediates》2010,36(1):27-37
Nitrogen and sulfur co-doped mesoporous TiO2 thin films were fabricated using thiourea as a doping resource by the combination of the sol–gel and evaporation-induced
self-assembly (EISA) processes. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy
(XPS), N2 adsorption–desorption, and UV–vis spectra were performed to characterize the as-synthesized mesoporous TiO2 materials. The XPS result shows that O–Ti–N and O–Ti–S bonds in the (S, N)-codoped mesoporous TiO2 were formed. The resultant mesoporous (S, N)-codoped TiO2 exhibited anatase framework with a high porosity and a narrow pore distribution. After being illuminated for 3 h, methyl
orange (MO) could be degraded completely by the co-doped sample under the ultraviolet irradiation, whereas mesoporous TiO2 film without doping could only degrade 60% MO. After being illuminated by visible light, the water contact angles of the
mesoporous co-doped TiO2 samples decreased slightly, but the pure TiO2 mesoporous film exhibited no change in the hydrophilicity. 相似文献
8.
Bin Peng Hui Chao Bin Sun Feng Gao Liang-Nian Ji Jian Zhang 《Transition Metal Chemistry》2007,32(2):271-277
Two novel cobalt(III) mixed-polypyridyl complexes
[Co(bpy)2(dpta)]3+ and [Co(bpy)2(amtp)]3+ (bpy = 2,2′-bipyridine, dpta = dipyrido-[3,2-a;2′,3′-c]-thien-[3,4-c]azine, amtp = 3-amino-1,2,4-triazino[5,6-f]-1,10-phenanthroline)
have been synthesized and characterized. The interaction of CoIII complexes with calf thymus DNA was investigated by spectroscopic and viscosity measurements. Results suggest that the two
complexes bind to DNA via an intercalative mode. Moreover, CoIII complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The mechanism studies
reveal that hydroxyl radical (OH•) is likely to be the reactive species responsible for the cleavage of plasmid DNA by [Co(bpy)2(dpta)]3+ and superoxide anion radical (O
2
•−
) acts as the key role in the cleavage reaction of plasmid DNA by [Co(bpy)2(amtp)]3+. 相似文献
9.
Lei Ge 《Journal of Sol-Gel Science and Technology》2007,44(3):263-268
Novel visible-light-activated In2O3–CaIn2O4 photocatalysts were developed in this paper through a sol–gel method. The photocatalytic activities of In2O3–CaIn2O4 composite photocatalysts were investigated based on the decomposition of methyl orange under visible light irradiation (λ > 400 nm).
The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive
spectrum (EDS), X-ray photoelectron spectroscopy (XPS) and UV–vis diffused reflectance spectroscopy (DRS). The results revealed
that the In2O3–CaIn2O4 composite samples with different In2O3 and CaIn2O4 content can be obtained by controlling the synthesis temperature, and the composite photocatalysts extended the light absorption
spectrum toward the visible region. The photocatalytic tests indicated that the composite samples demonstrated high visible-light
activity for decomposition of methyl orange. The significant enhancement in the In2O3–CaIn2O4 photo-activity under visible light irradiation can be ascribed to the efficient separation of photo-generated carriers in
the In2O3 and CaIn2O4 coupling semiconductors. 相似文献
10.
P. N. Bourosh E. B. Koropchanu A. A. Desyantnik O. A. Bologa Zh. P. Tyurina M. V. Stratan O. A. Chiobenike Ya. Lipkovsky I. I. Bulkhak Yu. A. Simonov 《Russian Journal of Coordination Chemistry》2009,35(10):751-757
The coordination compound [Co(DH)2(PP)2][BF4]2 · 2H2O (DH− is the dimethylglyoxime residue, PP is nicotinamide) was synthesized and studied by X-ray diffraction. The equatorial plane
of the octahedral Co(III) complex contains two DH− residues combined by intramolecular hydrogen bonds O-H…O, while the apical positions are occupied by two PP molecules. A
method for the optimal use of the complex for enhancement of the biosynthesis of standard and acid-stable amylases of the
micromycete Aspergillus niger 33–19 CNMN FD 02A and lipases of the micromycete Rhizopus arrhizus Fischer CNMN FD 03L was depeloped. The introduction of the complex in a concentration of 1–5 mg/l into the culture medium of Aspergillus niger 33-19 CNMN FD 02A reduces the process cycle by 24 h. The stimulating effect of the introduction of the complex (5 mg/l) into
the culture medium of the Rhizopus arrhizus Fischer CNMN FD 03L strain is 55.5%. 相似文献
11.
Nanocrystalline TiO2 powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl4 solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m2/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO2 nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic
mixed-phase TiO2 powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO2 (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated
that rutile TiO2 crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This
result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after
the photocatalytic process over the rutile TiO2 photocatalysts of larger crystallite size. 相似文献
12.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
13.
N, B, Si-tridoped mesoporous TiO2, together with N-doped, N, B-codoped and N, Si-codoped TiO2, was prepared by a modified sol–gel method. The samples were characterized by wide-angle X-ray diffraction (WAXRD), N2 adsorption–desorption, transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, UV–visible
adsorbance spectra (UV–vis) and X-ray photoelectron spectra (XPS). The N, B, Si-tridoped mesoporous TiO2 showed small crystallite size, large specific surface area (350 m2/g), uniform pore distribution (3.2 nm) and strong absorption in the visible light region. The photocatalytic activities of
the samples were evaluated by the photodegradation of 2,4-dichlorophenol (2,4-DCP) aqueous solution. The N, B, Si-tridoping
sample exhibited much higher photocatalytic activity compared with other synthesized photocatalysts. The high activity could
be attributed to the strong absorption in the visible light region, large specific surface area, small crystallite size, large
amount of surface hydroxyl groups, and mesoporosity. 相似文献
14.
Soraia Meghdadi Mehdi Amirnasr Mohammad H. Habibi Ahmad Amiri Fatemeh Ahmadi Keiko Kihara Takayoshi Suzuki Hamid Reza Bijanzadeh 《Transition Metal Chemistry》2008,33(7):879-886
The structure, spectroscopic, and electrochemical properties of [Co{(BA)2pn}(L)2]ClO4 complexes, where (BA)2pn = N,N′-bis(benzoylacetone)-1,3-propylenediimine dianion and the two ancillary ligands (L) are pyridine, py (1), and 4-methylpyridine, 4-Mepy (2), have been investigated. These complexes have been characterized by elemental analyses, IR, UV–Vis and 1H-NMR spectroscopy. The crystal structure of [Co{(BA)2pn}(py)2]ClO4 (1) has been determined by X-ray diffraction. The coordination geometry around cobalt(III) is best described as a distorted
octahedron. The electrochemical reduction of these complexes at a glassy carbon electrode in acetonitrile solution indicates
that the first reduction process corresponding to CoIII–CoII is electrochemically irreversible, which is accompanied by the dissociation of the axial N(py)–cobalt bonds. This process
becomes quasi-reversible upon the addition of excess py ligands. The second reduction step of CoII/I shows reversible behavior and is not influenced by the nature of the axial ligands.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
15.
K. Ramalingam R. Thiruneelakandan G. Bocelli L. Righi 《Transition Metal Chemistry》2012,37(3):265-270
The complexes trans-[Ni(4-MP)2(NCS)2]·MeCN (1) and trans-[Ni(3-MP)2(NCS)2] (2) (4-MP = tri(4-methylphenyl)phosphine, 3-MP = tri(3-methylphenyl)phosphine) were prepared and characterized by IR, UV–visible,
NMR spectra, CV, TGA and single crystal X-ray crystallography. Both the complexes have planar geometry and are diamagnetic.
The Ni–P distances in both complexes are relatively short as a result of strong back donation from nickel to phosphorus. The
phenyl rings in the 3-MP analogue (2) show increased pitching with reference to the plane formed by the ipso carbons due to increased steric effects. For complex
(2), the N–Ni–N and P–Ni–P angles are significantly lower than the almost linear N–Ni–N and N–Ni–P angles observed for both
complex (1) and trans-[Ni(PPh3)2(NCS)2]. This observation indicates that the 3-methylphosphine ligand forces complex (2) to distort towards a tetrahedral geometry. IR spectra of both complexes show strong bands around 2,090 cm−1 due to N-coordinated thiocyanate, while the electronic spectra contain d–d transitions around 452 nm. Cyclic voltammograms
show that the irreversible one-electron reduction potentials increase in the following order: trans- [Ni(PPh3)2(NCS)2] < trans- [Ni(3-MP)2(NCS)2] < trans-[Ni(4-MP)2(NCS)2], revealing the electron releasing effect of the methyl groups. The planar complexes exhibit interallogony in coordinating
solvents. 相似文献
16.
V. V. Drozdova E. A. Malinina L. V. Goeva I. N. Polyakova N. T. Kuznetsov 《Russian Journal of Inorganic Chemistry》2010,55(1):34-39
A method for the synthesis of the silver(I) complex with the closo-decaborate anion and triphenylphosphine [Ag2(Ph3P)2B10H10]
n
was developed and the structure of this complex was studied. The polymeric chain of the complex is formed with participation
of Ag(I) atoms, which coordinate the B10H102− anions through the apical (B(1)–B(2), B(9)–B(10)) and equatorial (B(3)–B(6), B(5)–B(8)) edges, the metalligand bonding occurring
through three-center two-electron bonds (MHB). The P atoms of two triphenylphosphine molecules are also incorporated in the
inner coordination sphere of the metal: the CN of the silver atom is 4 + 1. 相似文献
17.
T. N. Kropacheva V. I. Kornev D. A. Loginov V. I. Meshcheryakov E. V. Mutseneck D. V. Muratov D. S. Perekalin L. S. Shul’pina A. R. Kudinov 《Russian Chemical Bulletin》2005,54(10):2354-2358
New dinuclear ruthenium manganese complexes of general composition (bpy)2Ru(L)MnClx(H2O)2 (L is 1,10-phenanthroline-5,6-dione, 3,3′-dicarboxy-2,2′-bipyridyl, or bis(pyrazolyl); x = 2 or 4) were synthesized by the reaction of (bpy)2Ru(L) with MnCl2 · 4H2O. These compounds and the starting mononuclear ruthenium complexes were studied by spectrophotometric and electrochemical
methods in MeCN. The position of the charge-transfer band RuII → L in the spectra depends on the donor-acceptor characteristics of the ligand L. For the dinuclear complex under study,
the formal potentials of reversible one-electron oxidation of RuII are in the range of 0.9–1.2 V (vs. the standard hydrogen electrode), whereas oxidation of MnII occurs at more positive (by 0.1–0.2 V) potentials.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2281–2285, October, 2005. 相似文献
18.
Qiang Li Pingfan Wu Panchao Yin Jin Zhang Lu Shi Yongge Wei 《Journal of Cluster Science》2010,21(2):181-186
The α-octamolybdate-supported compound: [Fe(2,2′-bipy)3]2[α-Mo8O26] has been unexpectedly synthesized during a diffuse process and characterized by the IR spectroscopy, UV–Vis diffuse reflectance
spectroscopy and the single crystal X-ray diffraction. The title compound exhibits an interesting 3D honeycomb ‘host’ supramolecular
network with 1D channels, in which only α-octamolybdate anions ‘guests’ reside. The title compound shows the anisotropic property
and probably will be applied as a novel semiconductor in the future. 相似文献
19.
Lijun Wei Huifen Xia Zhaopin Wang Ping Yuan Tong Zhou Baojun Zhang Xianglei Cheng 《Chemical Papers》2011,65(6):761-768
The chemiluminescence behaviour and mechanism of peroxynitrous acid and Ru(bpy)32+ were studied in the presence of short-chain alcohols (methanol, ethanol, propan-1-ol, propan-2-ol, butanol, 2-methylpropan-1-ol,
pentanol). It was found that the chemiluminescence intensity of peroxynitrous acid and Ru(bpy)32+ system could be significantly enhanced by these seven short-chain alcohols. The maximum chemiluminescence wavelength of 608
nm of [Ru(bpy)32+]* in the excited state was attributed to the reaction between Ru(bpy)32+ and dihydroxyalkyl radicals which were generated during the redox course of peroxynitrous acid and alcohols. In addition,
the chemiluminescence signals of the system presented depended largely on the solubility and branched-chain structure as well
as the length of carbon chain. The analytical characteristics and parameters of the peroxynitrous acid/Ru(bpy)32+/alcohols chemiluminescence system were investigated under optimum conditions. 相似文献
20.
Four new triphenylgermylruthenium carbonyl compounds HRu(CO)4GePh3, 14; Ru(CO)4(GePh3)2, 15; Ru2(CO)8(GePh3)2, 16; and Ru3(CO)9(GePh3)3(μ-H)3, 17 were obtained from the reaction of Ru(CO)5 with Ph3GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)5 and an oxidative addition of the GeH bond of the Ph3GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh3 ligands in the six coordinate complex. Compound 16 contains two Ru(CO)4(GePh3) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh3 ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru3(CO)10(μ-GePh2)2, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh2 ligands bridging two different edges of the cluster and one bridging CO ligand. Ru3(CO)12 was found to react with Ph3GeH at 97 °C to yield three products: 15, and two new compounds Ru3(CO)9(μ-GePh2)3, 19 and Ru2(CO)6(μ-GePh2)2(GePh3)2, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh2 ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh2 ligands and a terminal GePh3 ligand on each metal atom. All compounds were characterized by a combination of IR, 1H NMR, single-crystal X-ray diffraction analyses.
This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions
to the chemistry of metal chalcogenide cluster complexes. 相似文献