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991.
采用与文献不同的路线合成了4,4′-二(p-甲基苯基)-2,2′-二联吡啶,与文献结果相比,总收率由4.0%提高至15.3%.该化合物和4,4′-二羧基-2,2′-二联吡啶组成混合配体与金属钌配位,合成了两亲性、混配型配合物cis-N,N-4,4′-二(p-甲基)苯基-2,2′-二联吡啶-N,N-4,4′-二羧基-2,2′-二联吡啶-N,N-二异硫氰钌配合物,并用IR,UV-Vis,NMR和Maldi-TOF等手段进行表征.将该两亲性混配钌配合物首次用于对Hg2+的识别中,发现此配合物对Hg2+表现出灵敏的选择性“肉眼”识别:在DMF/乙醇溶液(体积比1∶9)中加入Hg2+后,MLCT态吸收由530nm蓝移到485nm.该配合物与Hg2+以1∶1(摩尔比)结合,检测限可低至0.5×10-6mol/L. 相似文献
992.
Assembly of [Ag(CN)2]^- units with M(Ⅱ)-diamine complex cations [Cu(LN-N)2]^2+, where LN-N represents L2-diaminopropane (pn) and ethylenediamine (en), afforded two complexes, [Cu(pn)2][Ag2(CN)4] (1) and [Cu(en)2][Ag3(CN)5] (2), which were characterized by elemental analysis, IR, UV-Vis and ESR spectra. Single crystal X-ray analyses show that these complexes have 2D and 3D architectures through silver-silver interactions and other weak interactions. The luminescence behaviors of the two complexes were also studied by means of emission spectra. 相似文献
993.
Andreas Rahm Evgeni M. Kaidashev Heidemarie Schmidt Mariana Diaconu Andreas Pöppl Rolf Böttcher Christoph Meinecke Tilman Butz Michael Lorenz Marius Grundmann 《Mikrochimica acta》2006,153(1-2):21-25
A flow injection chemiluminescence method is proposed for the determination of cobalt, based on the strong catalytic effect
of Cobalt(II) (1,10-phenanthroline)3 complex on the lucigenin-periodate reaction in alkaline medium. Under the optimum experimental conditions, the chemiluminescence
signal responded linearly to the concentration of cobalt(II) in the 1.0 × 10−9–3.0 × 10−7 g mL−1 range with a detection limit of 4.4 × 10−10 g mL−1 cobalt(II). The relative standard deviation for the determination of 5.0 × 10−8 g mL−1 of cobalt was 2.3% in eleven replicated measurements. The method was successfully applied to the determination of cobalt(II)
in pharmaceutical preparations. 相似文献
994.
Marco Arfelli Giovanni Cossu Giulia Mattogno Carla Ferragina Maria Antonietta Massucci 《Journal of inclusion phenomena and macrocyclic chemistry》1990,9(2):161-170
X-ray photoelectron spectroscopy provides evidence that when [Cu(phen)2]2+(phen = 1,10-phenanthroline) is diffused between the layers of -zirconium phosphate, the complex species does not remain intact after intercalation, but some Cu-N bonds are broken, replaced with Cu-O bonds and the released nitrogen atoms can now interact with the PO3-OH groups of the host. XPS also provides evidence for coordination of the Cu2+ ions when they are diffused by ion exchange in the phenanthroline--zirconium phosphate intercalation compound. Although Cu2+ and phen are in a 1 : 1 molar ratio in the interlayer region of the host, so that a 1 : 1 coordination could be expected between the two species, the characteristic peaks of the uncoordinated phenanthroline, even though at a low intensity, are still present. The differences between the two Cu(II)-intercalation compounds are discussed. 相似文献
995.
Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me2]2}2][AsF6] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO2)m [AsF6]n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me2]2}2][AsF6], which is also formed by the reaction of Ag[AsF6] with O[P(S)Me2]2. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively. 相似文献
996.
Mao Jiang-Gao 《结构化学》1994,(5)
Preparation and Crystal Structures of LaCl_3(12-crown-4)(MeOH)and[LaCl_3(phen)_2(H_2O)]·MeOHMaoJiang-Gao(FujianInstituteofResea... 相似文献
997.
利用核磁共振方法研究了取代吡唑对炔基Fischer卡宾化合物的Michael加成的动力学行为,该反应为典型的二级反应。当吡唑的3,5-位由较大基团取代时,反应速率常数变小,而活化焓和活化熵明显增大。利用密度泛函理论研究了炔基钨卡宾为底物的Michael加成反应机理,发现吡唑上取代基团的增大可以导致第三步反应的活化能大于第一步,从而使反应的决速步骤由原来的第一步转变为第三步。 相似文献
998.
Wagner J. Barreto Henrique de Santana Flaveli A. S. Almeida Dilson N. Ishikawa Yoshio Kawano 《Journal of Analytical and Applied Pyrolysis》2003,70(2):719-210
The synthesis, characterization, and thermal decomposition of the [Ni(SCN)2(H+SCN)2(4-mepy)2] compound with an octahedral structure in polymeric chain were reported, in which SCN groups form bridges among Ni(II) ions. The compound decomposes in water resulting in a pH<4 solution. The FT-IR spectrum presented doublet bands at 2117; 2128 cm−1, 788; 773 cm−1 assigned to ν(C---N) and ν(C---S) stretching modes, respectively, and δ(SCN) deformation modes at 468; 476 cm−1. The Raman spectrum of the compound presented the ν(C---N) stretching as a strong doublet at 2122; 2128 cm−1, ν(C---S) at 783; 770 cm−1, and δ(SCN) at 468; 477 cm−1. No significant changes were observed in the 4-mepy ligand bands compared with the vibrational frequencies of the pure compound or the compound in aqueous solution 0.2 mol l−1. The crystal UV–vis reflectance spectrum presented two bands centered in 626 and 424 nm tentatively assigned to the d→d type transitions, 3A2g→3T1g and 3A2g→3T1g, for a symmetry close to Oh. The TG curve showed a mass loss between 120 and 200 °C assigned to the loss of the two 4-mepy molecules; from 200 to 265 °C, the loss of the two H+SCN groups; and from 265 to 450 °C, the loss of the two SCN groups that formed the bridges among the nickel atoms. Based on these mass loss data, a mechanism of thermal decomposition for the compound was proposed. 相似文献
999.
Katsuhiko Ono Kyohei Yoshikawa Hiroyuki Yamaguchi Masaaki Tomura Katsuhiro Saito 《Tetrahedron》2007,63(38):9354-9358
BF2 complexes with 1,3-diketone ligands were synthesized, and their optical and electrochemical properties were studied. The colors of the complexes varied depending on the structures of the 1,3-diketone ligands. The absorption and emission maxima of the complexes with 1,3-diaryl-1,3-diketone ligands were considerably red shifted as compared to those of the complexes with 1-aryl-3-trifluoromethyl-1,3-diketone ligands, suggesting an extended π-conjugation of the 1,3-diaryl-1,3-diketone moieties. The molar absorption coefficients and quantum yields of the complexes with 1,3-diaryl-1,3-diketone ligands were larger than those of the complexes with 1-aryl-3-trifluoromethyl-1,3-diketone ligands. Cyclic voltammetry measurements revealed that the reduction potentials of the BF2 complexes were higher than those of the free ligands. These complexes exhibited various emission colors in the solid states due to the intermolecular interactions. 相似文献
1000.
Two novel supramolecular complexes [Cu(bpapa)(dhbd)]·CHaOH (1) and [Cu(bpapa)(ma)]·ma (2) (bpapa= bis[6-(2-pyridylamino)pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate) were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2. 相似文献