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1.
Donmez E Kara H Karakaş A Unver H Elmali A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,66(4-5):1141-1146
N,N'-(2-Hydroxy-propane-1,3-diyl)-bis(5-nitrosalicylaldiminato-N,O)-copper(II) has been synthesized. The crystal structure has been determined by X-ray diffraction analysis, and linear optical characterization has been determined by UV-vis spectroscopy. It was found that the molecule under investigation has solvatochromic behaviour in the UV region, implying non-zero microscopic first hyperpolarizability. To reveal the microscopic nonlinear optical (NLO) properties, the static first hyperpolarizabilities (beta) and the electric dipole moments (mu) were evaluated by using the ab initio finite field (FF) method. According to the results of the FF calculations, the synthesized compound exhibits non-zero beta values, and it might have microscopic NLO behaviour. 相似文献
2.
Ying-Zhong Shen Yi Pan Le-Yong Wang Gang Dong Xiao-Ping Jin Xiao-Ying Huang Hongwen Hu 《Journal of organometallic chemistry》1999,590(2):1865-247
The reaction of trialkylgallium or indium R3M (M=In, Ga; R=Me, Et) with N,N′-ethylenebis(salicylideneimine) or 1,2-N,N′-phenylenebis(salicylideneimine) yields seven intramolecularly coordinated organogallium or organoindium complexes. Two hydroxyl protons in the ligands react with both trialkylindium and trimethylgallium, while one hydroxyl group reacts exclusively with triethylgallium. The complexes obtained have been fully characterised by elemental analysis, 1H-NMR, IR and mass spectroscopy. The structure of methyl-N,N′-bis(salicylidene)-1,2-phenylenediaminoindium (1) has been determined by single-crystal X-ray analysis. The In atom is five coordinate in the structure. Fluorescence spectroscopy has shown that the maximum emission wavelength of 1 is 499 nm upon radiation by UV light. 相似文献
3.
M. Dolores Santana Gabriel García Consuelo Vicente-Hernndez Luís García Jos Prez Tefilo Rojo Luís Lezama 《Journal of organometallic chemistry》2008,693(11):2009-2016
The preparation, spectroscopic characterization and magnetic study of N,N′-bis(substituted-phenyl)oxamidate-bridged nickel(II) dinuclear complexes of formula {[Ni(N3-mc)]2(μ-CONC6H4-X)}(PF6)2 (N3-mc = 2,4,4-trimethyl-1,5,9-triazacyclo-dodec-1-ene (Me3-N3-mc) or 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene (Me4-N3-mc), X = 2-Cl, 4-Cl, 2-OCH3, 4-OCH3) are reported. These paramagnetic nickel(II) complexes have been characterized by both one- and two-dimensional (COSY) 1H NMR techniques. The COSY spectrum of 5 has allowed to achieve the assignment of the phenyl protons of the N,N′-diphenyloxamidate. The crystal structures of [Ni(Me3-N3-mc)(μ-CONC6H4-4-Cl)]2(PF6)2 (6), [Ni(Me3-N3-mc)(μ-CONC6H4-4-OMe)]2(PF6)2 (8) and [Ni(Me4-N3-mc)(μ-CONC6H4-2-Cl)]2(PF6)2 (9) have been determined and their magnetic properties have been studied. The value of magnetic coupling between the two nickel(II) ions across the oxamidate bridge [J = − 37.6 (6), −39.9 (8) and −39.7 cm−1 (9)] is sensitive to the distortion of the coordination sphere of the metal ions and the topology of the molecular bridge. 相似文献
4.
Mehdi Amirnasr Amir H. Mahmoudkhani Alireza Gorji Saeed Dehghanpour Hamid Reza Bijanzadeh 《Polyhedron》2002,21(27-28)
A series of complexes of the type M(Phca2en)X2, where Phca2en=N,N′-bis(β-phenyl-cinnamaldehyde)-1,2-diiminoethane, M(II)=Co, Ni or Zn and X=Cl, Br, I or NCS have been synthesized and characterized. The crystal and molecular structures of Co(Phca2en)Cl2 (2), Ni(Phca2en)Br2 (5) and Zn(Phca2en)Cl2 (6) were determined by X-ray crystallography from single-crystal data. Complexes 2 and 5 are isomorph and isostructure, in which the coordination polyhedron about the central metal ion is distorted tetrahedron with Cl---Co---Cl, 110.17(6)°; N---Co---N, 84.16(13)° and Cl---Zn---Cl, 112.02(6)°; N---Zn---N, 83.45(16)°. The complex 5 crystallizes in triclinic system with two molecules per asymmetric unit, both having nickel ion in distorted tetrahedral geometry, Br---Ni---Br, 122.645(18)° and 125.729(18)°; N---Ni---N, 84.63(9)° and 85.08(9)°. These structures consist of intermolecular hydrogen bonds of the type C---HX. The formation of the C---HM weak intramolecular hydrogen bonds due to the trapping of C---H bonds in the vicinity of the metal atoms are reported for 2, 5 and 6. A 1H NMR study of Zn complexes gives further evidence for the presence of such interactions and their significance. The spectral properties of the above complexes are also discussed. 相似文献
5.
Karakaş A Elmali A Unver H Svoboda I 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2979-2987
N-(4-nitrobenzylidene)-o-fluoroamine (1) and N-(3-nitrobenzylidene)-p-fluoroamine (2) have been synthesized. The crystal structures of both compounds have been defined by X-ray diffraction analysis, and characterized by FT-IR and UV-visible instrumental methods. The recorded spectrum by UV-visible spectroscopy for the investigated compounds show good transparency in the visible region, and have solvatochromic behavior in the UV region, implying nonzero microscopic first hyperpolarizability. We also report ab initio quantum chemical calculations of the electric dipole moments (mu) and the first hyperpolarizabilities (beta) of the studied compounds. Our results suggest that the investigated ligands might have microscopic nonlinear optical (NLO) behavior with nonzero values. 相似文献
6.
Flaviana T. Vieira Geraldo M. de Lima James L. Wardell Solange M.S.V. Wardell Klaus Krambrock Antnio F. de C. Alcntara 《Journal of organometallic chemistry》2008,693(11):1986-1990
The compound, [chloro{2(1H)-pyridinethione-S}{tris(pyridin-2-ylthiolato)methyl-C,N,N′,N″]}nickel(II)], [Ni(TPTM)(SPyH)Cl], was isolated from the reaction between NiCl2 · 6H2O and tris(pyridin-2-ylthiolato)methane in aqueous EtOH. X-ray crystallography at 120 K revealed an octahedral arrangement about Ni with a tetradentate tris(pyridin-2-ylthio)methyl-C,N,N,N ligand, a monodentate 2(1H)-pyridinethione-S ligand and a chloride. The 2(1H)-pyridinethione-S ligand was derived from tris(pyridin-2-ylthio)methane probably via an acid catalysed hydrolysis reaction. Intramolecular N–H–Cl and C–H–Cl interactions help to cement the molecular structure. Weak C–H–Cl and C–H–S hydrogen bonding interactions link molecules of [Ni(TPTM)(SPyH)Cl] into a 3D array. EPR and UV spectra, and Hartree–Fock theoretical calculations are reported. 相似文献
7.
Marek Daszkiewicz Wiesawa Bronowska Adam Pietraszko Zbigniew Staszak Maria Cielak-Golonka 《Journal of Molecular Structure》2005,754(1-3):124-132
Nickel(II) chromate complex with imidazole (HIm) was isolated from the [Ni2+–HIm–CrO42−] system in various experimental conditions, i.e. reagent molar ratios and nickel(II) salts. The catena(μ-CrO4-O,O′)[Ni(HIm)3H2O] (1) crystallizes in monoclinic crystal system—space group P21/n with cell parameters: a=11.784(2), b=8.899(2), c=13.934(3) (Å), β=95.19(3) (°). The unit cell contains two independent helixes, left- and right-handed, stabilized by intrahelical and interhelical hydrogen bonds (HB) and π–π interactions. The cis coordination of the CrO42− anions and the HB systems appeared to be the main determinants of the helical architecture. To the best of our knowledge the cis-chromate coordination was observed for the first time. The cis coordination causes the distortion of the nickel octahedron, which was analysed by 4 K single crystal electronic spectra with D4h symmetry approximation (gaussian resolution and crystal field parameters). This symmetry was also confirmed with the polarised electronic spectra. The magnetic properties of the complex suggest the occurrence of weak intrachain antiferromagnetic interactions between the magnetic NiII center. The computational DFT studies of complex 1 assuming three possible isomers mer[(HIm)3]–cis[(CrO42−)2], mer–trans and fac–cis suggested that the main contribution to the stability of 1 might have interhelical and intrahelical hydrogen bonds. 相似文献
8.
Infrared and Raman spectra of 1,1-(methylphosphinylidene) bis(methanamine) [mpbm, (CH3)PO(CH2NH2)2] and its N,N′-coordinated Pt(II) and Pd(II) have been studied in the 4000–200 cm−1 frequency range. Ab initio calculations have been carried out for different conformations of the mpbm at HF/6-31G* level of the theory from which structural parameters, conformational stability and predicted infrared and Raman spectra have been obtained. A complete vibrational assignment of the lowest energy conformer, tttg−, as well as of its N,N′-coordinated Pt(II) and Pd(II) chloro-complexes was done on the basis of the calculated frequencies, relative infrared intensities, Raman activities and potential energy distribution (PED). The theoretical predictions are compared with the experimental results where appropriate. 相似文献
9.
O. V. Krokhin O. V. Kuzina H. Hoshino O. A. Shpigun T. Yotsuyanagi 《Journal of chromatography. A》2000,890(2)
Two aromatic polyaminocarboxylate ligands, ethylenediaminedi(o-hydroxyphenylacetic acid) (EDDHA) and N,N′-bis(hydroxybenzyl)ethylenediamine-N,N′-diacetic acid (HBED), were applied for the separation of transition and heavy metal ions by the ion-exchange variant of electrokinetic chromatography. EDDHA structure contains two chiral carbon centers. It makes it impossible to use the commercially available ligand. All the studied metal ions showed two peaks, which correspond to meso and rac forms of the ligand. The separation of metal–HBED chelates was performed using poly(diallyldimethylammonium) polycations in mixed acetate–hydroxide form. Simultaneous separation of nine single- and nine double-charged HBED chelates, including In(III), Ga(III), Co(II)–(III) and Mn(II)–(III) pairs demonstrated the efficiency of 40 000–400 000 theoretical plates. The separation of Co(III), Fe(III) complexes with different arrangements of donor groups and oxidation of Co(II), Mn(II), Fe(II) ions in reaction with HBED have been discussed. 相似文献
10.
Pierre Thury Martine Nierlich Marie-Christine Charbonnel Christophe Den Auwer Jean-Pierre Dognon 《Polyhedron》1999,18(27):3620-3603
A monoclinic form of the complex between lanthanum(III) nitrate and tetraethylmalonamide (TEMA), La(NO3)3(TEMA)2, 1, differing from the triclinic form 2 previously reported, is described. 1 undergoes an evolution with time which leads to the form 2, which in its turn undergoes a temperature-driven phase transition previously unreported, leading to the formation of 3. 相似文献
11.
Daniela Rusanova Kevin J. Pike Ingmar Persson Ray Dupree Mats Lindberg John V. Hanna Oleg N. Antzutkin Willis Forsling 《Polyhedron》2006,25(18):3569-3580
Polycrystalline octa-nuclear copper(I) O,O′-di-i-propyl- and O,O′-di-i-amyldithiophosphate cluster compounds, {Cu8[S2P(OR)2]6(μ8-S)} where R = iPr and iAm, were synthesized and characterized by 31P CP/MAS NMR at 8.46 T and static 65Cu NMR at multiple magnetic field strengths (7.05, 9.4 and 14.1 T). The symmetries of the electronic environments around the P sites were estimated from the 31P chemical shift anisotropy (CSA) parameters, δaniso and η. Analyses of the 65Cu chemical shift and quadrupolar splitting parameters for these compounds are presented with the data being compared to those for the analogous octa-nuclear cluster compounds with R = nBu and iBu. The 65Cu transverse relaxation for the copper sites in {Cu8[S2P(OiPr)2]6(μ8-S)} and {Cu8[S2P(OiAm)2]6(μ8-S)} was found to be very different, with a relaxation time, T2, of 590 μs (Gaussian) and 90 μs (exponential), respectively. The structures of {Cu4[S2P(OiPr)2]4} and {Cu8[S2P(OiPr)2]6(μ8-S)} cluster compounds in the liquid- and the solid-state were studied by Cu K-edge EXAFS. The disulfide, [S2P(OiAm)2]2, was obtained and characterized by 31P{1H} NMR. The interactions of the disulfide and of the potassium O,O′-di-i-amyldithiophosphate salt with the surfaces of synthetic chalcocite (Cu2S) were probed using solid-state 31P NMR spectroscopy and only the presence of copper(I) dithiophosphate species with the {Cu8[S2P(OiAm)2]6(μ8-S)} structure was observed. 相似文献
12.
Marina Cindric Tanja Kajfe Novak Krunoslav Uarevic 《Journal of Molecular Structure》2005,750(1-3):135-141
Two macrocyclic ligands, N,N′-propylene-diylbis[3-(1-aminoethyl)-6-methyl-2H-pyran-2,4(3H)-dione] I and N,N′-phenylene-diylbis[3-(1-aminoethyl)-6-methyl-2H-pyran-2,4(3H)-dione] II, have been prepared by the condensation of dehydroacetic acid (3-acetyl-4-hydroxy-6-methyl-2H-pyran-2-one) with 1,2-phenylenediamine and 1,3-propylenediamine. They have been characterized by means of elemental analysis, IR spectroscopy as well as by X-ray crystallography. The molecular structures of the compounds I and II can be described as consisting of two β-enaminone-2-pyrone rings interlaced with either alkyl chain in I or phenyl ring in II. The X-ray studies confirmed the existence of strong N–HO intramolecular hydrogen bonds in both structures. Their lengths are in accordance to lengths of RAHB intramolecular hydrogen bonds in 1,3-diketones, aryl-hydrazones, β-enaminones and related heterodienes (2.5–2.6 Å) [P. Gilli, V. Bertolasi, V. Ferretti and G. Gilli, J. Am. Chem. Soc., 122 (2000) 10405]. 相似文献
13.
Andrey I. Poddelsky Nina N. Vavilina Nikolay V. Somov Vladimir K. Cherkasov Gleb A. Abakumov 《Journal of organometallic chemistry》2009,694(21):3462-3469
The novel triethylantimony(v) o-amidophenolato (AP-R)SbEt3 (R = i-Pr, 1; R = Me, 2) and catecholato (3,6-DBCat)SbEt3 (3) complexes have been synthesized and characterized by IR, NMR spectroscopy (AP-R is 4,6-di-tert-butyl-N-(2,6-dialkylphenyl)-o-amidophenolate, alkyl = isopropyl (1) or methyl (2); 3,6-DBCat is 3,6-di-tert-butyl-catecholate). Complexes 1–3 have been obtained by the oxidative addition of corresponding o-iminobenzoquinones or o-benzoquinones to Et3Sb. The addition of 4,6-di-tert-butyl-N-(3,5-di-tert-butyl-2-hydroxyphenyl)-o-iminobenzoquinone to Et3Sb at low temperature gives hexacoordinate [(AP-AP)H]SbEt3 (4) which decomposes slowly in vacuum with the liberation of ethane yielding pentacoordinate complex [(AP-AP)]SbEt2 (5). [(AP-AP)H]2− is O,N,O′-tridentate amino-bis-(3,5-di-tert-butyl-phenolate-2-yl) dianion and [(AP-AP)]3− is amido-bis-(3,5-di-tert-butyl-phenolate-2-yl) trianion. The decomposition of 4–5 accelerates in the presence of air. o-Amidophenolates 1 and 2 bind molecular oxygen to give spiroendoperoxides Et3Sb[L-iPr]O2 (6) or Et3Sb[L-Me]O2 (7) containing trioxastibolane rings. This reaction proceeds slowly and reaches the equilibrium at 15–20% conversion five times more than for (AP-R)SbPh3 analogues. Molecular structures of 1 and 5 were determined by X-ray analysis. 相似文献
14.
Megumu Munakata Jing Han Atsuhiro Nabei Takayoshi Kuroda-Sowa Masahiko Maekawa Yusaku Suenaga Nozomu Gunjima 《Polyhedron》2006,25(18):3519-3525
Two novel Cu(II) complexes with 1,2-bis(2′-methyl-5′-(2″-pyridyl)-3′-thienyl)perfluorocyclopentene (BM-2-PTP) or its closed-form (closed-BM-2-PTP) were synthesized and characterized by X-ray crystallographic analysis. Both complexes are tetra-coordinated to two N atoms from distinct ligands and two Cl atoms from anions, forming 1-D polymeric structures. [Cu(BM-2-PTP)Cl2] (1) showed typical spectral changes as analogous Ag(I) complexes with the same ligand upon appropriate light stimulus. However, closed-BM-2-PTP displayed different photocyclization from its open-ring form upon irradiation with UV light, indicating the photogenerated closed form turned into two kinds of closed-ring isomers. Furthermore, [Cu(closed-BM-2-PTP)Cl2] (2) was revealed to contain two conformers by X-ray crystallographic analysis and displayed similarities in photocyclization to its free ligand. The distinct absorptions of the UV spectrum were attributed to the coexistence of two conformers in complex 2, both of which showed effective photoreactivities in the crystalline phase. The photochromic mechanism of complex 2 is tentatively concluded as two conformers displaying independent photoreactions. 相似文献
15.
Samuel P. Kusumocahyo Kimio Sumaru Takashi Iwatsubo Toshio Shinbo Toshiyuki Kanamori Hideto Matsuyama Masaaki Teramoto 《Journal of membrane science》2006,280(1-2):73-81
The facilitated transport mechanism of cerium(III) ions through polymer inclusion membrane (PIM) consisting of cellulose triacetate (CTA) as a polymer matrix, 2-nitrophenyl n-octyl ether (NPOE) as a solvent and N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) as a carrier was studied. In order to evaluate the mass transport phenomena in the PIM, a mathematical model was derived from the Fick's first law and the equations for the extraction and the material balance. Methods to determine the values of the transport parameters such as the diffusion coefficient are described, and the dependency of the flux on the experimental condition was calculated. The model is very useful as a design tool to analyze and optimize the concentration process of low level radioactive wastewater using the PIM. 相似文献
16.
Holger Braunschweig Barbara Gehrhus Peter B. Hitchcock Michael F. Lappert 《无机化学与普通化学杂志》1995,621(11):1922-1928
Cyclic bis(amido)tin(II) compounds 1,2- [R = SiMe3] ( 4 ), SiMe2But ( 5 ) and CH2But ( 6 )], as well as ( 4 )2(μ-tmeda) 7 have been obtained either from (i) the corresponding dilithium compound 1,2-C6H4[N(R)Li]2 1–3 and SnCl2 for 4–6 , respectively, (or for 4 ) 2 1 + [Sn(μ-Cl){N(SiMe3)2}]2; or (ii) 1,2-C6H4[N(H)R]2 + Sn[N(SiMe3)2]2 for 4–6 ; or for 7 from 4 and tmeda. Compounds 4–6 are monomeric, yellow, thermochromic (becoming redder on heating), diamagnetic, crystalline and are lipophilic and sublimable in vacuo. Compound 7 is colourless. The molecular structures of 6 and 7 have been determined from single crystal X-ray diffraction data. Compound 6 crystallises in bimolecular aggregates, in which there is a weak η-C6 … Sn contact. 相似文献
17.
Tatiyana V. Serebryanskaya Ludmila S. IvashkevichAlexander S. Lyakhov Pavel N. GaponikOleg A. Ivashkevich 《Polyhedron》2010
Complexes ML12 and ML22, with M = FeII, CoII, NiII, and 1,3-bis(2-R-tetrazol-5-yl)triazenide ligands L1 (R = Me) and L2 (R = tBu), have been synthesized by the reaction of corresponding 1,3-bis(2-R-tetrazol-5-yl)triazenes with metal(II) salts in basic media and characterized by IR, UV–Vis spectroscopy, thermal and X-ray diffraction analyses. Both 1,3-bis(2-R-tetrazol-5-yl)triazenes were found to deprotonate on coordination and act as tridentate chelating ligands forming distorted MN6 octahedra around metal(II) cations. 相似文献
18.
der T. G. Cavalheiro Francisco C. D. Lemos Júlio Zukerman Schpector Edward R. Dockal 《Thermochimica Acta》2001,370(1-2):129-133
The Schiff base complexes were prepared and characterised by UV, IR and NMR (1H and 13C) spectroscopy, elemental analysis and X-ray powder diffractometry. Free ligands and some new complexes were submitted to thermal analysis (TG and DSC) under dynamic air atmosphere. The differences in the decomposition profiles were related to the structure of isomers and decomposition intermediates were characterised according to their X-ray diffraction pattern. 相似文献
19.
The reaction of succinamic acid (H2sucm) with Ca(NO3)2·4H2O yielded compounds [Ca(Hsucm)(NO3)(H2O)]n (1) and [Ca(Hsucm)2]n (2). The succinamate(-1) ligand presents two new ligation modes and coordinates through the two carboxylato and the amide O-atoms, thus bridging three CaII ions which assemble into zig-zag 1D chains in 1 and 2D networks in 2. Intermolecular hydrogen bonding interactions in the crystal structures of 1 and 2 result in overall 3D framework structures. Both compounds have been characterized by IR and 1H NMR spectroscopy, and their thermal decomposition was monitored by TG/DTG and DSC measurements. The structural comparison of 1 and 2 with known lanthanide(III) succinamate(-1) complexes reveals differences in the coordination mode of the ligand and in the coordination number of the metal ions; the biological relevance of these differences is discussed. 相似文献
20.
Ling-Yan Kong Taka-aki Okamura Norikazu Ueyama 《Journal of solid state chemistry》2004,177(7):2271-2280
Five novel coordination polymers, [Co(bpb)2Cl2] (1), [Co(bpb)2(SCN)2] (2), [Cd(H4bpb)0.5(dmf)(NO3)2] (3), [Cd2(H4bpb)Br4] (4), and [Hg2(H4bpb)I4] (5) [bpb=N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine, H4bpb=N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethylamine], were synthesized and their structures were determined by X-ray crystallography. In the solid state, complex 1 is a 1D hinged chain, while 2 has 2D network structure with the ligand bpb serving as a bridging ligand using its two pyridyl N atoms. The imine N atoms keep free of coordination and bpb acts as a bidentate ligand in both 1 and 2. Complexes 3, 4, and 5 with reduced bpb ligand, i.e. H4bpb, show similar 2D network structure, in which ligand H4bpb serves as a tetradentate ligand. Thermogravimetric analyses for complexes 1-5 were carried out and found that they have high thermal stability. The magnetic susceptibilities of compounds 1, 2 were measured over a temperature range of 75-300 K. 相似文献