首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 359 毫秒
1.
Dimethyl diphenyldithiophosphate complexes of titanium(IV), [(C5H5)2Ti{S2P(OAr)2}nCl2-n] (Ar?= 2,4-(CH3)C6H3, 2,5-(CH3)C6H3, 3,4-(CH3)C6H3, 3,5-(CH3)C6H3, 3-CH3-4-Cl-C6H3O; n?=?1 and 2) have been synthesised and characterised by various physicochemical techniques along with computational analysis of the complexes (2), (9) and (10) using density functional theory (DFT) and time-dependent DFT (TDDFT). Comparison of antimicrobial activity of the free ligands and complexes has shown that the complexes are more effective than the free ligands. The in vitro cytotoxic by using a MTT staining method with RAW 264.7 cells (mouse macrophages) have been investigated. On the basis of analytical and DFT data, a distorted trigonal bipyramidal around titanium(IV) may be assigned to the complexes (1–5) and distorted octahedral geometries for the complexes (6–10).  相似文献   

2.
A series of organotin(IV) complexes of composition R3Sn[O2CC6H4{N= C(H)C6H3-2-OH(N=NC6H4R)}-p] (R = Ph or Bz; R = H, 2-CH3, 3-CH3, 4-CH3) have been investigated by 119Sn Mössbauer, 1H, 13C, 119Sn NMR and IR spectroscopic techniques. 119Sn Mössbauer data indicated a distorted tetrahedral geometry for the triphenyltin(IV) complexes while the tribenzyltin complexes exhibit a distorted trigonal bipyramidal coordination geometry with equatorial benzyl groups and the axial positions occupied by an O atom from the carboxylate ligand and the O atom from the water ligand. The 119Sn-NMR chemical shifts confirm that the Sn atom in triorganotin complexes is four-coordinate in CDCl3 solution.  相似文献   

3.
Folgende Komplexe des funfuertigen Tichnitiums wurden dargestellt und charakterisiert TcNCl2[P(C6H5)3]2 (A)

Tc NCl2 (PR2C6H5)3 [R = CH3 (B) bzw. C2H5 (C)]

TcN[(C2H5)2NCS2]2 (D)

Die Darstellung von (A) erfolgt anlog der entsprechenden Rheniumkomplexes; (B), (C) und (D) wurden durch Reaktron von (A) mit uberschunssigem PR2C6H5 bzw. Na(C2H5)2NCS2 durch Substitutionsreaktionen orhalten. Die genannten Komplexe sind bomerkenswert hydrolysebestandig. Here IR- und 1H-NMR-Spektren warden diskutiert  相似文献   

4.
The new organic–inorganic hybrid [5-Cl-2-(CH3)C6H3NH3]4H2P6O18 has been synthesized by the slow evaporation method. X-ray diffraction on a single crystal shows that this acidic cyclohexaphosphate crystallized in the monoclinic space group C 2/c with a?=?33.89(11) Å, b?=?9.16(16) Å, c?=?13.68(3) Å, β?=?91.35(2)°, V?=?4244.9(19) Å3 and Z?=?4. 31P MAS-NMR and 13C CP/MAS-NMR results are in accordance with X-ray findings. Fluorescent study shows the blue photoluminescence. Furthermore, FT-IR analysis was studied and the complete vibrational assignments were done. Intermolecular interactions were analyzed using Hirshfeld surface analysis and the associated 2D fingerprint plots.  相似文献   

5.
Rare-earth complexes [(TbxTmy)L5(ClO4)2](ClO4)·3H2O(x:y=1.000:0.000, 0.999:0.001, 0.995:0.005, 0.990:0.010, 0.950:0.050, 0.900:0.100, 0.800:0.200, 0.700:0.300; L=C6H5COCH2SOCH2COC6H5) were synthesized and characterized with elemental analysis, infrared spectra (IR) and 1H NMR. The photophysical properties of these complexes were studied in detail with ultraviolet absorption spectra, fluorescent spectra and lifetimes. The fluorescence spectra and decay curves of complexes indicated that the fluorescence emission intensity was enhanced and the fluorescence lifetime was prolonged by Tm (III), which may be due to the intra-molecular energy transfer between inert rare-earth ions and active rare-earth ions. The complexes showed the best properties when the mole ratio of Tb (III) to Tm (III) is 0.995:0.005. The intensity of fluorescence can be increased to 208%. Additionally, the energy-transfer mechanisms between the ligand and the central Tb (III) ions were discussed.  相似文献   

6.
Abstract

Rh(II) complexes are rather scarce1 and often form dimeric structures, which are diamagnetic. The ESR spectra of definite Rh(II) species have so far been claimed for Rh in ZnWO3 2, [Rh S4C4(CN)4]2 ?, 3′4 [Rh(π-C5H5)2]5, [(π-C5H5)Rh(π-C2H4)2]+6, and an irradiation produced [RhCπ2(CN)4]2 ? complex.7 A detailed analysis has been performed on the first2, the second4 and the last7 complexes. The first system shows an almost axial symmetry and the unpaired electron has been assigned to the dxy orbital2 (the x,y,z axes are defined along the octahedral metal-ligand directions). The sulfur ligand complex and the dichlorotetracyano system have their unpaired electron in the dZ 2 orbital. 4,7 In the course of studies 8-10 on oxygenation of a Rh(I) complex, [RhCπ(C8H14)2]2, we observed 10 that a well defined ESR spectrum develops during the reaction in N,N′-dimethylacetamide (DMA) - lithium chloride media. For experimental detail, reference 10 should be consulted. The data summarized in the table refer to the spectrum B in that reference and are attributed to a Rh(II) species.  相似文献   

7.
L. Sun  Y. Chang  S. Tang  Z. Wang 《Molecular physics》2013,111(23-24):2945-2949
Geometries, relative energies, and stabilities of endo- and exohedral complexes, X@Si20H20 and XSi20H20, (X = H+, H, N, P, C?, and Si?) are calculated at B3LYP/6-31G* level. The energy minimum structure of Si20H21 + shows that the proton cannot be positioned in the Si20H20 centre, but prefers attach to Si20H20 exohedrally with C2v symmetry. Most investigated Ih endohedral complexes X@Si20H20 (X = H, N, P, C?, and Si?) are local minima, except for 2N@Si20H20, which is a high-order saddle point. Inclusions energies of the endohedral complexes are calculated, and it reveals that energy penalties caused by encapsulation are rather small. Exohedral complexes XSi20H20 (X = H, N, P, C?, and Si?) have C2v or Cs local minima, and most of them are more stable than their endohedral isomers with the exception of C2v 4PSi20H20 and 4Si?Si20H20.  相似文献   

8.
Four novel dmit complexes: [(C2H5)4N][Ni (dmit)2], [(C3H7)4N][Ni(dmit)2], [(C2H5)4N][Au(dmit)2] and [(C3H7)4N][Au(dmit)2], abbreviated as EtNi, PrNi, EtAu, and PrAu, were synthesized. The third-order nonlinear optical properties of them in acetonitrile solutions were investigated by using the Z-scan technique with 20 ps pulses width at 1064 nm. When the on-axis irradiance at focus I 0 was 5.025 GW/cm2, the nonlinear refraction coefficient n 2, the third-order nonlinear susceptibility χ (3), the molecular second-order hyperpolarizability γ of the four types of material were obtained with subject to Z-scan curves, and these indexes were with the magnitudes of 10−18 m2/W, 10−13 esu, and 10−31 esu, respectively. The nonlinear absorption coefficient β of Ni samples had the 10−12 m/W scale. The impact of different metals and cations on the third-order nonlinear optical properties of materials was analyzed. Through the derivation, the result suggests that these dmit complexes are promising candidates for applications to nonlinear optical devices manufacture in the near-infrared waveband.  相似文献   

9.
In this work, the experimental and theoretical UV, NMR and vibrational spectra of 2-chloro-6-methylaniline (2-Cl-6-MA, C7H8NCl) were studied. The ultraviolet absorption spectra of compound that dissolved in ethanol were examined in the range of 200–400 nm. The 1H, 13C and DEPT NMR spectra of the compound were recorded. FT-IR and FT-Raman spectra of 2-Cl-6-MA in the liquid phase were recorded in the region 4000–400 cm?1 and 3500–50 cm?1, respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational frequencies were calculated and scaled values were compared with experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies were found to be in good agreement. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method. Comparison of the calculated NMR chemical shifts and absorption wavelengths with the experimental values revealed that DFT method produces good results.  相似文献   

10.
Abstract

2,2′-Biimidazole complexes of MoO2 +2, MoO2 + and UO2 +2 have been prepared and characterized by elemental analysis, conductance; and 1H NMR, IR and electronic spectra. Two types of complexes have been identified. Those obtained from slightly acidic solutions have the formulae MoO2 (H2bim)Cl2.2H2O 1, UO2(H2bim) (Ac)2 2 and UO2(H2bim)Cl2.2H2O 3; whereas those from alkaline solutions have the formulae Mo2O4(Hbim)2.2H2O 4, and MO2(Hbim)2 (M = Mo(VI) 5, U(VI) 6). The infrared spectra of these complexes show characteristic biimidazole frequencies in the 3200–2500, 1550–1000 and 750 cm?1 regions as well as metal oxygen double bonds in the 900 cm?1 region. The stoichiometries of the acetate complex has been confirmed from 1H NMR signal ratios of bimidazole to acetate protons at 7.3 and 2.3 ppm, respectively. The electronic spectrum of molybdenum(V) complex showed d-d transition band at ?13,500 cm?1 in accord with that reported for copper (d9) imidazole complexes; as well as peaks due to charge transfer bands at 30,000–26,000 cm?1 Peaks assignable to BIM → U(VI) were located at ?26,600 cm?1. The most probable structures of these complexes have been suggested.  相似文献   

11.
The luminescence quenching of excited Tris(2,2-bipyridine)ruthenium(II) ions by trans-[RuCl2{P(OR)3}4] complexes with different alkyl chain ligands (R=C2H5, C2H5Cl, nC4H9, iC3H7 o-tolyl and tC4H9) was investigated. None of the acceptor Ru(II) phosphite complexes were luminescent, and the rate constants of the bimolecular system were determined within the range of 1.15 and 0.28×108 M−1 s−1 for R=C2H5 and tC4H9, respectively. The results indicate a direct effect of the alkyl chains in the rate constants, showing a decrease of kq as a function of increased of the alkyl chains (R) in the ruthenium(II) tetraphosphite complexes. The greater the R group content in the phosphite ligand, the more difficult the electron transfer is.  相似文献   

12.
Mössbauer spectra of alkali tris(malonato) ferrates(III) i.e. M3[Fe(C3H2O4)3].4H2O(M=Li, Na, K, NH4) at 298±2K display a single broad absorption band due to spin lattice relaxation effect. The isomer shift values indicate these complexes to be high spin with octahedral symmetry. The isomer shift shows a decreasing trend with the increase in electronegativity/polarizing power of the substituent cation (Li+, Na+, K+, NH4 +). A linear correlation between isomer shift values and the (Fe-O) stretching freguencies has also been observed.  相似文献   

13.
Some one-electron molecular properties are calculated for BH3, BH4 -, B2H6, B4H4, CH4, C2H2, C2H4, C2H6, and C3H4. The wave functions used are constructed from minimal basis sets of STO's and FSGO's. The results obtained from the latter wave functions show that the good agreement with the STO values of the molecular energy is not always maintained with one-electron properties.  相似文献   

14.
Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L′) had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, 1HNMR and UV spectra. The results indicated that the composition of these complexes was REL5L′(ClO4)2·nH2O (RE= Tb(III), Dy(III); L=C6H5COCH2SOCH2COC6H5, L′=C6H5COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL5·(ClO4)3·2H2O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL5L′(ClO4)2·nH2O (RE= Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.  相似文献   

15.
Abstract

A number of studies have demonstrated the dependence of both the fluorescence lifetimes and quantum yields of tyrosine in solution upon the nature of the solvent as well as upon the absence or the presence of air in the tyrosine solutions employed. Photobleaching of tyrosine in vacuum at pH 6.1 was found to be practically zero, whereas exposure of tyrosine to the full light of a Hglamp for 10 to 20 minutes gave rise to formation of non-fluorescing photoproducts(1). In addition, the phosphorescence lifetimes of tyrosine were determined as 2.7+?0.2 sect 2.7+0.2 sec. and < 1 sec in 1% ETOH in aqueous solution and at pH 6.1 and pH 13, respectively(l). The very long phosphorescence lifetimes are definitely responsible to a considerable extent as far as photobleaching is concerned. However, the participation of the excited singlet state cannot be ruled out. In a review, the fluorescence lifetimes of tyrosine in queous solutions were found to vary between 2.6 nsec to 3.6 nsec(2). On the other hand, the fluorescence quantum yields of tyrosine and various anologous compounds displayed a strong dependence upon the solvent. Such solvents used were water, n-butanol and p-dioxane. The following values of φfl were obtained: For p-HO-C6H4 -CH2COOH; φfl=0.01, 0.22 and 0.34; for p-HO-C6H4-CH3; φfl= 0.23, 0.39 and 0.45 and for p-HO-C6H4-CH2CN; φfl =0.16, 0.34 and 0.34, respectively(3). Furthermore, the value φfl of p-HO-C6H4-CH2CH(NH+ 3)C00? in aqueous solutions was found to be 0.21, where- as that of p-HO-C6H4-CH2CH(NH+ 3)COOH in similar solutions was 0.06. The fluorescence lifetime and quantum yield of phenol in Ethanol were found to be 4.7 nsec and 0.10, respectively(4).  相似文献   

16.
New triethylammonium salts: [(C2H5)3NH]SbCl6 (TCA) and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P21/n and P21/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C2H5)3NH]SbCl6 consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N-H?Cl hydrogen bonds. The crystal structure of [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.  相似文献   

17.
本文研究了B3o+u激发态I2分子在高振动态v′=62时的碰撞猝灭过程。实验中得到了该能级I2分子和其自身以及与其他气体分子(He,Ar,Kr,H2,CO,N2,O2,CH4,NH3,C2H6,CCl4)的碰撞猝灭速率常数,并且发现,在I关键词:  相似文献   

18.
This paper reports on the synthesis, characterization and photophysical properties of the Tb3+ organophosphonates, TbH(O3PR)2, methylphosphonate (R=CH3), ethylphosphonate (R=C2H5), propylphosphonate (R=C3H7), and phenylphosphonate (R=C6H5). The layered Tb3+ organophosphonates were characterized by X-ray diffraction, IR spectroscopy, TG and elemental analysis. The interlayer distances of the Tb3+ organophosphonates evaluated by the X-ray diffractogram were 9.50 Å for TbH(O3PCH3)2, 12.18 Å for TbH(O3PC2H5)2, 14.84 Å for TbH(O3PC3H7)2 and 15.20 Å for TbH(O3PC6H5)2. The Tb3+ luminescence data revealed highly green emissive materials when they were excited at 368 nm, where the characteristic 5D4 → 7F J (J=6, 5, 4 and 3) transitions of Tb3+ were observed at 488, 543, 585 and 619 nm, respectively. The lifetime of the Tb3+ 5D4 → 7F5 transition (λexc=368 nm and λem=543 nm) for the Tb3+ organophosphonates was evaluated from the decay curves, which values were of 2.88, 2.22, 2.14 and 2.59 ms, respectively for TbH(O3PCH3)2, TbH(O3PC2H5)2, TbH(O3PC3H7)2 and TbH(O3PC6H5)2. TG analysis revealed that these materials are thermally highly stable, with no water molecule in their composition, which makes them potential luminophores.  相似文献   

19.
Single-pulse shock-tube experiments were used to study the thermal decomposition of selected oxygenated hydrocarbons: Ethyl propanoate (C2H5OC(O)C2H5; EP), propyl propanoate (C3H7OC(O)C2H5; PP), isopropyl acetate ((CH3)2HCOC(O)CH3; IPA), and methyl isopropyl carbonate ((CH3)2HCOC(O)OCH3; MIC) The consumption of reactants and the formation of stable products such as C2H4 and C3H6 were measured with gas chromatography/mass spectrometry (GC/MS). Depending on the considered reactant, the temperatures range from 716–1102 K at pressures between 1.5 and 2.0 bar. Rate-coefficient data were obtained from first-order analysis. All reactants primarily decompose by six-center eliminations: EP → C2H4 + C2H5COOH (propionic acid); PP → C3H6 + C2H5COOH; IPA → C3H6 + CH3COOH (acetic acid); MIC → C3H6 + CH3OC(O)OH (methoxy formic acid). Experimental rate-coefficient data can be well represented by the following Arrhenius expressions: k(EP → products) = 1013.49±0.16 exp(−214.95±3.25 kJ/mol/RT) s−1; k(PP → products) = 1012.21±0.16 exp(–191.21±2.79 kJ/mol/RT) s−1; k(IPA → products) = 1013.10±0.31 exp(–186.38±5.10 kJ/mol/RT) s−1; k(MIC → products) = 1012.43±0.29 exp(–165.25±4.46 kJ/mol/RT) s−1. The determination of rate coefficients was based on the amount of C2H4 or C3H6 formed. The potential energy surface (PES) of the thermal decomposition of these four reactants was determined with the G4 composite method. A master-equation analysis was conducted based on energies and molecular properties from the G4 computations. The results indicate that the length of a linear alkyl substituent does not significantly influence the rate of six-center eliminations, whereas the change from a linear to a branched alkyl substituent results in a significant reactivity increase. The comparison between rate-coefficient data also shows that alkyl carbonates have higher reactivity towards decomposition by six-center elimination than esters. The results are discussed in in the context of reactivity patterns of carbonyl compounds.  相似文献   

20.
Three novel complexes [Nd(L)(NO3)(H2O)2]·NO3·2H2O (HL1 = N-pyrimidine norcantharidin acylamide acid, C12H13N3O4; HL2 = N-pyridine norcantharidin acylamide acid, C13H14N2O4; HL3 = N-phenyl norcantharidin acylamide acid, C14H15NO4) were synthesized. HL1, HL2 and HL3 are the ligand of complex(1), complex(2) and complex(3), respectively. Their structures were characterized by elemental analysis, conductivity measurement, infrared spectra and thermogravimetric analysis. The DNA-binding properties of the complexes have been investigated by fluorescence spectroscopy and viscosity measurements. The results suggest that the complexes can bind to DNA by partial intercalation. The liner Stern-Volmer quenching constant Ksq values are 3.3(±0.21)(1), 1.7(±0.19)(2) and 0.9(±0.04)(3), respectively. Complex (1) and (2) have been found to cleave pBR322 plasmid DNA at physiological pH and temperature. The test of antiproliferation activity indicates that complex(1) has strong antiproliferative ability against the SMMC7721 (IC50 = 131.7 ± 23.4 μmol·L−1) and A549 (IC50 = 128.4 ± 19.9 μmol·L−1) cell lines. The inhibition rates of complex(2) (IC50 = 86.3 ± 11.3 μmol·L−1) are much higher than that of NCTD (IC50 = 115.5 ± 9.5 μmol·L−1) and HL2 (111.0 ± 5.7 μmol·L−1) against SMMC7721 cell lines.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号