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1.
Three novel aza-crown ether derivatives incorporating 4-amino-7-nitrobenzaoxa-1,3-diazole (NBD) chromophore were synthesized and their structure confirmed by 1H-NMR, IR and elemental analysis. The influence of the solvent polarity and protonation on the photophysical properties of NBD-15-crown-5 was studied by UV/Vis and fluorescence methods. The influence of the investigated cations on the absorption spectra of the ligands was negligible, however emission was strongly affected. Complexation and binding stability of NBD-aza-15-crown-5 and NBD-aza-18-crown-6 were studied using fluorescence spectroscopy. NBD-aza-18-crown-6 exhibits strong selectivity toward Ca2+ and Sr2+ ions with formation constants about 103 times higher than the formation constants with the other ions included in the study.  相似文献   

2.
New 2-acyl-1,3-indandione derivatives, compounds 1–4, were obtained by condensation of 2-acetyl-1,3-indandione with benzaldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde and furane-2-aldehyde, respectively. The structures of the newly synthesized 2-substituted 1,3-indandiones were characterized by means of spectroscopic methods (FT-IR, 1H and 13C NMR, UV-Vis and MS). Based on the obtained results it is suggested that the compounds exist in the exocyclic enolic form. Mass spectral fragmentation paths are also proposed. In order to verify the possibility for tautomerization processes of the newly synthesized compounds their absorption spectra were recorded in various solvents. Furthermore, the complexation properties of the compounds with metal(II) ions were also studied. A series of non-charged complexes with Cu(II), Cd(II), Zn(II), Co(II) and Ni(II) was isolated and analyzed by elemental analyses and IR. The paramagnetic Cu(II) complexes were studied by EPR and distorted, flattened tetrahedral structures are predicted. The other metal complexes show the presence of water molecules, most probably coordinated to the metal ion, thus forming octahedral geometry. Ultimately, the studied properties of the newly synthesized compounds, 1–4, suggest that they may find application as extracting agents for metal ions, rather than as optical sensors.   相似文献   

3.
The molecular structures of 1,3-benzodioxole and 1,3-indandione partially oriented in nematic solvents have been studied by NMR. Results for 1,3-indandione agree well with a planar model. The structural parameters are similar to those obtained by X-ray studies. No keto-enol tautomerism is observed. An anomalous structural result is obtained for 1,3-benzodioxole if the molecule is assumed to be planar. Dipolar couplings agree well with puckered model. The puckering angle is found to be about 15.5° ± 2°, similar to the values observed for TTF, TSeF and 2,5-dihydrofuran.  相似文献   

4.
Summary. Novel glass-forming 2-(1-phenyl-1,2,3,4-tetrahydroquinoline-6-ylmethylene)-1,3-indandione derivatives were synthesized and their thermal properties were studied. The results of a preliminary investigation of the photoelectric properties of amorphous films of the title compounds are briefly reported. The ionization potential of these molecular glasses is ca. 5.6 eV and the hole drift mobility exceeds 10−8 cm2 V−1 s−1 at strong electric fields.  相似文献   

5.
The electron impact-induced fragmentation of 2,2-dimethyl- and 2-ethyl-1,3-indandione, 1 and 2, and their isomers, 3-isopropylidene- and 3-propylidenephthalide, 3 and 4, respectively, was studied in detail by mass-analysed ion kinetic energy (MIKE) and collision-induced dissociation (CID-MIKE) spectrometry, including 2H and 13C. labelled analogues of 1 and 2. In all regimes of internal energy, the molecular ions 1+. ? 4+. interconvert by up to seven consecutive, reversible isomerization steps prior to the main fragmentation processes, viz. loss of CH3. and C2H4. 1,3-Indandione and 3-methylenephthalide ions with identical alkylidene moieties (i.e. 1+.?3+. and 2+.?4+.) equilibrate rapidly and completely prior to fragmentation, whereas these pairs of isomers interconvert only slowly via a five-step rearrangement of the indandione ions 1+.?2+.. Distinct from the behaviour of simpler ionized carbonyl species, a 1,2-C shift of a (formally) neutral carbonyl group is found to occur along with that of a protonated one. Also distinct from simpler cases, methyl loss does not take place from the ionized enol intermediates formed within the interconversion 1+.?2+. of the diketone ions but rather from the n-propylidenephthalide ions 4+.. This follows from CID-MIKE spectrometry of the [M ? CH3]+ ions of 1–4 and two reference C10H7O2+ (m/z 159) ions of authentic structures (protonated 2-methylene-1,3-indandione and protonated 1,4-naphthoquinone). The characteristic CID fragmentation of the C10H7O2+ ions is rationalized. Finally, the multistep isomerization of ionized 1,3-indandiones apparently also extends to higher homologues [e.g. 5+. from 2-ethyl-2-methyl-1,3-indandione (5) and 6+. from 2,2-diethyl-1,3-indandione (6)]: the ionized phthaloyl group of 1,3-indandione radical cations 1+., 2+., 5+. and 6+., originally attached with its two acyl functionalities to the same carbon of the aliphatic chain, performs, in fact, a ‘multi-step migration’.  相似文献   

6.
Abstract

Methods for the preparation of the 4-diphenylphosphino derivatives of N-phenylaza-15-crown-5 and -18-crown-6 are described. The properties of these systems and the 4′-diphenylphosphino derivative of benzo-15-crown-5 have been examined by way of picrate ion extraction abilities and IR spectra of their Ni(CO)3L (L = these phosphines) complexes. All three have abilities to extract Na+ and K+ that are comparable to benzo-15-crown-5. The IR studies (νCO, A1 band) indicate that the azacrown systems have better ability than the benzocrown system to increase the electron density on the nickel center. Further, the addition of alkali metal ions, Na+ and K+, to the Ni(CO)3L solutions results in maximum shifts of ca 1.5 cm?1 for the former systems and 0.7 cm?1 for the latter system. A rationale for this observation is presented in terms of Hammett substituent constants. Finally, an X-ray structure of the phosphine oxide of the phenylaza-15-crown-5 derivative is presented. A prominent feature of the structure is that the nitrogen atom is essentially planar with the result that the crown ether ring is large and not preorganized for coordination of spherical ions.  相似文献   

7.
The complexation of a series of new Schiff bases containing theN-phenylaza-15-crown-5 (Ph-A15C5) moiety with alkali and alkaline-earth metal ions (incl. Be2+ and Mg2+, is studied by means of UV-Vis spectroscopy. The corresponding stability constant values are determined and discussed from two aspects: the position of the Ph-A15C5 moiety in the ligand molecule and the nature of the metal ion.  相似文献   

8.
The synthesis, structure and spectral properties of a new cinnamoyl derivative of 2-acetyl-1,3-indandione (2AID), p-fluoro-cinnamoyl-1,3-indandione, LH and its metal(II) complexes with Cu(II), Zn(II) and Cd(II), are described. In order to verify the molecular structure of the free ligand and its metal complexes, model geometries based on the spectroscopic data were optimized using quantum chemical methods. The experimental spectroscopic data (IR and NMR) of the ligand, LH, complemented by the calculated ones, show that it exists in the exocyclic enolic form in the gas phase, solution and solid state. Good quality single crystals of Cd(II) complex were obtained from a DMSO solution and were studied by means of single-crystal X-ray diffraction. The data show bidentate coordination of the ligand and two DMSO molecules coordinated to the metal centre, thus forming a complex with octahedral geometry. On the contrary, the spectroscopic data on the amorphous samples indicate a square planar geometry of the Cu(II) complex and distorted octahedral geometry for Zn(II) and Cd(II) complexes with two water molecules coordinated to the metal centre. The used quantum chemical method for structure optimization of the transition metal complexes, B3LYP/LANL2DZ, shows very good agreement with the crystallographic data and, therefore, was also employed for structural determination for the non-crystalline complexes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

9.
The coordination reaction of Na+, K+, Rb+ and Cs+ with benzo- 15-crown-5, 18-crown-6 and the newly synthesized cyclic polyethers 2, 3-benzo-8, 15-dimethyl-18-crown-6, 2, 3-benzo-8, 11, 15-trimethyl-18-crown-6 in methanol at 25`C has been studied by conductometric titration. The stability constants for the 1:1 coordination compounds were calculated. The marked selectivity of 18-crown-6 toward alkali metal ions was not found in its methyl derivatives. The induction effect of the benzene ring and methyl group on polyether ring reduced the stability of the coordination compounds. In methanol, the stability sequence of te compounds of alkali metal ions with 18-crown-6 was K+>Rb+>Cs+>Na+, that of its dimethyl derivative was K+>Rb+>Na+>Cs+ and that of its trimethyl derivative was K+>Na+>Rb+>Cs+, that is, the methyl substituent had a weaker influence on the stability of Na+ compound than on that of Rb+ or Cs+ compound. In the range of concentration studied, decrease in equivalent conductance is in agreement with the prediction on the basis of the structure of the complexes. The above results may give a clue for modifying the structure of a crown ether for specified selectivity.  相似文献   

10.
A number of N-alkylnitrobenzoaza-15-crown-5 with the macrocycle N atom conjugated with the benzene ring were obtained. The structural and complexing properties of these compounds were compared with those of model nitrobenzo- and N-(4-nitrophenyl)aza-15-crown-5 using X-ray diffraction, 1H NMR spectroscopy, and DFT calculations. The macrocyclic N atom of benzoazacrown ethers are characterized by a considerable contribution of the sp3-hybridized state and a pronounced pyramidal geometry; the crownlike conformation of the macrocycle is preorganized for cation binding, which facilitates complexation. The stability constants of the complexes of crown ethers with the NH4 +, EtNH3 +, Na+, K+, Ca2+, and Ba2+ ions were determined by 1H NMR titration in MeCN-d3. The most stable complexes were obtained with alkaline-earth metal cations, which is due to the higher charge density at these cations. The characteristics of the complexing ability of N-alkylnitrobenzoaza-15-crown-5 toward alkaline earth metal cations are comparable with analogous characteristics of nitrobenzo-15-crown-5 and are much better than those of N-(4-nitrophenyl)aza-15-crown-5.  相似文献   

11.
The complexation reaction of phenylaza-15-crwon-5, 4- nitrobenzo- 15-crown-5, and benzo-15-crown-5 with Ag+, Tl+ and Pb2+ ions in methanol solution have been studied by a competitive potentiometric method. The Ag+/Ag electrode used both as an indicator and reference electrode in a concentration cell. The emf of cell monitored as the crown ethers concentration varies through the titration. The stoichiometry and stability constants of resulting complexes have been evaluated by MINIQUAD. The stoichiometry for all resulting complexes was 1:1. The stability of these metal ions with derivatives of 15-crown-5 are in order phenylaza-15-crown-5 > Benzo-15-crown-5 > 4-nitrobenzo-15-crown-5, and for the each used crown ethers are as Pb2+ > Ag+ > Tl+. The effect of the substituted group on the stability of resulting complexes was considered. The obtained results are novel and interesting.  相似文献   

12.
The electronic spectrum of 2-N-pyridinia-1,3-indandione betaine was calculated by the MO LCAO method within the CNDO/S approximation with the Del Bene-Jaffe parametrization in order to refine the concepts regarding the character of the longwave absorption band of this compound. It was established that the long-wave absorption band of this compound is due to an electron transition with charge transfer and has a vibrational structure.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 658–661, May, 1981.  相似文献   

13.
An X-ray structure of a Co(II) complex of bidentate chelating 2-acetyl-1,3-indandione (2AID) is reported–Co(2AID)2(H2O)2 · 2H2O. The compound crystallizes in the monoclinic space group P21/n with four molecules per unit cell. The molecular structure shows distorted octahedral geometry of the metal center. The complex is characterized by EPR and magnetic measurements, which show high-spin electronic structure for the metal ion.  相似文献   

14.
Abstract

7Lithium NMR measurements were used to determine the stoichiometry and stability of Li+ complexes with 12-crown-4, 15-crown-5 and benzo-15-crown-5 in acetonitrile solution. A competitive 7Li NMR technique was also employed to probe the complexation of Mg2+, Ca2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ ions with the same crown ethers. In all cases, the stability of the resulting 1:1 complexes was found to decrease in the order 15-crown-5 > benzo-15-crown-5 > 12-crown-4. Ca2+ and Cd2+ ions formed the most stable complexes in the series.  相似文献   

15.
Copper, cobalt, and zinc complexes of symmetrical and unsymmetrical macroheterocyclic ligands containing thiadiazole, pyridine, and 1,3-indandione fragments were prepared by reactions of these ligands with appropriate metal salts. The physicochemical properties of the complexes were studied.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1902–1906.Original Russian Text Copyright © 2004 by Berezina, Vorobev, Smirnov, Sokolova.This revised version was published online in April 2005 with a corrected cover date.  相似文献   

16.
Schiff bases derived from 7-hydroxy-4-methyl-2-oxobenzo[h]chromene-8-carbaldehyde in solution exist as equilibrium mixtures of benzoid and quinoid tautomers. The fraction of the quinoid tautomer increases with rise in solvent polarity. The Schiff base containing a benzo-15-crown-5 fragment on the nitrogen atom was shown to be a new ambident chemosensor capable of selectively binding transition metal cations via reaction at the o-hydroxyaldehyde imine fragment and alkaline-earth metals via host-guest interaction with the crown ether moiety. This compound exhibits a pronounced sensor activity toward Mg2+ and Ba2+ ions and is a selective naked-eye fluorescent chemosensor for Cu2+ and Co2+ ions.  相似文献   

17.
Mosher WA  Bechara IS  Pozomek EJ 《Talanta》1968,15(5):482-484
Derivatives of 2-diphenylacetyl-1,3-indandione have proved useful in identification of a wide variety of functional groups in organic compounds, and an account is given of their application in qualitative analysis.  相似文献   

18.
The structure of the synthesized compound of cobalt(II) with 2-diphenylacetyl-1,3-indandione (HL) and two dimethyl sulfoxide molecules was studied by X-ray single-crystal diffraction. One of the dimethyl sulfoxide molecules is disordered over two positions. Crystals of the compound are triclinic: Z = 2, space group P1, a = 11.510(6) Å, b = 11.686(6) Å, c = 16.667(8) Å, α = 93.14(1)°, β = 108.48(1)°, γ = 96.34(1)°. The deprotonated ligand molecules in the inner coordination sphere are located in the equatorial plane of the cobalt coordination polyhedron in the cis configuration. The two DMSO molecules are monodentate coordinated to the central atom through oxygen donor atoms and occupy axial positions.  相似文献   

19.
Crown-containing arylimines of 5-hydroxy- and 5-hydroxy-6-nitro-2,3-diphenylbenzo[b]furan-4-carbaldehydes were synthesized and their structure, spectral, luminescent, and complexing properties were studied by means of 1H and 13C NMR, IR, UV, and mass-spectrometry. In solution, these compounds exist as equilibrium mixtures of benzenoid and quinoid tautomers. The relative concentration of the quinoid form increases in the order of solvents: toluene, acetonitrile, 2-propanol, chloroform. The presence in the benzo[b]furan moiety of a strong withdrawing 6-NO2 group favors stabilization of the quinoid tautomer. This finding is in accord with the results of the DFT B3LYP/6-311++g(d,p) calculations. Complexation of 5-hydroxy-6-nitro-2,3-diphenyl-1-benzofuran-4-carbaldehyde crown-containing imines with alkali and alkali-earth metal ions shifts the tautomeric equilibrium to the quinoid forms and is accompanied by blue shifts of the emission spectra. The Schiff bases obtained represent a new type of fluorescent tautomeric chemosensor for Mg2+, Ca2+ (benzo-15-crown-5 derivative), and Ba2+ (benzo-18-crown-6 derivative) displaying diagnostic changes in both absorption and emission spectra.  相似文献   

20.
Compound [Zn(CF3CO2)2(Bpp)2], where Bpp is 1,3-bis(4-pyridyl)propane, was synthesized and its structure and luminescent properties were determined. Crystals are monoclinic, space group C2/c, a = 21.261(1) Å, b = 17.642(1) Å, c = 18.632(1) Å, β = 115.85(1)°, V = 6289.3(6) Å3, ρcalcd = 1.453 g/cm3, Z = 8. The structure comprises 2D neutral layers of conjugated multiunit rings composed of four Zn2+ ions united by four bridging Bpp ligands. Each of two crystallographically nonequivalent Zn atoms is coordinated at the octahedra apices to four nitrogen atoms of two Bpp ligands and two O(CF3CO2) atoms. Trifluoroacetate anions are coordinated to Zn2+ ions in monodentate manner. The compound exhibits photoluminescence in solid state.  相似文献   

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