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 62 毫秒
1.
In this paper are presented absorption and fluorescence emission properties of 3-styrylindoles viz. 3-(2-phenylethenyl-E)-NH-indole (1), 3-[2-(4-nitrophenyl)ethenyl-E)-NH-indole (2), 3-[2-(4-cyanophenyl)ethenyl-E]-N-ethylindole (3) and 3-[2-(4-cyanophenyl)ethenyl-E]-NH-indole (4) in organic solvents, 1,4-dioxane-water binary mixtures and micelles (SDS, CTAB and Triton-X-100). The fluorescence properties of 2-4 have been utilized to probe the microenvironment (binding constant, CMC, micropolarity and solubilization site) of the micelles.  相似文献   

2.
《Ultrasonics sonochemistry》2014,21(4):1417-1423
Reversible crystal-to-crystal transformations of 3D lead(II) coordination polymers with the ligand 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh), from nitrate analoge [Pb(4-bpdh)(NO3)2(H2O)]n (1) to [Pb(4-bpdh)(NO3)(Br)]n (2), [Pb(4-bpdh)(Br)2]n (3), [Pb(4-bpdh)(NO3)(Cl)]n (4) and [Pb(4-bpdh)(Cl)2]n (5) by solid state anion-replacement processes under mechanochemical reactions, have been studied. The reversible solid state structural transformations of compounds 15, by anion-replacement processes under mechanochemical reaction, have been verified by PXRD measurements. Nanoparticles of compounds were synthesized by sonochemical process and characterized by scanning electron microscopy (SEM), powder X-ray diffraction, IR spectroscopy and elemental analyses. The SEM images showed that morphology change occurs during solid state anion-replacements of nanocrystals.  相似文献   

3.
Three novel diphosphine-Pt-disulfide complexes were synthesized and characterized by 1H NMR, mass spectrometry and elemental analysis. As a diphosphine, 1,8-bis(diphenylphosphino)naphthalene (dppn), rac-2,2-bis(diphenylphosphino)-1,1-binaphthyl (dppbn), or 1,1-bis(diphenylphosphino)ferrocene (dppf) was employed and chelated to the Pt(II) center. As an anion, p-tolylsulfide (4-SC6H4CH3) was incorporated to Pt(II) center subsequently, yielding (dppn)Pt(4-SC6H4CH3)2 (1), (dppbn)Pt(4-SC6H4CH3)2 (2), or (dppf)Pt(4-SC6H4CH3)2 (3). The photophysical properties of the resulting Pt complexes were investigated with UV–VIS spectroscopy, photoluminescence (PL) spectroscopy and transient PL. Charge Transfer absorptions between the metal and the ligand of 2 and 3 were observed at 320–350 nm in the UV–VIS spectra whereas such noticeable absorption was not observed in 1. The solid films of 1 and 3 showed luminescence at 600 and 580 nm, respectively, while that of 2 did not show emission at the room temperature. The complex 3 exhibited two excited state lifetimes, 23 and 125 ns, at room temperature, and the weighting factor for 125 ns state is only 10% of that for 23 ns one. It means that the prominent luminescence was fluorescence and the intersystem crossing through LS coupling is relatively weak.  相似文献   

4.
《Journal of luminescence》1987,37(4):219-225
Fluorescence spectra, quantum yields and lifetimes of p-cyano-N,N-dimethylaniline (CDMA) were studied in various binary mixtures of n-hexane with chlorinated hydrocarbons. Solvent effects on the equilibrium between normal emission and fluorescence originating from the highly dipolar twisted internal charge transfer (TICT) state arise predominantly from non-specific solute-solvent interactions. The non-radiative deactivation rate of the TICT state is affected primarily by the solvent composition and slows down with the stabilization of the TICT state in environments of high polarity.  相似文献   

5.
Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (VmE), molar isentropic compressibility (Ks,m), excess molar isentropic compressibility (Ks,mE), deviation in speed of sound (uD) from their ideal values (uid) in an ideal mixture, and excess free volumes (VfE) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κS) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.  相似文献   

6.
With a new bis-azole molecular fragment (Htt) bearing 1,2,4-triazole and tetrazole, a mononuclear complex [Fe(tt)2(H2O)4]·2H2O (1), a trinuclear complex [Fe3(tt)6(H2O)6]·2H2O (2) and a 1D coordination polymer [Fe(tt)(Htt)2]BF4·2CH3OH (3) were obtained by varying reaction conditions. Htt acts either as an anionic or neutral ligand depending upon the reaction medium and pH. Thermal variation of spin states of 13 were investigated in the range 77–300?K by 57Fe M?ssbauer spectroscopy. 1 totally remains in high-spin state over the entire temperature range whereas no spin crossover was evidenced in 2. Nearly 1:1 high-spin and low-spin population ratio is found in 3, which remains constant over the entire temperature range investigated.  相似文献   

7.
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   

8.
J D Pandey  P Jain  V Vyas 《Pramana》1994,43(5):361-372
Sound velocity and density were measured in six binary liquid mixtures namely,n-heptane+toluene (I);n-heptane+n-hexane (II); toluene+n-hexane (III); cyclohexane+n-heptane (IV); cyclohexane+n-hexane (V), andn-decane+n-hexane (VI) at 298.15 K. The experimental isothermal compressibility has been evaluated from measured values of density and sound velocity. The isothermal compressibility of these mixtures has been calculated theoretically using different models for the hard sphere equation of state and also using Flory’s statistical theory. The computed values of isothermal compressibility were also compared with the experimentally evaluated values. A satisfactory agreement has been observed.  相似文献   

9.
The spin-spin interactions in a system that contains three different spin carriers, [{LCu}Gd(H2O)3×{Fe(CN)6}] n ·4nH2O (1) [L2−, N,N-propylenedi(3-methoxysalicylideneiminato)], were investigated by electron paramagnetic resonance spectroscopy. Additional information was obtained by analyzing the discrete heterobinuclear system [LCu(OH2)Gd(O2NO)3] (2), which contains the Cu(II)-Gd(III) pair also existing in the structure of 1, and the compounds [{LCu}Gd(H2O)3{Co(CN)6}] n ·3.5nH2O and [{LCu}La(H2O)3×{Fe(CN)6}] n ·4nH2O, which are isostructural with 1 and in which the paramagnetic low-spin Fe(III) and Gd(III) ions were replaced by diamagnetic low-spin Co(III) and La(III), respectively. The investigations were carried out in the temperature range of 293–4 K in both X- and Q-bands and also using a dual-mode X-band. The experimental spectra of the Cu(II)-Gd(III) pairs in 2 were interpreted as the sum of spectra of the ground spin state with total S = 4 and the excited state with S = 3 appearing due to the ferromagnetic exchange interaction between Cu(II) and Gd(III) ions. By fitting the experimental and simulated spectra, the zero-field splitting parameters of the Gd(III) ion are estimated and it is shown that no influence of the anisotropic interaction is detected. The magnetic properties of 1 are discussed from the perspective of the interaction of the Cu(II)-Gd(III) binuclear fragments with the Fe(III) ions.  相似文献   

10.
Carbocations are key intermediates in many important organic reactions. The remarkable effect of the solvent composition on the kinetic parameters of the carbocation decay and product composition was found in the photolysis of 1,2,2,3‐tetramethyl‐1,2‐dihydroquinoline ( 1 ) in 2,2,2‐trifluoroethanol (TFE)–H2O mixtures. The rate constant of the intermediate carbocation decay has a maximum, and the activation energy is minimal in the TFE–H2O mixture 3 : 7 (v/v). In the steady‐state photolysis, products of oligomerization of 1 with n up to 8 and their adducts with TFE and H2O were identified at this solvent composition. The results were rationalized in terms of TFE clustering in aqueous mixtures, with the maximum of cluster formation at 30 vol % TFE. The clusters form a pseudo‐phase, in which the molecules of 1 are concentrated and the carbocations are generated. TFE, H2O and 1 compete in the combination reaction with the photogenerated carbocation to afford the products. This effect was not observed for 1,2,2,4‐tetramethyl‐1,2‐dihydroquinoline ( 2 ), the isomer of 1 , due to steric hindrance at C(4) carbon atom of the heterocycle, the active site of the intermediate carbocation, which makes impossible for the carbocation from 2 to react further with 2 . Thus, the kinetic parameters and the product composition in the photolysis of 1 in TFE–H2O mixtures reflect the changes in the microstructure of the binary solvent. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

11.
Four Ln3+ coordination complexes with the formulas [Ln(p-toluylate)2(Ac)(H2O)]n (Ln=Ho 1, Yb 2) and {[Ln2(OOCCH2CH2COO)3(H2O)4]·6H2O}n (Ln=Ho 3, Yb 4) were synthesized hydrothermally. Their structures were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are isomorphic and form infinite 2D network structures comprising p-toluylate and acetate (Ac) moieties. Complexes 3 and 4 are also isomorphic and possess infinite 2D structures in which succinate acts as bridging ligands that are connected to a 3D hydrogen bonding network by O–H…O hydrogen bonds. Solid-state IR and UV-Vis-NIR spectra, excitation and emission spectra were determined for the four complexes at room temperature. Complexes 1 and 2 exhibit characteristic NIR emission bands of Ln3+ ions but these are shifted and split relative to the theoretical positions. This is also evident for their UV-Vis-NIR spectra. The influence of ligands on enhancing the NIR luminescence of Ln3+ ions in complexes is discussed.  相似文献   

12.
Abstract

The absorption, excitation and fluorescence spectra of the fluorescein dianion (FL2?) in N, N-Dimethylformamide (DMF)/water (H2O) and Dimethylsulphoxide (DMSO)/H2O solvent mixtures have been investigated. It is found that the absorption λmax and emission maxima EX, nax are both hypsochromic shifted when the H2O content in the solvent mixtures increases. However, the shoulder peaks λs remain constant at 483. 5nm within the range of H2O mole fraction, x= 0 to 0. 518 in a DMF/H2O solvent mixture and at 484. 4nm within the range, x=0 to 0. 304, in a DMSO/H2O mixture. Further increases in H2O content, cause a hypsochromic shift in λs. The molar energies for the electronic transition from the ground state (S0) to S1, the first excited singlet state, (ET(1)) and to S2, the 2nd excited singlet state, (ET(2)) of FL2?in the solvent mixtures are also plotted against x. Linear straight lines and intersection points are observed at x=0. 73 for ET(1) and at x=0. 51 for ET(2) in the DMF/H2O mixture and at x=0. 71 for ET(1) and at x=0. 31 &; 0. 69 for ET(2) in the DMSO/H2O mixture. Hydrogen-bonding stabilization effects are used to explain the above observations. The variation in relative fluorescence quantum yields of S1 and S2 of FL2? with x in the aprotic solvent-H2O mixtures to FL2? in pure aprotic solvent are determined and discussed.  相似文献   

13.
ABSTRACT

Effects of (H2O)n (n?=?1–3) on the H2O2?+?HO?→?HO2?+?H2O reaction have been investigated by the reactions of H2O2L(H2O)n (n?=?1–3)?+?HO and H2O2?+?HOL(H2O)n (n?=?1–3) at the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ level of theory, coupled with rate constant calculations by using canonical variational transition state theory. Interestingly, for the former reactions, one-step process and stepwise mechanism are involved, where one-step processes occurring though cage-like hydrogen bonding network complexes and the transition states are favourable. Due to larger effective rate constants, these favourable processes are also favourable than the corresponding latter reactions. Meanwhile, the catalytic effect of (H2O)n (n?=?1–3) is mainly taken from water monomer, because the effective rate constant (k'(R_WM2)) of H2O2···H2O?+?HO reaction is, respectively, larger by 3, 6–10 orders of magnitude than that of H2O2···(H2O)2?+?HO (k'(R_WD1)) and H2O2···(H2O)3?+?HO (k'(R_WT1)) reactions. Furthermore, the enhancement factor of water molecular (k'(R_WM2)/ktot) is only 0.28% at 240?K, while at high temperature (such as at 425?K), the positive water vapour effect enhances up to 27.13%. This shows that at high temperatures the positive water effect is obvious under atmospheric conditions.  相似文献   

14.
Two novel ternary rare-earth complexes SmL5·L·(ClO4)2·7H2O and EuL5·L·(ClO4)2·6H2O (the first ligand L = C6H5COCH2SOCH2COC6H5, the second ligand L = C6H4OHCOO) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL5·L·(ClO4)2·nH2O (Ln = Sm, Eu; n = 7, 6) enhanced more obviously than the binary complexes LnL5·(ClO4)3·2H2O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.  相似文献   

15.
Mg[Pt(CN)4]·7H2O belongs to the class of tetracyanoplatinates(II) which crystallize in columnar structures. In different Mx[Pt(CN)4yH2O (MCP) single crystals the in-chain Pt-Pt-distance R varies between 3.67 Å (NaCP) and 3.15 Å (MgCP). Two optical transitions can be observed in polarized emission with the electric field vector E either parallel or perpendicular to the columnar (c)-axis. Polarized emission spectra of MgCP are recorded under hydrostatic pressure up to p ≈ 18 kbar (at 295 K). The transition energy v?6 can be tuned from 17,600 cm-1 to about 12,000 cm-1 (2.18-1.48 eV). The pressure induced red shift for the two transitions is: E 6 c: dv?6/dp = -320±20 cm-1/kbar, Ec: dv?/dp = -270±20 cm-1/kbar. These values are discussed in the context of the known functional relationship (for ambient conditions) between v? and R.  相似文献   

16.
The reactions of lanthanide nitrates with a Schiff-base ligand HL (2-[(2-hydroxypropylimino)methyl] phenol) have produced five new complexes with formula as [Ln2(L)3(NO3)3]CH3OH(Ln=Gd 1, Tb 2, Dy 3, Ho 4, Er 5). These new complexes are characterized by elemental analysis, IR and X-ray diffraction, as well as fluorescence spectra. Single-crystal X-ray diffraction analysis reveals that all the complexes crystallize in the trigonal system, space group R-3. Fluorescence spectroscopy of Tb(III) and Dy(III) complexes display strong characteristic metal-centered fluorescence in solid state, which demonstrates that luminescence is sensitized by the effective energy-transfer from ligand to the metals. The fluorescence lifetimes of complex 2 and 3 are also determined.  相似文献   

17.
The experimental densities (ρ), dynamic viscosities (η), speeds of sound (υ) and relative permittivities (εr) of thirty six binary mixtures of esters (methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate) + organic solvents (n-hexane, benzene, toluene, o-, m-, p- xylenes), + halogenated benzene (chloro-, bromobenzene), + nitrobenzene have been measured over the complete composition range at atmospheric pressure and temperatures (298.15 to 313.15 K). The excess molar volumes, VmE, excess isentropic compressibilities, κsE, deviations in relative permittivities, δεr have been calculated and fitted to Redlisch–Kister type equation. The dynamic and kinematic viscosities have been correlated through Grunberg–Nissan and MacAllister equations. The qualitative analysis of various functions revealed that i.) esters lose their dipolar association in presence of inert and unlike n-hexane, ii.) specific but weaker nπ type interactions predominate in binary mixtures of esters + aromatic organic solvents and iii.) weak electron donor–acceptor complexes predominate in the mixtures of esters with halogenated and nitrated benzene.  相似文献   

18.
[Ca(H2O)6]Cl2 between 93 and 300 K possesses two solid phases. One phase transition (PT) of the first‐order type at = 218.0 K (on heating) and = 208.0 K (on cooling) was determined by differential scanning calorimetry. Thermal hysteresis of this PT (10 K), as well as the heat flow anomaly sharpness, suggests that the detected PT is a first‐order one. The entropy change value [ΔS ≈ 8.5 J mol−1 K−1 ≈ Rln(2.8)] associated with the observed PT suggests a moderate degree of molecular dynamical disorder of the high‐temperature phase. The temperature dependencies of the full width at half maximum values of the infrared band are due to ρ(H2O)A2 mode (at 205 cm−1), and two Raman bands are arising from τ(H2O)E and τ(H2O)A1 modes (at ca. 410 and 682 cm−1, respectively), suggesting that the observed PT is associated with a sudden change of speed of the H2O reorientational motions. The estimated mean value of activation energy for the reorientation of the H2O ligands in the high‐temperature phase is ca. 11.4 kJ mol−1 from Raman spectroscopy and 11.9 kJ mol−1 from infrared spectroscopy. X‐ray single‐crystal diffraction measurement and spectroscopic studies (infrared, Raman and inelastic neutron scattering) also confirm that [Ca(H2O)6]Cl2 includes two sets of differently bonded H2O molecules. Ab initio calculations of the complete unit cell of one molecule of calcium chloride with a different number of water molecules (2, 4 and 6) have also been carried out. A comparison of Fourier Transform Infrared (FT‐IR), Fourier Transform Raman Scattering (FT‐RS) and inelastic neutron scattering spectroscopies results with periodic density functional theory calculations was used to provide a complete assignment of the vibrational spectra of [Ca(H2O)6]Cl2. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

19.
Starting with H+[CH3C(O)CH2C(O)CH3] (denoted H+PD), the protonated diketone-water clusters H+PD(H2O) n (n = 1–3) have been characterized by density functional theory calculations in combination with vibrational predissociation spectroscopy to explore the conformational changes of a protonated bifunctional ion solvated by water in the gas phase. Theoretical calculations for H+PD revealed that the ion contains an intramolecular hydrogen bond (IHB), with two oxygen atoms bridged by the extra proton in an O—H+ … O form. Attachment of one water molecule to it readily ruptures this IHB, replacing the H+ by the H3O+ moiety. Further replacement of the IHB by two water molecules occurs at n = 2 and the ?C(O)CH2C(O)- chain is fully opened (or unfolded) after transfer of the extra proton to the water trimer at n = 3. To verify the computational findings, infrared spectroscopic measurements were performed using a vibrational predissociation ion trap spectrometer to identify cluster isomers from the signatures of hydrogen bonded and non-hydrogen bonded OH stretching spectra of H+PD(H2O)2,3 produced in a corona discharge supersonic expansion. Besides open form isomers, evidence for the formation of water-bridged structures has been found for H+PD(H2O)3 at an estimated temperature of 200 K. A detailed illustration of the unfolding steps as well as the energy profiles for the evolution of a two-water bridge isomer from the protonated H+PD monomer are analysed pictorially (including both stable intermediates and transition states) in the present investigation.  相似文献   

20.
Electronic absorption and fluorescence emission spectra of DMDMAQ (1,4-dimethoxy-2,3-dimethyl-9,10-anthraquinone) have been studied as a function of solvent composition in some binary mixtures and in different neat solvents. The binary mixtures consist CCl4 (Carbon tetrachloride)-DMSO (Dimethylsulfoxide), EtOH (Ethanol)-DMSO, and CCl4-EtOH combination of single solvents. The wavelength maxima of the absorption band for DMDMAQ are quite solvent sensitive in aprotic solvents. But, in protic solvent, there is no marked shift in absorption and emission maximum which shows the absence of specific interaction. Excited state shows increasing shift with increasing solvent polarity compared to ground state. The ratio of dipole moment in the excited state to that in the ground state was calculated. Different criteria were considered to analyse preferential solvation characteristics in different binary mixtures, viz., local mole fraction (), solvation index (δS2) and exchange constant (K12).  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