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1.
The synthesis, characterisation and binding and deprotonation studies with anions for four 5-(1H-indol-3-yl)-pyrazolyl derivatives (25) have been described. It is worthy to mention that sensor 2 shows a drastic change in absorption spectrum (ca. 335 nm) and colour (colourless to blue) upon addition of F? in DMSO solution due to the deprotonation of indole –NH proton, as confirmed by 1H NMR titration. Sensor 4 recognizes F? and CN? ions by deprotonation mechanism with visible colour change of the solution in a similar manner to that of 2. However, in contrary to 2 and 4, sensor 3 binds with F?, CN?, H2PO4 ?, AcO? and PhCOO? ions exploiting hydrogen-bonding interaction with the shifting of absorption band to longer wavelength and subsequent colour change of the solution. Compound 5 recognizes F? without any visual colour change and its binding is studied by 1H NMR titration to acquire the important information about the nature of binding between F? and 5.  相似文献   

2.
A novel fluorescent anion sensor 1 based on boradiazaindacenes (BODIPY) derivative was synthesized and its absorption and fluorescence properties were investigated in various solvents. 1 exhibited a red shift of absorption spectrum and fluorescence quenching in varying degree in the presence of F?, AcO?, H2PO4 ? and Cl? due to multiple hydrogen bonding interactions between these anions and calix[4]pyrrole receptor. As an anion sensor in the visible region, 1 displayed the similar selectivity and sensitivity toward anions compared to the parent calix[4]pyrrole. However, 1 can be used as an effective dual responsive optical sensor for F? via chromogenical and fluorogenical signals.  相似文献   

3.
The interaction between chemosensor, N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (1) and different halide ions (F ? , Cl? and Br?) has been investigated using density functional theory (DFT). A clear insight of the sensor anion binding process has been presented. Our calculations revealed that the observed colorimetric and fluorescent signals are induced due to the ground state deprotonation of the sensor molecule caused by F? which has two times higher binding affinity than other halide ions (Cl? and Br?). Derivatives of system 1 have been made to find a better sensor with higher binding affinity and longer wavelength of absorption. All the derivatives are better sensors than the parent 1 except 4-methyl-N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (2). Among these derivatives, trimethyl-[4-(2-methyl-1,3-dioxo-indan-5-ylcarbamoyl)-phenyl]-ammonium (8) and (5-benzoylamino-1,3-dioxo-indan-2-yl)-trimethyl-ammonium (9) showed a change to higher binding energies of about 58 Kcal/mol and longer absorption wavelengths of 53 nm after deprotonation process than the parent system 1 which is highly demanded in selective chemical sensing. Systems 8, 9 and their deprotonated zwitterionic forms (8z and 9z) have also been studied for their nonlinear optical responses. Systems 8, 9 showed significantly good first hyperpolarizability (β) of 84 × 10?30 and 40 × 10?30 esu, respectively. These β values increase in zwitterionic states up to 216 × 10?30 and 109 × 10?30 esu, respectively after deprotonation with F?, representing a new signal of deprotonation.  相似文献   

4.
The synthesis, characterization and binding studies with anions for biaryl-based anion receptors bearing thiourea groups have been described. The results revealed that receptors (1 and 2) showed good selectivity and binding affinity for F?, and among them binaphthyl-based receptor (1a) showed the best binding affinity for F? in comparison to other tested anions (Cl?, Br?, I?, $ {\text{NO}}_{3}^{ - } ,\;{\text{HSO}}_{4}^{ - } , $ AcO? and $ {\text{H}}_{2} {\text{PO}}_{4}^{ - } $ ). This is probably due to the fact that the moderate rigidity of binaphthyl skeleton in 1a is able to provide the better geometry of two thiourea groups for incorporating F? into the binding pocket. The higher basicity of F? also participated in this selectivity.  相似文献   

5.
The hydrothermal reactions of nitrate or chloride salts of Co(II), Zn(II), Cd(II), Hg(II) and Ag(I) with an unsymmetrical benzotriazole derivative 1H-1,2,3-benzotriazole-1-propionic acid (Hbtap) afforded five new metal–organic coordination polymers with formula of [M(btap)2(H2O)2] n (M = Co 1, Zn 2, Cd 3), [Hg(btap)Cl] n (4) and {[Ag(btap)]·H2O} n (5), which were characterized by X-ray diffraction and spectroscopic methods. The anionic btap? ligands in these complexes assume the same anti conformation, but show different coordination behaviors toward transition metal ions. Complexes 1, 2 and 3 are isostructural and reveal infinite one-dimensional (1D) looped-chain structures constructed by hexacoordinated metal centers and 2-connected btap? bridges. Complex 4 features 1D zigzag polymeric arrays, which are interlinked with each other resulting in a chiral three-dimensional (3D) 4-connected framework. In complex 5, the 3-connected ligands join Ag(I) atoms into a 1D ribbon motif. The photoluminescence spectra of three d10 metal complexes 2, 3 and 4 were measured at room temperature. The emission peaks of these complexes resemble that of the free ligand and can be ascribed to the intraligand π–π* transitions.  相似文献   

6.
Four 3d-4f heterometallic complexes, [CuⅡ LnⅢ (bpt) 2 (NO 3 ) 3 (MeOH)] (Ln = Gd, 1; Dy, 2; bptH = 3,5-bis(pyrid-2-yl)-1,2,4- triazole), [CuⅡ 2 LnⅢ 2 (μ-OH) 2 (bpt) 4 Cl 4 (H 2 O) 2 ]·6H 2 O (Ln = Gd, 3; Dy, 4), have been synthesized under solvothermal conditions. X-ray structural analyses reveal that 1 and 2 are isostructural while 3 and 4 are isostructural. In each complex, the copper and gadolinium or dysprosium ions are linked by two triazolate bridges and form a CuⅡ -LnⅢ dinuclear unit. The intramolecular Cu-Ln distances are 4.542, 4.525, 4.545 and 4.538 for 1, 2, 3 and 4, respectively. Two dinuclear CuLn units are bridged by two OH- groups into the zig-zag tetranuclear {CuⅡ 2 LnⅢ 2 } structures with the Ln(Ⅲ) Ln(Ⅲ) distances of 3.742 and 3.684 for 3 and 4, respectively. Magnetic studies show that the antiferromagnetic CuⅡ-LnⅢ interactions occur in 1 (J CuGd = 0.21 cm-1 ) and 2. The antiferromagnetic interaction occurs in complex 3 with J CuGd = 0.82 cm-1 and J GdGd = 0.065 cm-1 , while dominant ferromagnetic interaction occurs in complex 4.  相似文献   

7.
The products of UV photolysis of ternary Ar?CH4(CD4)?F2 mixtures (1:c:c 0,c, c 0=0.001–0.01) at 13–16 K were identified by ESR and FTIR spectroscopy. These products are?CH3 (?CD3) radicals of typesI andII and molecular CH3F?HF complexes. The latter were characterized by the IR bands of the stretching C?F (1003 cm?1) and H?F (3774 cm?1) vibrations. The ESR spectra of radicalsI are asymmetric. The anisotropy of theg-factor (Δg~10?3) of radicalI indicates that the structure of the radicals is nonplanar. The ESR spectrum of the typeII radical is identical to that of matrix-isolated?CH3 (?CD3) radicals with the planar structure (Δg<5·10?5). Under the experimental conditions, the amount of complexes formed in the photolysis is equal to 0.022·c. When the photolysis is ceased, radicalI disappears after ≈103 s and radicalII is stabilized. The limiting concentrations of the stabilized?CH3 and?CD3 radicals are equal to 2·10?2·c and 2·10?3·c, respectively. A mechanism of the formation of the products is suggested. It is based on the assumption that both matrix-isolated CH4 and F2 and their heterodimers CH4?F2 are present in the samples and it takes into account the long-range migration of translationally excited flourine atoms. The CH3F?HF complexes and radicalsI are generated by the photolysis of the CH4?F2 heterodimers. The decay of radicalsI is caused by geminate recombination of proximate F...CH3 pairs. RadicalsII are formed in the reaction of translationally excited fluorine atoms with isolated CH4 (CD4) molecules.  相似文献   

8.
We report here a selective, efficient and very simple receptor which can easily detect F? in the presence of a wide range of other anions [Cl?, Br?, I?, HSO 4 ? , NO 3 ? , Acetate (AcO ?) and Benzoate (BzO ?)] by use of colorimetric or fluorometric detection. 4-Chloro-2,6-bis(hydroxymethyl) phenol (CBHMP) is a simple and available phenolic receptor having no special chromophoric function. In this colorimetric method, naked-eye detection of F? with CBHMP is described. Interestingly, fluorometric detection of F? is also possible by highly selective fluorescent quenching response CBHMP in dimethyl sulfoxide (DMSO) media.  相似文献   

9.
Triphenylamine-based new chemosensors 1 and 2 have been designed and synthesized for fluorometric detection of anions. The urea-amide conjugates in 1 and 2 are involved in binding of anions via hydrogen bonding. UV?Cvis and fluorescence titration experiments revealed that the sensor 1 has the selectivity for acetate (AcO?), dihydrogenphosphate (H2PO4 ?) and fluoride (F?) over the other anions examined in the present study, in CHCl3. In comparison, receptor 2 is non responsive for the same anions under similar conditions. In more polar solvent CH3CN containing 0.1% DMSO, the receptor 1 shows a greater selectivity towards fluoride. The color of the solution of 1 is changed from colorless to light yellow and finally to yellowish brown only in the presence of fluoride in CH3CN containing 10% DMSO. In pure DMSO and CH3CN solvents, almost colorless solution of 1 is transformed into blood red and reddish brown in the presence of 30 equivalent amounts of F?, respectively.  相似文献   

10.
A systematic fluorescence and flash photolytic investigation of a series of covalently linked fullerene / ferrocene based donor-bridge-acceptor dyads is reported as a function of the nature of the bridge between the donor site and acceptor site. The fluorescence of the investigated dyads 2rel = 0.17 × 10?4, 3rel = 0.78 × 10?4), 4rel = 1.5 × 10?4), 5rel = 0.7 × 10?4), and 6rel = 2.9 × 10?4) were substantially quenched, relative to N-methyl fulleropyrrolidine (1) (Φrel = 6.0 × 10?4). Photolysis of N-methyl fulleropyrrolidine (1) in toluene revealed formation of the excited singlet state which was followed by a rapid intersystem crossing to the excited triplet state. On the other hand, the fate of the excited singlet state of 2, 3, 4, 5, and 6 was found to be governed by rapid intramolecular quenching, with rate constants of 28×109 s?1, 6.9×109 s?1, and 3.4×109 s?1, 14×109 s?1, 2.3×109 s?1 respectively. The electron transfer process and the charge separation were confirmed by monitoring the characteristic π-radical anion bands at λmax = 400 and 1055 nm in degassed benzonitrile with τ1/2 = 1.8 μs (3) and 2.5 μs (4).  相似文献   

11.
Three coumarin derivatives, 7-hydroxy-3-(2-pyridyl)coumarin (HPC), 7-(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)benzyloxy)-3-(2-pyridyl)coumarin (Ox-PC), and 7-(4-(9H-carbazol-9-yl)butoxy)-3-(2-pyridyl)coumarin (Cz-PC), were synthesized and characterized by elemental analysis, 1H NMR, FT-IR, and UV?Cvis absorption spectra. The fluorescence behaviors of the compounds in methanol solutions and solid states were investigated. HPC exhibits weak green emission, whereas Cz-PC and Ox-PC show strong blue emissions in dilute solutions.  相似文献   

12.
The reactions of 3(5)-(4-methoxyphenyl)-5(3)-phenyl-1H-pyrazole (L 1 ) with nitric acid and 5-(4-benzyloxyphenyl)-3-(furan-2-yl)-1H-pyrazole(L 2 ) with hydrochloric acid produced [HL 1 · NO3] (Salt-1) and [HL 2 · Cl] (Salt-2). The structures of Salt-1 and Salt-2 were determined by single crystal X-diffraction. In Salt-1, HL 1 showed [2 + 2] binding of NO3 ? ions in the solid state to form dimer architecture with R 1 2 (4) and R 4 4 (14) graph sets. An anion directed one-dimensional anion-assisted helical chain with active participation of the chloride ion and protonated pyrazole via N–H···Cl hydrogen bonding in Salt-2. In addition, the protonated HL 2 molecules interacted with each other through weak C–H···π interactions resulting in the formation of another one-dimensional helical chain.  相似文献   

13.
A new ligand, (2-ethoxy-6-(1H imadazo[4,5-f][1,10]phenanthroline-2-yl)phenol) (HEPIP) and its three Co(III) complexes [Co(phen)2(HEPIP)](ClO4)3 (1), [Co(bpy)2(HEPIP)](ClO4)3 (2) and [Co(dmb)2(HEPIP)](ClO4)3 (3) have been synthesized and characterized. All three Co(III) complexes exhibited antitumor activity against four human tumor cell lines. The interaction of these complexes with calf thymus DNA was studied by absorption and emission spectroscopy, viscosity measurements and DNA cleavage assays. The DNA-binding constants of complexes 1, 2 and 3 were determined as 6.13 × 105, 4.46 × 105 and 3.72 × 105 M?1, respectively. The complexes appear to interact with DNA through intercalation. Studies on the mechanism of photocleavage indicated that both superoxide anion radical and singlet oxygen may play an important role.  相似文献   

14.
(E)-1-[2-Hydroxy-4-(phenylethynyl)phenyl]-3-[4-(phenylethynyl)phenyl]prop-2-en-1-one (1), (E)-1-[2-hydroxy-4-(phenylethynyl)phenyl]-3-phenylprop-2-en-1-one (2), and (E)-1-(2-hydroxyphenyl)-3-[4-(phenylethynyl)phenyl]prop-2-en-1-one (3), which belong to a new class of 2′-hydroxychalcones with phenylethynyl group(s) at the para position of the phenyl ring, were synthesized, and their photochemical properties were investigated. The lowest energy absorption band of 1 peaks at a longer wavelength (383 nm) with a much larger molar extinction coefficient (5.0 × 104 M ?1 cm?1) than that of the parent 2′-hydroxychalcone (2′HC) (2.0 × 104 M ?1 cm?1 at 318 nm). Upon photoexcitation, all three compounds underwent excited-state intramolecular hydrogen atom transfer (ESIHT) to produce an excited tautomer that emitted fluorescence with a large Stokes shift in the longer wavelength region at 600–700 nm. The quantum yield of the tautomer fluorescence of 1 was not high at 298 K (Φ f = 9.1 × 10?5), but was highest among 2′HC and its analogues. The Φ f values of 13 increased 10–30 fold upon reducing the temperature from 298 to 77 K.  相似文献   

15.
Two new coordination polymers, [Pb(IDPT)2(NO3)2] (I) and [Mn(IDPT)(SO4)(H2O)2] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P21/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) Å3, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) Å3, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.  相似文献   

16.
Two DOTA-based proligands bearing a pendant diphenylphosphinamide 4a and 4b were synthesised. Their Eu(III) complexes exhibit sensitised emission when excited at 270 nm via the diphenylphosphinamide chromophore. Hydration states of q = 1.5 were determined from excited state lifetime measurements (Eu.4a $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 2. 1 4 \,{\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 0. 6 4 \,{\text{ms}}^{ - 1} $ ; Eu.4b $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 2. 6 7\, {\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 1. 1 8 \,{\text{ms}}^{ - 1} $ ). In the presence of human serum albumin (HSA) (0.1 mM Eu.4a/b, 0.67 mM HSA, pH 7.4) q = 0.4 for Eu.4a ( $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 1. 3 4\, {\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 0. 7 5\, {\text{ms}}^{ - 1} $ ) and q = 0.6 for Eu.4b ( $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 1. 8 3\, {\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 1.0 5 \,{\text{ms}}^{ - 1} $ ). Relaxivites (pH 7.4, 298 K, 20 MHz) of the Gd(III) complexes in the absence and presence of HSA (0.1 mM Gd.4a/b, 0.67 mM HSA) were: Gd.4a (r 1 = 7.6 mM?1s?1 and r 1 = 11.7 mM?1s?1) and Gd.4b. (r 1 = 7.3 mM?1s?1 and r 1 = 16.0 mM?1s?1). These relatively modest increases in r 1 are consistent with the change in inner-sphere hydration on binding to HSA shown by luminescence measurements on Eu.4a/b. Binding constants for HSA determined by the quenching of luminescence (Eu) and enhancement of relaxivity (Gd) were Eu.4a (27,000 M?1 ± 12%), Eu.4b (32,000 M?1 ± 14%), Gd.4a (21,000 M?1 ± 15%) and Gd.4b (26,000 M?1 ± 15%).  相似文献   

17.
Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis(3-(pyridin-2-yl)-1H-pyrazol-1-yl)ethane (bppe), formulated as [M 2 (N 3 ) 2 (bppe) 2 ](ClO 4 ) 2 (M = Co, 1; Ni, 2; Cu, 3), were successfully synthesized. They were structurally and magnetically characterized. In 1-3, the double azido ions link two adjacent octahedral metal centers together in the end-to-on mode (EO), with the M-N EO -M angles of 99.41°, 100.24° and 99.80°, respectively. The co-ligand bppe acts as terminal ligand to saturate the remaining coordination sites. The magnetic properties of 1-3 have been investigated in the temperature range of 2-300 K. Fitting of the magnetic susceptibility data revealed the occurrence of the strong ferromagnetic interactions [J = 26.32 cm-1 (1), J = 38.23 cm-1 (2) and J = 139.83 cm-1 (3)]. Density functional theory calculations have been performed on 1-3 to provide a magneto-structural correlation of the ferromagnetic behavior.  相似文献   

18.
The geometries, electronic structures, and spectroscopic properties of a series of [Os(II)(CO)3(tfa)(acac(X)2)] (tfa = trifluoroacetate; acac = acetoylacetonate; X = H (1), CF3 (2), C6H5 (3), and C10H7 (4)) complexes have been investigated theoretically. The ground and excited state geometries were optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. The optimized geometry structural parameters agreed well with the corresponding experimental results. As indicated in this paper, the highest occupied molecular orbitals were dominantly localized on the Os atom, ctfa (abbv. of CO and tfa), and acac ligand for 1 and 2, acac ligand and X substituent for 3 and 4, while the lowest unoccupied molecular orbitals were mainly composed of acac ligand and X substituent. Under the time-dependent density functional theory (TDDFT) level with the polarized continuum model (PCM), the absorption and phosphorescence in CH2Cl2 media were calculated based on the optimized ground- and excited-state geometries, respectively. The calculated results show that the lowest energy absorptions at 317 (1), 342 (2), 377 (3), and 420 nm (4) are attributed to a change of ππ*/MLCT mixing transition to pure ππ* transition for 1–4, while their phosphorescence emission have similar transition properties. This indicates that the absorption and emission transition characters could be altered by adjusting the π electron-donating ability.  相似文献   

19.
Quantum mechanical and Rice-Ramsperger-Kassel-Marcus (RRKM) calculations are carried out to study the thermal unimolecular decomposition of oxetane (1), 2-methyloxetane (2), and 2,2-dimethyloxetane (3) at the MPW1PW91/6-311 + G** level of theory. The results of the calculations reveal that decomposition reaction of compounds 1?C3 yields formaldehyde and the corresponding substituted olefin. The predicted high-pressure-limit rate constants for the decomposition compounds 1?C3 are represented as 6.61 × 1013exp(?32472/T), 9.33 × 1013exp(?29873/T), and 4.79 × 1013exp(?27055/T) s?1, respectively. The fall-off pressures for the decomposition of compounds 1?C3 are found to be 9.42 × 10?2, 3.67 × 10?3, and 7.26 × 10?4 mm Hg, respectively. As the fall-off pressure of the decomposition process of compounds 1?C3 are in the following order: P 1/2(1) > P 1/2(2) > P 1/2(3); therefore the decomposition rates are as follow: rate(1) < rate(2) < (3).  相似文献   

20.
Transition metal complexes of 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL), namely [Co(L)2(H2O)4] · 6H2O (I) and [Cu(L)2(H2O)2] · 4H2O (II), have been synthesized by a hydrothermal procedure and characterized by X-ray crystallography, CIF files CCDC nos. 1007524 (I), 1007525 (II). Both I and II are mononuclear molecules. In I, the Co2+ ion is in octahedral coordiantion environment and surrounded by four O atoms from water molecules and two carboxylate O atoms of two deprotonated ligand (L?) occupied six culmination. While in II, the Cu2+ ion is located in a square-planar geometry, bounded to two aqua O atoms and two carboxylate O atoms from L?.  相似文献   

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