On an Expression of Extraction Constants without the Interfacial Equilibrium-Potential Differences for the Extraction of Univalent and Divalent Metal Picrates by Crown Ethers into 1,2-Dichloroethane and Nitrobenzene

An idea on interfacial equilibrium-potential differences () which are generated for the extraction of univalent metal picrate (MPic) and divalent ones (MPic2) by crown ethers (L) into high-polar diluents was improved. These potentials were clarified with some experimental extraction-data reported before on the M = Ag(I), Ca(II), Sr(II) and Ba(II) extraction with 18-crown-6 ether (18C6) and benzo-18C6 into 1,2-dichloroethane (DCE) and nitrobenzene (NB). Consequently, it was demonstrated that the? values from the extraction-experimentally obtained logKD,Pic ones are in agreement with or close to those calculated from charge balance equations in many cases, where the symbol, KD,Pic, denotes an individual distribution constant of Pic﹣ into the DCE or NB phase. Also, it was experimentally shown that extraction constants based on the overall extraction equilibria do not virtually contain the? terms in their functional expressions.

Spectral Properties of Extracted Complexes of MetalPicrates with Crown Ethers

The investigation on UV-visible spectra of species formed by extracting some metal picrates with benzo-15-crown-5(B15C5) and dibenzo-18-crown-6(DB18C6) verified that there are some interactions of picrate anion with K+, Na+ and rare earth ions in loaded organic phase. By the study of the charge transfer band and absorption spectra of picrate anion, it can be determined whether an ion pair has been formed and either a 1 : 1 contact ion pair or a 1 : 2 crown-separated ion pair involved in organic phase can be distinguished for an ion-pair extraction.

An Electrochemical Understanding of Extraction of Silver Picrate by Benzo-3<i>m</i>-Crown-<i>m</i>Ethers (<i>m</i>= 5, 6) into 1,2-Dichloroethane and Dichloromethane

Two extraction constants (Kex± and Kex) for extraction of silver picrate (Ag﹢Pic﹣) by benzo-15-crown-5 ether (B15C5) and benzo-18-crown-6 one (B18C6) into 1,2-dichloroethane (DCE) and dichloromethane (DCM) were determined at 298 K and given values of ionic strength. Here, Kex± and Kex were expressed as [AgL﹢]o[Pic﹣]o/[Ag﹢][L]o[Pic﹣] and [AgLPic]o/[Ag﹢][L]o[Pic﹣], respectively: L symbolizes B15C5 or B18C6 and the subscript “o” denotes the organic phase composed of DCE or DCM. Individual distribution constants (KD,Pic) of picrate ion, Pic﹣, into the two diluents were also determined with the determination of Kex. From comparison of these KD,Pic values with those standardized, interfacial potential differences () at extraction equilibria were evaluated. Then, using these values, relations of the experimentally-determined logKex± or logKex values with their electrochemically-standardized ones were precisely discussed. Consequently, it was indicated that logKex± should be expressed as a function of .

Comparative Spectroscopic Studies on Pure, 10 and 50 mol% Glycine Mixed L-Valinium Picrate Crystals

Nonlinear optical crystals of pure, 10 and 50 mol% glycine mixed L-valinium picrate have been grown from saturated aqueous solution by slow evaporation method at a temperature of 36℃ using a constant temperature bath of accuracy of ±0.01℃. The synthesized organic optical material has been purified by repeated recrystallization. The cell parameters were calculated using single crystal X-ray diffraction technique which confirmed the crystal system. Optical behavior was examined by UV-Vis-NIR spectrometer in the range from 190 nm to 1100 nm, which revealed the absence of absorption in the entire visible region. Functional groups and modes of vibration were identified by FT-IR spectrometer in the range between 400 cm-1 and 4000 cm-1. The 1H- and 13C NMR spectra of grown crystals were recorded using D2O as solvent on a Bruker 300 MHz (Ultrashield) TM instrument at 23℃ (300 MHz for 1H NMR and 75 MHz for 13C NMR) to confirm the molecular structure. The second harmonic generation conversion efficiency was investigated by Kurtz powder method using Nd: YAG laser as a source to explore the NLO characteristics.

The Mixed LB film of Crowned Phthalocyanine and Picrate

The mixed LB film of mono crown ether substituted phthalocyanine (CPc) and potassium picrate (PiK) were prepared by adding potassium picrate in subphase. The pi-A isotherms show that the addition of PiK in subphase increases the orientation angles of phthalocyanine in monolayers. The absorption spectra revealed that the monolayer can be transferred to substrates easily. X-ray diffraction results show that the mixed film possesses the same thickness as that of pure phthalocyanine film.

Synthesis and spectroscopic properties of rare earth picrate complexes with a new dinaphthalenelamide

The new ligand N-benzyl-2-{2’-[(benzyl-ethyl-carbamoyl)-methoxy]-dinaphthalene-2-yloxy}-N-ethyl-acetamide(L) and its complexes of rare earth picrates were synthesized.The complexes were characterized by elemental analysis,IR,UV-vis spectra and conductivity measurements.The fluorescence properties of the europium complex in solid state and CHCl3,ethyl acetone,acetonitrile and DMF were investigated.Under the excitation,the europium complex exhibited characteristic emissions of europium.The lowest triplet state energy level of the ligand indicated that the triplet state energy level of the ligand matched better to the resonance level of Eu(Ⅲ) than Tb(Ⅲ) ion.

Crystal structures of the complexes of rare earth picrates with N, N, N', N'-tetraphenyl-3, 6-dioxaoctanediamide

The complexes of rare earth picrate with N,N,N’,N’-tetraphenyl-3,6-dioxaoctanediamide(TDD),Eu(picc(TDD)] 2CH3CN and [ Y(pic)3(TDD)],have been synthesized.The crystal structures reveal that TDD at is as n tetradentate ligand,forming a ring-like coordination structure with its oxygen atoms together with one oxygen atom of the bidentate pterate In the Eu(Ⅲ) complex,the europium ion with a larger ionic radius lies out of the ring,while in the Y(Ⅲ) complex,the yttrium ion with a smaller ionic radius enters the cavity of the ligand.The structures of the complexes are greatly affected by the ionic radii due to participation of the picrates in coordination.

Synthesis of New Aza-crown Ethers Containing Pyridine Ring and their Liquid Membrane Transport of Alkali Cations

Five new aza-crown ethers have been prepared by the condensation of 2,6-bis[(2-formylphenyl)oxymethyl] pyridine with different diamino compounds in hot methanol, the bis-Schiff bases without isolation were reduced with NaBH4 to afford the corresponding aza-crown ethers. The liquid membrane transport or alkali cations using the five new macrocycles as the ion-carriers was also studied.

Crystal Structure and Spectroscopic Properties of [Ni(phen)_3]Pic_2·2CH_3CN

The crystal structure of the title complex having the stoichiometric formula [Ni\|(phen) 3]Pic 2·2CH 3CN (Pic=picrate anion; phen=1,10\|phenanthroline) has been determined by single-crystal X-ray diffraction. The crystal (C 52 H 34 N 14 O 14 Ni, M r=1137.63) belongs to the triclinic system, space group P1(#2) with the following crystallographic parameters: a = 14\^130(1), b=15\^256(3), c=13.673(2); α=109.11(1), β =90.92(4), γ=66.75(3)°; V=2537\^72 3, D c=1.489g/cm 3, μ(MoKα)=4.66cm -1 , F(000)=1168, Z=2, and final R=0.062 and R w=0.078 for 4917 observed reflections (I>2.00σ(I)). The analytical results of crystal structure and spectroscopic properties show that nickel(II) cation coordination environment is a distorted octahedral geometry, the Ni 2+ ion is coordinated with six nitrogen atoms~ of three phen directly, while two picrate anions and two acetonitrile molecules do not take part in coordination~.

Detection of Oxidized Ferrocenes by LC-MS with Electrospray Ionization Using Picric Acid as the Counter Ion

Ferrocene is an organometallic compound that readily undergoes oxidation in atmosphere under acidic conditions. However, because of its diamagnetic nature, ferrocene does not lend itself to structural analysis by nuclear magnetic resonance (NMR) spectroscopy. In this work, the oxidation of ferrocene and several of its derivatives were analyzed by liquid chromatography-mass spectrometry (LC-MS). An electrospray ionization (ESI) source was used, with picrate serving as the counter ion. This method is particularly effective for studying oxidation of ferrocenes because their reactivity toward oxygen under ambient conditions is low.

Calix[4]crowns with Methoxynaphthoylmethyl Pendant Groups

The novel calixcrowns with two pendant groups were prepared by the alkylation of calixcrowns with 6-methoxy-2-bromoacetylnaphthalene. 1H NMR titration and picrate extraction experiments indicated that they exhibit higher complexing efficiency than their parent compounds and possess obvious selectivity for Na + or K +, respetively, and that the cation is encapsulated inside the preorganized ionophoric cavity defined by carbonyl oxygens, the crown ether and the phenoxy oxygens. From UV and fluorescent spectra it is revealed that calix-crown-4 3a with 6-methoxy-2-naphthoylmethyl pedant groups exhibits remarkable cation-induced photophysical effects and it could be utilized as a selective fluorescent sensor for Ca 2+ .