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PubMed2006

Synthesis and characterization of novel oxo-centered phosphanylzincates of potassium and cesium with a central Zn6O2P4 double-heterocubane cage.

The hydrolysis reaction of K(2)(MeZn)(2)(PSitBu(3))(2) in THF/toluene solution yields the [(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)](4-) anions independent of the applied stoichiometry. If the applied molar ratio resembles the composition of the anion, [(thf)K](2)[(eta(6)-toluene)K](2)[(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)] (1) crystallizes from a mixture of THF and toluene. In the case with less water, a phosphanediylzincate moiety is bonded to this anion, and [Zn(PSitBu(3))(2)K(4)(thf)(6)](2)[(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)] (2) crystallizes. However, again the major product is 1. The same anion is also observed with larger and softer cations, and [(thf)(3)Cs(2)](2)[(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)] (3) is obtained if the cesium zincate is used in this reaction. In all of these compounds, the anion is a slightly distorted Zn(6)O(2)P(4) double-heterocubane cage with a central Zn(2)O(2) ring having Zn-O bond lengths of approximately 207 pm.

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PubMed1997

Preparation of Cesium Trithionate by the Ultrasonic Reaction of CsF with SO(2).

Cesium fluoride reacts with SO(2) under an ultrasonic treatment, with the formation of Cs(2)S(3)O(6) and SO(2)F(2) instead of CsSO(2)F. The trithionate salt crystallizes with one solvent molecule (Cs(2)S(3)O(6).SO(2)) in the monoclinic space group P2(1)/c with a = 9.702(3) Å, b = 15.315(6) Å, c = 7.558(4) Å, beta = 97.17(4) degrees, and 4 formula units per unit cell. The reaction route for the CsF/SO(2) system is discussed with regard to the activation or reactivation of CsF as catalyst.

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PubMed2000

Preparation, characterization, X-ray crystal structure, and energetics of cesium 5-cyano-1,2,3,4-tetrazolate: Cs[NCCNNNN].

Cesium 5-cyano-1,2,3,4-tetrazolate, Cs[NCCNNNN] (Cs1), was prepared in 100% yield by a 3 + 2 cycloaddition reaction of CsN3 and (CN)2 in SO2. Cs1 forms monoclinic crystals (a = 8.297(2) A, b = 11.040(3) A, c = 6.983(2) A, beta = 120.31(2) degrees, space group C2/c, Z = 4, R1 = 0.048, wR2 = 0.120 for 1217 independent reflections). Cs1 is best described as a three-dimensional array of cations and anions connected by weak Cs(+)-N delta- contacts. The cations and anions each form a diamond-type lattice (tetrahedral arrangement of ions) with the counterions lying in hexagonal channels running parallel to the c-axis. The anions in the channels form stacks with the CN groups pointing in opposite directions in adjacent layers. The calculated (RB3PW91/6-311 + G*) geometry of 1 is in agreement with the X-ray crystal structure, and the calculated vibrational spectrum is in good agreement with the observed FT-IR and FT-Raman spectra. The lattice enthalpies and heats of formation of M1 (M = Cs, K) as well as the enthalpy of formation from MN3(s) and (CN)2(g) were estimated. The 13C and 14N NMR spectra of Cs1 are also reported. The ionization potential (450.7 kJ mol) and electron affinity (427.4 kJ/mol) of 1 were calculated. Attempts to oxidize 1 with AsF5 led to the formation of Cs1.xAsF5 (x approximately 2). The 7 pi dianion [NCCNNNN].2- is calculated to be a stable entity in the gas phase, but Cs(2)1 is estimated to be unstable with respect to dissociation to 2 CsCN and 3/2 N2 (delta Hdiss = -132.4 kJ/mol). The preparation of the potassium salt of 1 and the corresponding thermodynamic quantities are reported.

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PubMed2000

Unusual ligand coordination for cesium.

When complexed by tetrabenzo-24-crown-8, the cesium ion can accommodate unprecedented ligation. The structures of the following complexes are presented. [Cs(tetrabenzo-24-crown-8)(eta 1-NCMe)2(eta 2-NCMe)][NO3] (1): triclinic P1, a = 12.0119(14) A, b = 13.3680(15) A, c = 13.7859(12) A, alpha = 89.124(8) degrees, beta = 66.928(9) degrees, gamma = 71.536(10) degrees, V = 1916.7(4) A3, Z = 2. [Cs(tetrabenzo-24-crown-8)(eta 1-NCMe)2(eta 2-CH2Cl2)][NO3] (2): triclinic, P1, a = 12.295(3) A, b = 13.295(3) A, c = 13.782(3) A, alpha = 89.105(17) degrees, beta = 66.096(18) degrees, gamma = 71.980(19) degrees, V = 1929.5(8) A3, Z = 2. These structures are the first reported examples of linear eta 2-acetonitrile coordination to any metal ion and the first structures illustrating eta 2-acetonitrile and dichloromethane ligation to an alkali metal ion. Possible steric and electronic origins of these unusual metal-ligand interactions are discussed.

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PubMed2001

Photoinduced ferrimagnetic systems in Prussian blue analogues C(I)xCo4[Fe(CN)6]y (C(I) = alkali cation). 3. Control of the photo- and thermally induced electron transfer by the [Fe(CN)6] vacancies in cesium derivatives.

We synthesized a series of CoFe Prussian blue analogues along which we tuned the amount of cesium cations inserted in the tetrahedral sites of the structure. Structure and electronic structure have been investigated, combining XANES, infrared spectroscopy, powder X-ray diffraction experiments, and magnetization measurements. The change of the magnetization induced by light along the series shows that the efficiency of the photoinduced magnetization, evidenced a few years ago in similar compounds by Hashimoto et al. (Sato, O.; Iyoda, T.; Fujishima, A.; Hashimoto, K. Science 1996, 272, 704-705; Sato, O.; Einaga, Y.; Iyoda, T.; Fujishima, A.; Hashimoto, K. J. Electrochem. Soc. 1997, 144, L11-L13; Sato, O.; Einaga, Y.; Iyoda, T.; Fujishima, A.; Hashimoto, K. J. Phys. Chem. B 1997, 101, 3903-3905; Einaga, Y.; Ohkoshi, S.-I.; Sato, O.; Fujishima, A.; Hashimoto, K. Chem. Lett. 1998, 585-586; and Sato, O.; Einaga, Y.; Fujishima, A.; Hashimoto, K. Inorg. Chem. 1999, 38, 4405-4412), depends on a compromise between the number of excitable diamagnetic pairs and the amount of [Fe(CN)6] vacancies giving the network flexibility. Besides the efficiency of the photoinduced process, the amount of [Fe(CN)6] vacancies also controls a thermally induced electron transfer.

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PubMed2005

Observation of an Fe(II) spin-crossover in a cesium iron hexacyanochromate.

In this work, we observed a spin-crossover phenomenon in a cesium iron hexacyanochromate, which is a Prussian blue analogue. This compound showed a thermal phase transition with transition temperatures of 211 K (T1/2 downward arrow) and 238 K (T1/2 upward arrow) due to a spin-crossover on FeII sites. This spin-crossover phase transition is accompanied by a lattice contraction of 0.38 A, but maintains a face-centered cubic structure (F3m). This is the first observation of FeII spin-crossover in a series of Prussian blue analogues.

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PubMed2004

A novel and highly efficient synthetic route to unsymmetrical organoselenides using cesium bases.

A new and convenient one-pot method for the preparation of unsymmetrical selenides has been developed. In the presence of cesium hydroxide, molecular sieves, and DMF, benzeneselenol undergoes direct alkylation with various alkyl halides for the synthesis of alkyl phenyl selenides in moderate to excellent yields. Another method to prepare unsymmetrical organoselenides was also completed by coupling terminal alkynes with benzeneselenyl bromide. As an application, the synthesis of a selenopeptide was also accomplished. Furthermore, this methodology was extended to the synthesis of an organoselenide on solid support.

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PubMed1999

Aggregation and Alkylation of the Cesium Enolate of 2-p-Biphenylylcyclohexanone(1).

The cesium enolate of 2-biphenylylcyclohexanone (CsBPCH), generated by deprotonation of 2-biphenylylcyclohexanone with diphenylmethylcesium, is shown to be a mixture of monomer and dimer in THF, with a dimerization constant of 1.9 x 10(3) M(-)(1). The ion pair acidity corresponds to pK = 19.30 +/- 0.05. Even in the presence of excess dimer, only monomeric CsBPCH is found to react with methyl tosylate (MeOTs), methyl p-bromobenzenesulfonate (MeOBs), hexyl tosylate (HexOTs), hexyl bromide (HexBr) and p-tert-butylbenzyl chloride (BBCl). The relative reactivities of these alkylating reagents toward monomeric CsBPCH are BBCl, 1.00; MeOTs, 1.21; MeOBs 6.7; HexBr, 0.10; HexOTs, 0.050. CsBPh(4) has essentially no effect on the rates.

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PubMed2006

Aggregation of cesium perfluorooctanoate on poly(ethylene glycol) oligomers in water.

The interaction of cesium perfluorooctanoate (CsPFO) with poly(ethylene glycol) (PEG) of different molecular weight (300 < or = MW < or = 20000 Da) has been investigated at 298.15 K by isothermal titration calorimetry (ITC), density, viscosity, and conductivity measurements. Calorimetric titrations exhibited peculiar trends analogous to those already observed for sodium dodecyl sulfate (SDS). Micelles of the perfluorosurfactant, as compared to those of SDS, yield complexes with the polymer of similar thermodynamic stability but are able to interact with shorter PEG oligomers. The average number of surfactant molecules bonded per polymer chain at the saturation is about twice that observed for SDS. ITC data at 308.15 K indicate a larger thermodynamic stability of the aggregates but an almost constant stoichiometry. The peculiar thermal effects and the viscosity trend observed during the titration of an aqueous PEG solution with the surfactant appear consistent with a conformational change of the polymer. The PEG chain would evolve from a strained to an expanded conformation, induced by the growing of the surfactant micellar clusters bonded to the polymer, as suggested in a previous study of the PEG/SDS/H2O system.

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PubMed2000

Comparative analysis of the low molecular weight and enzymatic antioxidants in response to the phototoxicity of accumulating uroporphyrin and protochlorophyllide in barley leaves treated with cesium chloride.

Cesium chloride treatment of illuminated barley leaves leads to accumulation of uroporphyrinogen which is subsequently either oxidised to uroporphyrin in continuous light or converted to protochlorophyllide in darkness [Shalygo et al. (1998) J Photochem Photobiol 42: 151-158]. We were interested to elucidate the differences in the phototoxicity of uroporphyrin and protochlorophyllide in the CsCI-treated leaves. Photosensitization and the induction of oxidative stress responses in the barley leaves occurred much faster upon protochlorophyllide than upon uroporphyrin accumulation. We compared the time resolved changes in the pool sizes of low molecular weight antioxidants, such as ascorbate, glutathione and tocopherol, as well as of the enzymatic activities of catalase, ascorbate peroxidase, glutathione reductase and superoxide dismutase in illuminated barley leaves which accumulated uroporphyrin or protochlorophyllide. A rapid loss of the antioxidant levels correlated with the accumulation of reactive oxygen species. The contents of low molecular weight antioxidants and the activities of most of the antioxidative enzymes declined more rapidly in the presence of protochlorophyllide than of uroporphyrin. Due to its high lipophilicity, free protochlorophyllide is associated with biomembranes. Therefore, it is assumed that it exerts its phototoxic effects to membranes more rapidly than uroporphyrin.

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PubMed2004

Aqua dissociation nature of cesium hydroxide.

To understand the mechanism of aqueous base dissociation chemistry, the ionic dissociation of cesium-hydroxide in water clusters is examined using density functional theory and ab initio calculations. In this study, we report hydrated structures, stabilities, thermodynamic quantities, dissociation energies, infrared spectra, and electronic properties of CsOH(H(2)O)(n=0-4). With the addition of water molecules, the Cs-OH bond lengthened significantly from 2.46 A for n=1 to 3.08 A for n=4, which causes redshift in Cs-O stretching frequency. It is found that three water molecules are needed for the dissociation of Cs-OH, in contrast to the case of strong acid dissociation which requires at least four water molecules. However, the dissociation for n=3 could be considered as incomplete because a very weak CS em leader OH stretch mode is still present, while that for n=4 is complete since the Cs em leader OH mode no longer exists. This study can be related with hydration chemistry of cations and anions, and extended into the intra- and intercharge-transfer phenomena.

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PubMed2005

First-principles study of the adsorption of cesium on Si(001)(2 x 1) surface.

First-principles calculations based on density functional theory-generalized gradient approximation method have been performed on cesium adsorption on Si(001)(2 x 1) surface. The optimized geometries and adsorption energies have been obtained and the preferred binding sites have been determined for the coverage (Theta) of one monolayer and half a monolayer. At Theta = 0.5 ML the most stable adsorption site is shown to be T3 site. At Theta = 1 ML two Cs atoms are adsorbed at HH and T3 sites, respectively. It was found that the saturation coverage of Cs for the Si(001)(2 x 1)-Cs surface is one monolayer instead of half a monolayer. This finding supports the majority of experimental observations but does not support recent coaxial impact collision ion scattering spectroscopy investigations [Surf. Sci. 531, L340 (2003)] and He(+) Rutherford backscattering spectroscopy studies [Phys. Rev. B 62, 4545 (2000)]. Mulliken charge and overlap population analysis showed that the Cs-Si bond is indeed ionic rather than polarized covalent as generally assumed for alkali metal (AM) on Si(001)(2 x 1) surface. Geometrical structure analysis seems to have limitations in determining the nature of AM-substrate bond. We also found that the silicon surface is metallic and semiconducting for the coverages of 0.5 and 1 ML, respectively.

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PubMed2000

Equilibrium Chemistry in a Brown Dwarf's Atmosphere: Cesium in Gliese 229B.

The distribution of Cs in Gliese 229B's atmosphere reveals how equilibrium chemistry establishes the atmospheric composition. The rapid kinetics of cesium chemistry keeps the Cs abundance in thermochemical equilibrium and renders Cs a sensitive measure of chemical processes in brown dwarf atmospheres. Observations of Gliese 229B indicate a subsolar bulk abundance of Cs, the depletion of alkali metals in the upper atmosphere from condensation, and a partitioning of heavy elements different from that of the Sun.

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PubMed2001

Nature of the liquid crystalline phase transitions in the cesium pentadecafluorooctanoate (CsPFO)-water system: the nematic-to-isotropic transition.

Deuterium NMR spectroscopy of 2H2O has been used to monitor the magnetic-field-induced order on approaching a transition to a nematic phase in isotropic solutions of disklike micelles of cesium pentadecafluorooctanoate. Highly accurate data on the phase boundaries and spinodals have been obtained for solutions with volume fraction concentration straight phi between 0.078 and 0.201. The quantity TIN-T*, where T* is the spinodal limit of the isotropic phase and TIN is the temperature at which the nematic phase first appears on cooling, decreases linearly with decreasing concentration, extrapolating to zero only at zero concentration. Thus, there is no evidence to support the presence of a Landau point along the transition line as has previously been conjectured. The values for (TIN-T*)/TIN are in the range 10(-5)-10(-4), up to two orders of magnitude smaller than corresponding values reported for calamitic thermotropic nematics. The transition gap (phiNI-phiIN)/phiIN approximately 0.33% for phi<0.20 is also very small, although finite as required for a first-order phase transition. These data, when combined with previously measured properties, present an intriguing picture of the isotropic-to-nematic phase transition in a paradigmatic system of self-assembled diskotic particles. However, it is not completely clear, within the context of current theoretical understanding, whether the behavior of this system is explicable by hard-particle models, or if the self-assembly plays a crucial role in weakening the phase transition.

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