Synthesis and Crystal Structure of a New 2D Honeycomb-like Cadmium(II) Complex with Tripodal Ligand

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N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

Single-crystal X-ray structure analyses of N(nPr)₄[B₅O₆(OH)₄][B(OH)₃]₂,1, and N(nBu)₄ [B₅O₆(OH)₄][B(OH)₃]₂,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B₅O₆(OH)₄]^– ionsand B(OH)₃ molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) ₄ ⁺ and N(nBu) ₄ ⁺ ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP2₁/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both¹¹B and¹³C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).     

Two—dimensional Network Crown Ether Complex.Synthesis and Crystal Structure of 18—Crown—6 Complex：[K（18—C—6）]2[Cd—（nmt）2]

The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units.     

两组份互穿网络聚合物的合成研究

以蓖麻油聚氨酯和聚醚聚氨酯的不同重量比与光敏剂、催化剂、稀释剂、促进剂所组成的多相体系为反应物,分别在紫外光照射和加热的条件下合成网络Ⅰ和网络Ⅱ的互穿网络聚合物(IPN)。改变网络Ⅱ聚醚聚氨酯中各组份的摩尔比制得系列样品。红外光谱,应力-应变曲线和动态力学性能测定发现,样品的力学性能与两组份重量比和网络Ⅱ中不同组成都存在着一定关系。这些结果,为该体系IPN的合成和应用提供了一定依据。     

Synthesis and Crystal Structure of [{Cd(hmbdc)(H_2O)_3}·2H_2O]_n

A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc = 5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a = 9.599(3), b = 18.699(5), c = 7.557(2) , β = 108.198(4)°, V = 1288.6(6) 3, Z = 4, Mr = 382.60, Dc = 1.972 g/cm3, F(000) = 760, μ = 1.740, the final R = 0.0555 and wR = 0.0995 for 1732 observed reflections with I > 2σ(I). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.     

Repeatability and pattern recognition of bacterial fatty acid profiles generated by direct mass spectrometric analysis of in situ thermal hydrolysis/methylation of whole cells

Direct CI mass spectrometry profiling of fatty acid methyl esters (FAMEs) from in situ thermal hydrolysis/methylation (THM) of whole bacterial cells with tetramethylammonium hydroxide (TMAH) has been demonstrated as a potential method for real time and fieldable detection/identification of microorganisms. Bacillus anthracis (Ames), Yersinia pestis (Nair. Kenya), Vibrio cholerae (E1 Tor), Brucella melitensis (Abortus wild) and Francisella tularensis (LVS vaccine) were profiled by this method during a 10-month period. Repeatability of the in situ FAME data was calculated using one-way analysis of variance (ANOVA) and a t-test. Artificial neural network (ANN) and multivariate statistics of the FAME profiles were also compared for bacterial identification/classification. Equivalent results were obtained with a multivariate rule building expert system (MuRES) and the ANN. However, the ANN analysis required much less computer time and was deemed the best choice for this application. In situ THM FAME profiles of the bacterial samples provided comparable results with those obtained from the Microbial Identification System (MIDI) (Newark, DE) wet chemistry-gas chromatographic based system.     

Thermodynamic simulation of four-component carnallite type systems

Summary The standard method ofPitzer for predicting the solubility isotherms of systems in which solid phases with a constant composition crystallize is applied to cases when mixed crystals are formed. The four-component carnallite type systems RbCl-CsCl-MgCl₂-H₂O, RbCl-KCl-MgCl₂-H₂O, and RbCl-RbBr-MgCl₂-MgBr₂-H₂O and the corresponding subsystems are thermodynamically simulated at 25°C. It is established that the solubility diagrams consist of crystallization regions of the simple saltsMX,MX, MgX ₂·6H₂O, and MgX₂·6H₂O and of the corresponding carnallite type double salts with the composition 1:1:6. A method of calculation of the integralGibbs energy of mixingG ^mix(s) of crystals formed in water-salt systems has been proposed. The results on the systems RbCl-KCl-H₂O, RbCl-RbBr-H₂O, and MgCl₂-MgBr₂-H₂O are compared with experimental data from the literature and with values calculated using various models.

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Thermodynamische Simulation von Vierkomponentensystemen des Carnallit-Types

Zusammenfassung DiePitzer-Methode zur Voraussage der Löslichkeitsisothermen in Mehrstoffsystemen, in welchen feste Phasen mit konstanter Zusammensetzung auskristallisieren, wurde auch für Fälle angewendet, bei denen sich Mischkristalle bilden. Die Vierstoffsysteme RbCl-CsCl-MgCl₂-H₂O, RbCl-KCl-MgCl₂-H₂O und RbCl-RbBr-MgCl₂-MgBr₂-H₂O, aus welchen Carnallit-Typ-Mischkristalle auskristallisieren, und die dazugehörigen Dreistoff-Randsysteme wurden bei 25°C simuliert. Man stellt fest, daß die Löslichkeitsdiagramme sowohl Kristallisationsbereiche der einfachen SalzeMX,M'X, MgX ₂·6H₂O und MgX ₂·6H₂O als auch der entsprechenden carnallitartigen Doppelsalze mit der Zuzammensetzung 1:1:6 umfassen. Eine Methode zur Berechnung derGibbs-EnergieG ^mix(s) für die in Wasser-Salz-Systemen gebildeten Mischkristalle wird vorgeschlagen. Die für die Systeme RbCl-KCl-H₂O, RbCl-RbBr-H₂O und MgCl₂-MgBr₂-H₂O erhaltenen Ergebnisse werden mit experimentellen Literaturdaten und Resultaten von Berechnungen aufgrund verschiedener Modelle verglichen.

     

Preparation of a Star Network PEG-based Gel Polymer Electrolyte and Its Application to Electrochromic Devices

A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ^1H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83 × 10 ^-4 S·cm^-1 at room temperature. Thermogravimetry （TG） of the polymer electrolyte showed that the thermal stability was up to at least 150 ℃. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochrornic devices.     

Synthesis, crystal structure and properties of the Cu complex of a tetradentate imidazole-functionalized diazamesocyclic ligand, 1,4-bis(N-1-methylimidazol-2-yl-methyl)-1,4-diazacycloheptane

A new potential tetradentate ligand, 1,4-bis(N-1-methylimidazol-2-ylmethyl)-1,4-diazacycloheptane (l), together with its Cu^II complex [CulCl]ClO₄ (1), has been reported. The crystal structure of 1, determined by single-crystal X-ray analysis, shows that it is in chiral P2₁2₁2₁ space group. The Cu^II centre is penta-coordinated in square pyramidal geometry and the diazacycloheptane (DACH) ring adopts normal boat configuration. The most striking feature of this complex is the formation of a 3D network bridged through the C-H?Cl hydrogen bonds with the perchlorate anions in the cavities, and stabilized via π-π stacking interactions along the a-direction. The solution behaviour of 1 has been further investigated by UV/Vis and ESR techniques.