Consequences of an algorithm for bridged graphs

Chepoi showed that every breadth first search of a bridged graph produces a cop-win ordering of the graph. We note here that Chepoi's proof gives a simple proof of the theorem that G is bridged if and only if G is cop-win and has no induced cycle of length four or five, and that this characterization together with Chepoi's proof reduces the time complexity of bridged graph recognition. Specifically, we show that bridged graph recognition is equivalent to (C₄,C₅)-free graph recognition, and reduce the best known time complexity from O(n⁴) to O(n^3.376).     

苯二甲酰基桥联铁硫配合物［（μ－RS）Fe_2（CO）_6］_2（μ－OCC_6

通过由Ｆｅ３（ＣＯ）１２、ＲＳＨ和Ｅｔ３Ｎ所形成的［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］Ｅｔ３ＮＨ于室温下分别与对或间苯二甲酰氯的原位反应，首次合成６个结构新颖的苯二甲酰基桥联铁硫配合物［（μ－ＲＳ）·Ｆｅ２（ＣＯ）６］２（μ－ｐ－ＯＣＣ６Ｈ４ＣＯ－ｐ－μ）（Ｒ＝Ｅｔ，ｎ－Ｂｕ，ｔ－Ｂｕ）以及［（μ－ＲＳ）Ｆｅ２（ＣＯ）６］２（μ－ｍ－ＯＣＣ６Ｈ４ＣＯ－ｍ－μ）（Ｒ＝ｎ－Ｐｒ，ｎ－Ｂｕ，ｔ－Ｂｕ）。经元素分析、ＩＲ光谱及１ＨＮＭＲ表征了它们的结构，并讨论了产物的生成过程。此外，还提出了合成对苯二甲酰氯的一种新方法。     

New aspects of the protonation of biliverdins

Biliverdins undergo appreciable self association in acidic solutions especially if solvents like benzene or chloroform are employed. The population of aggregates further depends on the concentration of both the acid and the solute. In chloroform and benzene solutions at high acidity a doubly protonated species is formed. This is concluded from a combinatory evaluation of the CD and electronic absorption spectra of chiral optically active biliverdins (1–6) in benzene, chloroform, and ethanol solutions containing trifluoroacetic acid or hydrochloric acid. The aggregates formed at medium acid concentrations exhibit largeCotton effects in the long-wavelength absorption bands and thus dominate the CD spectra. Similarly, agrregates are the main contributors to theCotton effects of achiral, protonated biliverdins in (S)-(–)-ethyl lactate (SICD) at usual concentrations. The consequence and relevance of these findings with regard to the recent literature is briefly discussed.Dedicated to Prof. Dr.Karl Schlögl on occasion of his 60^th birthday.     

桥联双（甲巯咪唑）化合物的合成和配位性能

研究了桥联双(甲巯咪唑)化合物(Ⅰ_a—Ⅳ_a、Ⅰ_b)的合成和配位性能。UV谱显示Ⅰ_a—Ⅳ_a与UO_2~(2+)离子(硬酸)配位,溶液中形成3:1的配合物。Ⅰ_b与Hg~(2+)、Au~(3+)离子(软酸)配位形成2:1的配合物,用CNDO/2方法计算了各配体分子中原子净电荷密度和HOMO、LUMO能量。     

Crystal and molecular structures of binuclear caesium complexes with 1,3-calix[4]-bis-crown-6 and 1,3-calix[4]-bis-benzo-crown-6

The crystal structures of two binuclear complexes between caesium and 1,3-calix[4]-bis-crowns have been determined. Cs₂ Bis-benzoC6(NO₃)₂. 3CHCl₃ (1) in whichBis-benzoC6 is 1,3-calix[4]-bis-benzo-crown-6, crystallizes in the orthorhombic system: space groupPca2 ₁ a=19.513(10),b=15.382(5),c=23.708(9) Å,V=7116(5) ų,Z=4. Refinement led to a final conventionalR value of 0.065 for 2321 reflections. The structure of (1) is analogous to those already reported withBis-C6, (in whichBis-C6 is, 1,3-calix[4]-bis-crown-6) and NO ₃ ^– as a counter-ion. Cs₂ Bis-C6(NCS)₂ (2) crystallizes in the monoclinic system: space, groupC2 a=36.57(2),b=11.47(1),c=13.65(1) Å, =109.03(5)°.,V=5415(6) ų,Z=4. Refinement led to a final conventionalR value of 0.063 for 2227 reflections. Compound (2) is made of dimers bridged by a disordered NCS^– ion. The crown ether chain conformations are discussed. Supplementary data relating to this article (atomic coordinates, anisotropic displacement parameters, bond distances and angles and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82199 (52 pages).     

Synthesis and Structural Characterization of a New Cadmium(Ⅱ) Complex Bridged by Endo-norbornene-cis-5,6-dicarboxylic Acid

A polynuclear complex [Cd(endc)(H2O)]n·nH2O (endc = endo-norbomene-cis5,6-dicarboxylate anion) has been synthesized by the hydrothermal reaction of cadmium nitrate tetrahydrate with endo-norbomene-cis-5,6-dicarboxylic acid in 1:1 molar ratio,and structurally characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a = 1.16471(7),b = 0.95334(7),c = 0.91109(9) nm,Z = 4,V= 1.01035(14)nm3,Dc.= 2.160 g/cm3,μ= 2.172 mm-1,F(000) = 648,R =0.0302 and wR = 0.0752.According to structural analysis,each Cd(Ⅱ) ion is coordinated to six O atoms from three endc anions and one water molecule,giving a distorted octahedral geometry.Two- dimensional layer arrangement of the title complex is constructed from the bridging nature of endc.It is worth notice that adjacent two-dimensional layers are joined together to form a three-dimensional supramolecular framework via intermolecular hydrogen bonding interactions.     

Bis(<Emphasis Type="Italic">β</Emphasis>-cyclodextrin)s Linked with an Aromatic Diamine as Fluorescent Sensor for the Molecular Recognition of Bile Salts

The binding behavior of three aromatic diamino-bridged bis(β-cyclodextrin)s (2–4) with four bile salts {cholate (CA), deoxycholate (DCA), glycocholate (GCA) and taurocholate (TCA)} has been investigated at 25 °C in a phosphate buffer (pH=7.20) by fluorescence and 2D NMR spectroscopy. The results indicate that these bis(β-cyclodextrin)s act as fluorescent sensors. From the ROESY spectra, it is deduced that the phenyl moieties of bis(β-cyclodextrin)s 2–4 are partially self included in the cyclodextrin cavity, and are not expelled from the cavity upon complexation with bile guests. Owing to the cooperative host-tether-guest binding mode in which the linker and guest are co-included in the two cyclodextrin cavities, these bis(β-cyclodextrin)s significantly enhance the binding ability and selectivity as compared with the native β-cyclodextrin 1. Possessing suitable tether length, bis(β-cyclodextrin) 3 gives the highest K _S values, ranging up to 39,900 mol⋅L⁻¹, for complexation with CA. The complex stability constants are discussed from the viewpoint of multiple recognitions between host and guest.     

Synthesis of an unsymmetrically doubly bridged calix[4]arene in the 1,3-alternate conformation

We report the synthesis of the first calix[4]arene constrained to a 1,3-alternate conformation by one crown ether and one di-aza-benzo crown ether bridgings. Preliminary binding properties are also given.     

Bridged silsesquioxanes containing a chiral diphosphine substructure. Catalytic properties in asymmetric hydrogenation

Bridged silsesquioxanes with asymmetric catalytic properties are described. These new silica-based materials are obtained by the sol-gel hydrolysis of an organosilylated chiral compound bearing rhodium-complexed diphosphine ligands. The incorporation of the organometallic species in various hybrid networks was achieved upon co-hydrolysis of the latter silylated ligands with TEOS or with 1,4-bis(trimethoxysilyl)benzene. These amorphous hybrids have been tested as enantioselective catalysts for the hydrogenation of (Z)α-(acetamido)cinnamic acid to the corresponding aminoacid and the results were compared with that obtained from the complexed precursor in homogeneous medium and related grafted silica. Enantioselectivities slightly higher than for homogeneous reaction were obtained in the case of the heterogeneous catalysts prepared by the direct hydrolysis of the rhodium-complexed diphosphine compound or by its co-hydrolysis with 1,4-bis(trimethoxysilyl)benzene. Conversely, a significant decrease in selectivity was observed when the organometallic species was immobilised in silica or grafted at the surface of silica.     

Copper(II) complexes of thioarylazo-pentanedione: Structures,magnetism, redox properties and correlation with DFT calculations

Copper(II) complexes of 3-((2-(alkylthio)phenylazo)-2,4-pentanedione, tridentate O, N, S donor ligands, are described in this work. Chloride bridged copper(II) polymers (1) and thiocyanato bridged copper(II) dimmers (2) are characterized by a single crystal X-ray diffraction study. The complexes show antiferromagnetic interactions, with J = −0.5 ± 0.1 cm⁻¹ (1a) and −25.8 ± 0.5 cm⁻¹ (2b), which implies stronger coupling in the –SCN-bridging compound. The spectra, redox and magnetism are explained by DFT studies.