Syntheses and Crystal Structures of Ammoniates with the Phenyl‐Substituted Polytin Anions Sn2Ph$\rm{_{\bf 4}^{{\bf 2} - } }$, cyclo‐Sn4Ph$\rm{_{\bf 4}^{{\bf 4} - } }$, and Sn6Ph$\rm{_{{\bf 12}}^{{\bf 2} - } }$

The reaction of diphenyltin dichloride with the binary Zintl phase K₄Sn₉ in the presence of excess lithium and 18‐crown‐6 in liquid ammonia led to the ammoniate [K(18‐crown‐6)(NH₃)₂]₂Sn₂Ph₄ ( 1 ). The analogous reaction with K₄Ge₉ and potassium in the absence of further alkali metal ligands resulted in the compound [K₂(NH₃)₁₂]Sn₆Ph₁₂ ? 4 NH₃ ( 3 ). Cs₆[Sn₄Ph₄](NH₂)₂ ? 8 NH₃ ( 2 ) was prepared by reacting diphenyltin dichloride with a surplus of caesium in liquid ammonia. The low‐temperature single‐crystal structure determinations show all compounds to contain phenyl‐substituted polyanions of tin. Compound 1 is built from Sn₂Ph anions consisting of Sn dumbbells with two Ph substituents at each Sn‐atom. Compound 2 contains cyclo‐Sn₄Ph anions formed by a four‐membered tin ring in butterfly conformation with one Ph substituent at each Sn‐atom in an (all‐trans)‐configuration. Sn₆Ph in 3 is a zig‐zag Sn₆ chain with two substituents at each of the Sn‐atoms. Both 1 and 3 have molecular counter cations, in the latter case the unprecedented dinuclear potassiumammine complex [K₂(NH₃)₁₂]²⁺ is observed. Compound 2 shows a complicated three‐dimensional network of Cs? Sn interactions.     

Manganese(II) Coordination Polymers [{Mn(tren)}(As2Se4)] and [{Mn(tren)}(As4Se7)] with Infinite Selenidoarsenate(III) Chains $^{1}_{\infty}\rm [AsSe_{2}^{-}]$ and $^{1}_{\infty}\rm [As_{4}Se_{7}^{2-}]$

Solvothermal reaction of [MnCl₂(tren)] with elemental As and Se at 1:1:2 and 1:6:12 molar ratios in H₂O/tren (10:1) affords the 1D coordination polymers [{Mn(tren)}(As₂Se₄)] ( 1 ) and [{Mn(tren)}(As₄Se₇)] ( 2 ), respectively. 1 contains vierer infinite chains, which coordinate [(tren)Mn]²⁺ fragments through every second terminal Se atom of their corner‐sharing pyramidal AsSe₃ building units. The double chains of compound 2 are related to the chains 1 by a simple rearrangement of the connectivity pattern between the participating AsSe₃ pyramids and contain condensed centrosymmetric As₈Se₈ and As₄Se₄ rings.     

Electrochemical Detection of ClO$\rm{ {_{3}^{-}}}$, BrO$\rm{ {_{3}^{-}}}$, and IO$\rm{ {_{3}^{-}}}$ at a Phosphomolybdic Acid Linked 3‐Aminopropyl‐Trimethoxysilane Modified Electrode

A composite film modified electrode containing a Keggin‐type heteropolyanion, H₃(PMo₁₂O₄₀)?H₂O, was fabricated with 3‐aminopropyltrimethoxysilane (APMS) attached on an electrochemically activated glassy carbon (GC) electrode through the formation of C? O? Si bond. PMo₁₂O was then complexed with APMS through the electrostatic interaction between the phosphate groups of PMo₁₂O and amine groups of APMS (PMo₁₂O ‐APMS). XPS and cyclic voltammetry were employed for characterization of the composite film. The PMo₁₂O ‐APMS modified electrode showed three reversible redox pairs with smaller peak‐separation and was stable in the larger pH range compared with that in a solution phase. The catalytic properties of the modified electrode for the reduction of ClO , BrO , and IO were studied and the modified electrode exhibited good electrocatalytic activities for the three anions. The experimental parameters, such as pH, temperature, and the applied potential were optimized. The detection limits were determined to be 7.0±0.35 μM, 4.0±0.17 μM, and 0.1±0.04 μM for ClO , BrO , and IO , respectively. The modified electrode was applied to natural water samples for the detection of ClO , BrO , and IO .     

Crystal Structure of di-(L-alanine)Monophosphite Monohydrate [{\rm C}_3{\rm O}_2{\rm NH}_7 ]_2 \cdot {\rm H}_3 {\rm PO}_3 \cdot {\rm H}_2{\rm O}

An X-ray analysis of the crystal structure of di-(L-alanine)monophosphite monohydrate was carried out. The symmetrically nonequivalent L-alanine molecules were found to be present in the structure in two different forms coupled by a strong hydrogen bond: monoprotonated positively charged [CH₃CH(NH₃)COOH] molecule and CH₃CH(NH₃)COO zwitterion. Two layers are distinguished in the structure: one is a positively charged layer formed by L-alanine molecules and the other is a negatively charged layer composed of phosphite ions and water molecules. These layers, alternating along the a axis, are connected to each other by a network of hydrogen bonds.     

Chiral Coordination Polymers with Amino Acids: $\rm ^{2}_{\infty}[Cu_{2}(\mu-L-tryptophanato)_{2}(\mu-4,4\prime-bipyridine)(H_{2}O)_{2}](NO_{3})_{2}$

The two‐dimensional mixed‐ligand network catena‐[(μ‐4,4′‐bipyridine)‐bis(μ‐L‐tryptophanato‐κ³N,O,O′)‐diaqua‐dicopper(II) dinitrate] is constructed through the bridging action of both the tridentate amino carboxylato and the bidentate 4,4′‐bipyridine ligand. The enantiomeric L‐tryptophanato ligand acts as an N,O chelate towards one copper atom and bridges through the second carboxylate oxygen atom to the adjacent copper ion. Stacking of the corrugated nets creates channels which are occupied by the hydrogen‐bonded and very weakly Cu‐coordinating nitrate ions.     

The vinyloxonium cation, \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 2} = {\rm CH - }\mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2}$\end{document}, a stable [C2H5O]+ species in the gas phase

The charge stripping mass spectra of [C₂H₅O]⁺ ions permit the clear identification of four distinct species: \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} - {\rm O - }\mathop {\rm C}\limits^{\rm + } {\rm H}_{\rm 2}$\end{document}, \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} - \mathop {\rm C}\limits^{\rm + } {\rm H - OH}$\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 2} = {\rm CH - }\mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2}$\end{document}. The latter, the vinyloxonium ion, has not been identified before. It is generated from ionized n-butanol and 1,3-propanediol. Its heat of formation is estimated to be 623±12 kJ mol^?1. The charge stripping method is more sensitive to these ion structures than conventional collisional activation, which focuses attention on singly charged fragment ions.     

On the loss of ethylene from [C3H7O]+ ions of structure \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH}_{\rm 2} \mathop {{\rm CHOH}}\limits^{\rm + } $\end{document}

The results of some ³C and ²H labelling experiments plus some measurements of reaction thermochemistry and translational energy releases, permit a significant simplification of the mechanistic pathways by which [C₃H₇O]⁺ ions of structure fragment by loss of C₂H₄. The relationships between these ions and some of their isomeric forms are explored and clarified.     

Controlled Ethylene Polymerization Catalyzed by Cp$\rm{{_{2}^{\ast}}}$ZrBu2/[Ph3C] [B(C6F5)4]/iBu4Al2O above Room Temperature

The ternary system composed of Cp ZrBu₂ (Cp*=Me₅Cp), [CPh₃][B(C₆F₅)₄], and tetraisobutyldialuminoxane (TIBAO) catalyzed the polymerization of ethylene in a controlled fashion at temperatures up to 60 °C. The consumption of ethylene remained constant during the polymerization process, the molecular weight of the polyethylene increased linearly with time, and polydispersity indexes down to 1.3 were obtained. Characterization of the polyethylene by ¹³C‐NMR and FT‐IR spectroscopy did not indicate any branching or CC linkages, even for polymer produced at 40 °C or above. The linear and saturated polymer structure is due to the absence of β‐hydride transfer, β‐hydride elimination and chain walking during the polymerization. The absence of termination reactions is consistent with the system's demonstrated controlled polymerization.     

Voltammetric Behavior of MoS$\rm{ {_{4}^{2-}}}$ and SbS$\rm{ {_{4}^{3-}}}$ as Possible Components of “Dissolved Sulfide” in Oxic Natural Waters

Nanomolar concentrations of dissolved sulfide have been observed in O₂‐ bearing natural waters. The sulfide consists of oxidation‐resistant, unknown chemical components that might include metal‐sulfide complexes, elemental sulfur in various forms or organic sulfur compounds. Here we show that thioanions are also plausible components. Tetrathiomolybdate and tetrathioantimonate ions deposit respectively 3 and 4 equivalents of HgS at mercury electrodes. In cathodic stripping voltammetry, a common method to quantify nanomolar sulfide in nature, MoS and SbS would therefore contribute to “total dissolved sulfide.” Limited evidence suggests that thioanions may be powerful complexing agents that would be capable of affecting trace metal speciation and bioavailability in natural waters.     

Polytellurides and Polyselenides – Compounds Containing $_{\infty}^{1}\rm [Te_{6}-Te_{4}]^{4-}$ and [Sn(Se4)3]2− Anions

The reactions of the Zintl phase K₂Cs₂Sn₉ with elemental tellurium and selenium in ethylenediamine have been investigated. From the reaction of K₂Cs₂Sn₉ with elemental tellurium [K‐(2,2,2‐crypt)]₄Te₆Te₄ ( 2 ) and [K‐(2,2,2‐crypt)]₂Sn₂Te₃ ( 3 ) were obtained, whereas the reaction of K₂Cs₂Sn₉ with elemental selenium led to the formation of [K‐(2,2,2‐crypt)]₂Sn(Se₄)₃ ( 4 ) and [K‐(2,2,2‐crypt)]₂Cs₂Sn₂Se₆·2en ( 5 )¹⁾. Compounds 2 , 4 , 5 have been characterized by single crystal X‐ray structure determination.     

Gamma Ray Radiation Effect on \begin{document}$\rm{{Bi}}_{2}$\end{document}W\begin{document}$\rm{{O}}_{6}$\end{document} Photocatalyst

The development of \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document}-based materials has become one of research hotspots due to the increasing demands on high-efficient photocatalyst responding to visible light. In this work, the effect of high energy radiation (\begin{document}$\gamma$\end{document}-ray) on the structure and the photocatalytic activity of \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document} nanocrystals was first studied. No morphological change of \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document} nanocrystals was observed by SEM under \begin{document}$\gamma$\end{document}-ray radiation. However, the XRD spectra of the irradiated \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document} nanocrystals showed the characteristic 2\begin{document}$\theta$\end{document} of (113) plane shifts slightly from 28.37\begin{document}$^{\rm{o}}$\end{document} to 28.45\begin{document}$^{\rm{o}}$\end{document} with the increase of the absorbed dose, confirming the change in the crystal structure of \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document}. The XPS results proved the crystal structure change was originated from the generation of oxygen vacancy defects under high-dose radiation. The photocatalytic activity of \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document} on the decomposition of methylene blue (MB) in water under visible light increases gradually with the increase of absorbed dose. Moreover, the improved photocatalytic performance of the irradiated \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document} nanocrystals remained after three cycles of photocatalysis, indicating a good stability of the created oxygen vacancy defects. This work gives a new simple way to improve photocatalytic performance of \begin{document}$\rm{Bi}_2$\end{document}W\begin{document}$\rm{O}_6$\end{document} through creating oxygen vacancy defects in the crystal structure by \begin{document}$\gamma$\end{document}-ray radiation.     

Two Glutarato Bridged Coordination Polymers: ${_{\infty}^1}${[Mn(phen)]2L4/2} and ${_{\infty}^1}${[Zn(phen)(H2O)]L2/2}·H2O with H2L = Glutaric Acid

Two new glutarato bridged coordination polymers {[Mn(phen)]₂(C₅H₆O₄)_4/2} ( 1 ) and {[Zn(phen)(H₂O)](C₅H₆O₄)_2/2}· H₂O ( 2 ) were structurally characterized on the basis of single crystal X‐ray diffraction data. Crystal data: ( 1 ) P2/c (no. 13), a = 10.340(2)Å, b = 10.525(2)Å, c = 13.891(2)Å, β = 98.31(1)°, U = 1495.9(5)ų, Z = 2; ( 2 ) P2₁/n (no. 14), a = 6.738(1)Å, b = 25.636(3)Å, c = 10.374(1)Å, β = 106.13(1)°, U = 1721.4(4)ų, Z = 4. Complex 1 consists of 1D ribbon‐like {[Mn(phen)]₂(C₅H₆O₄)_4/2} chains, in which the [Mn(phen)] units were interlinked by glutarato ligands to generate 8‐ and 16‐membered rings. The Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three glutarato ligands with d(Mn‐N) = 2.270, 2.276Å, d(Mn‐O) = 2.114—2.283Å. Through the interchain π‐π stacking interactions, the 1D chains are assembled into 2D puckered layers, which are further held together by interlayer π‐π stacking interactions into a 3D network. Complex 2 is built up by 1D {[Zn(phen)(H₂O)](C₅H₆O₄)_2/2} linear chains and hydrogen bonded H₂O molecules. The Zn atoms are coordinated by two N atoms of one phen ligand and three O atoms of one H₂O molecule and two glutarato ligands to form slightly elongated trigonal bipyramids with the water O atom and one phen N atom at the apical positions (d(Zn‐N) = 2.101, 2.168Å, d(Zn‐O) = 1.991—2.170Å). The 1D linear chains result from [Zn(phen)(H₂O)] units bridged by bis‐monodentate glutarato ligands. The resulting 1D chains are assembled by π‐π stacking interactions into 2D layers, between which the hydrogen bonded H₂O molecules are situated.     

含硫有机膦多酸衍生物α–[RP(S)]2PW9O345-(R = –C6H5, –C6H11)的合成及结构表征

In the presence of Bu4NBr acting as phasetransfer reagent, organothiophosphoryl polyoxotungstate derivatives α-[RP(S)]2PW9O54^5- (R=C6Hs, C6H11) have been obtained by reaction of the trivacant β-[PW9O34]^9- anions with electrophilic C6H5P(S)Cl2 or C6H11P(S)Cl2 in acetonitrile. These new organic-inorganic hybrid anions have been characterized by elemental analysis, IR, ^31P and ^183W NMR spectroscopy. The collective application of the spectroscopy data of these new species indicates that the hybrid anion consists of an α-[PW9O34] framework on which are grafted two RP(S) groups through P-O-W bridges. The five-line ^183W spectra indicate that the hybrid anions possess Cs symmetry in acetonitrile.     

The Photochemical Behavior of the Uranyl Ion (UO$\rm{{_{2}^{2+}}}$): a Dimer Perspective and Outlook

The complex formation of uranyl (UO ) with oxalic acid (HOOC? COOH) in acetone is studied by UV/VIS, absorption, luminescence, and excitation spectroscopy. Based on solid‐state crystallographic data, we propose a dimer structure with D_2h symmetry for the complex in solution. This symmetry is vibrationally distorted to D₂ by the out‐of‐plane equatorial‐ligand vibration. From the spectroscopic point of view, this vibration induces intensity in the transitions Π_g←Σ and one component of Δ_g←Σ . From the photochemical point of view, this vibration induces a twisting mechanism that destroys the complex. From the theoretical point of view, it is worthwhile to notice that the symmetry of the odd out‐of‐plane vibration is the same as the symmetry of the odd LUMO (f_xyz). By vibrating accordingly to the LUMO symmetry, the complex is self‐destroying by absorption of light, and the uranyl is regenerated. A small comment is devoted to a possible δ–δ interaction and the quintuple U₂ bond distance proposed by Gagliardi and Ross [29].     

Pb5I2P28, $^{1}_{\infty}\rm [PbP_{14}]{\rm ^{2-}}$ Strands Coordinated to a Unique [Pb3I2]4+ Unit

Pb₅I₂P₂₈ is the first compound containing a former unseen [P₃I₂]⁴⁺ unit, connecting two crystallographically independent adjacent [PbP₁₄]^2? polyphosphide strands. The polyanion substructure is closely related to the one realized in the HgPbP₁₄ structure type, with a homo‐nuclear coordination of the cations to the polyanions. It has been prepared by using the mineralizator concept for polyphosphides from the elements and PbI₂ as the mineralizator species. The new polyphosphide has a pronounced tendency to form easy cleavable, needle shaped crystals featuring massive stacking vaults. Nevertheless, a single crystal structure determination was possible from inter‐grown crystals. Pb₅I₂P₂₈ crystallizes monoclinically in the space group P2₁/n (No. 14) with lattice parameters of a = 9.792(2), b = 17.717(2), c = 19.191(3) Å, β = 96.39(1)°, V = 3308.6(8) ų. Depending on the preparation route, the aspect ratio of the needle shaped crystals can be varied.