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 .     

Structures and formation of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm 8}} } \right]_{}^{_.^ + } $\end{document} ions

Several \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm\ 8}} } \right]_{}^{_.^ + } $\end{document} ion isomers yield characteristic and distinguishable collisional activation spectra: \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm 1-butene} } \right]_{}^{_.^ + } $\end{document} and/or \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm 2-butene} } \right]_{}^{_.^ + } $\end{document} (a-b), \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm isobutene} } \right]_{}^{_.^ + } $\end{document} (c) and [cyclobutane]⁺ (e), while the collisional activation spectrum of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm methylcyclopropane} } \right]_{}^{_.^ + } $\end{document} (d) could also arise from a combination of a-b and c. Although ready isomerization may occur for \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm 8}} } \right]_{}^{_.^ + } $\end{document} ions of higher internal energy, such as d or e → a, b, and/or c, the isomeric product ions identified from many precursors are consistent with previously postulated rearrangement mechanisms. 1,4-Eliminations of HX occur in 1-alkanols and, in part, 1-buthanethiol and 1-bromobutane. The collisional activation data are consistent with a substantial proportion of 1,3-elimination in 1- and 2-chlorobutane, although 1,2-elimination may also occur in the latter, and the formation of the methylcycloprpane ion from n-butyl vinyl ether and from n-butyl formate. Surprisingly, cyclohexane yields the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm linear butene} } \right]_{}^{_.^ + } $\end{document} ions a-b, not \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm cyclobutane} } \right]_{}^{_.^ + } $\end{document}, e.     

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.     

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.     

Unimolecular reactions of isolated organic ions: The chemistry of the unsaturated oxonium ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 2} = {\rm CHCH =}\mathop {{\rm OCH}_{\rm 3}}\limits^{\rm +} $\end{document}

The reactions of metastable $ {\rm CH}_{\rm 2} = {\rm CHCH =}\mathop {{\rm OCH}_{\rm 3}}\limits^{\rm +} $ oxonium ions generated by alkyl radical loss from ionized allylic alkenyl methyl ethers are reported and discussed. Three main reactions occur, corresponding to expulsion of H₂O, C₂H₄/CO and CH₂O. There is also a very minor amount of C₃H₆ elimination. The mechanisms of these processes have been probed by ²H- and ¹³C-labelling experiments. Special attention is given to the influence of isotope effects on the kinetic energy release accompanying loss of formaldehyde from ²H-labelled analogues of $ {\rm CH}_{\rm 2} = {\rm CHCH =}\mathop {{\rm OCH}_{\rm 3}}\limits^{\rm + } $. Suggestions for interpreting these reactions in terms of routes involving ion–neutral complexes are put forward.     

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.     

Electrochemiluminescent Determination of Chlorphenamine Maleate Based on Ru(bpy)$\rm{ {_{3}^{2+}}}$ Immobilized in a Nano‐Titania/Nafion Membrane

The immobilization of tris(2,2'‐bipyridyl)ruthenium(II) [Ru(bpy) ] in a TiO₂/Nafion nanocomposites membrane modified glassy carbon electrode (GCE) was achieved via both an ion‐exchange process and hydrophobic interactions .The surface‐confined Ru(bpy) shows good electrochemical and photochemical activities. The Ru(bpy) underwent reversible surface process and reacted with chlorphenamine maleate (CPM) to produce electrochemiluminescence. The modified electrode was used for the ECL determination of CPM. It showed good linearity in the concentration range from 2×10^?8 g/mL to 1×10^?6 g/mL (R=0.9995) with a detection 6×10^?9 g/mL (S/N=3). The relative standard derivation (n=11) was 2%. This method is developed for the determination of CPM with simplicity and high sensitivity.     

Structural Characterization of Some Coinage Metal(I) Thiosulfate Complexes, $\rm M^{1}_{a}M\rm ^{2}_{b}(X_{c}) (S_{2}O_{3})_{d}(\cdot eS)$ (M1 = Group 1 Cation,X = Univalent Anion,M2 = CuI,AgI, S = Solvent)

Building on previous single crystal X‐ray structure determinations for the group 1 salts of complex thiosulfate/univalent coinage metal anions previously defined for (NH₄)₉AgCl₂(S₂O₃)₄, NaAgS₂O₃·H₂O and Na₄[Cu(NH₃)₄][Cu(S₂O₃)₂]·NH₃, a wide variety of similar salts, of the form , M¹ = group 1 metal cation, M² = univalent coinage metal cation (Cu, Ag), (X = univalent anion), most previously known, but some not, have been isolated and subjected to similar determinations. These have defined further members of the isotypic, tetragonal series, for M¹ = NH₄, M² = Cu, Ag, X = NO₃, Cl, Br, I, together with the K/Cu/NO₃ complex, all containing the complex anion [M²(SSO₃)₄]^7? with M² in an environment of symmetry, Cu, Ag‐S typically ca. 2.37, 2.58Å, with quasi‐tetrahedral S‐M‐S angular environments. Further salts of the form , n = 1‐3, have also been defined: For n = 3, M² = Cu, M¹/x = K/2.25 or 1 5/6, NH₄/6, (and also for the (NH₄)₄Na/4H₂O·MeOH adduct) the arrays take the form with distorted trigonal planar CuS₃ coordination environments, Cu‐S distances being typically 2.21Å, S‐Cu‐S ranging between 105.31(4)–129.77(4)°; the silver counterparts take the form for M¹ = K, NH₄. For n = 2, adducts have only been defined for M² = Ag, the anions of the M¹ = Na, K adducts being dimeric and polymeric respectively: Na₆[(O₃SS)₂Ag(μ‐SSO₃)₂Ag(SSO₃)]·3H₂O, K₃[Ag(μ‐SSO₃)₂]_(∞|∞)·H₂O; a polymeric copper(I) counterpart of the latter is found in Na₅Cu(NO₃)₂(S₂O₃)₂ ≡ 2NaNO₃·Na₃[Cu(μ‐SSO₃)₂]_(∞|∞). For n = 1, NaAgS₂O₃, the an‐ and mono‐ hydrates, exhibit a two‐dimensional polymeric complex anion in both forms but with different contributing motifs. (NH₄)₁₃Ag₃(S₂O₃)₈·2H₂O takes the form (NH₄)₁₃[{(O₃SS)₃Ag(μ‐SSO₃)}₂Ag], a linearly coordinated central silver atom linking a pair of peripheral [Ag(SSO₃)₄]^7? entities. In Na₆[(O₃SS)Ag(μ‐SSO₃)₂Ag(SSO₃)]·3H₂O, the binuclear anions present as Ag₂S₄ sheets, the associated oxygen atoms being disposed to one side, thus sandwiching layers of sodium ions; the remarkable complex Na₅[Ag₃(S₂O₃)₄]_(∞|∞)·H₂O is a variant, in which one sodium atom is transformed into silver, linking the binuclear species into a one‐dimensional polymer. In (NH₄)₈[Cu₂(S₂O₃)₅]·2H₂O a binuclear anion of the form [(O₃SS)₂Cu(μ‐S.SO₃)Cu(SSO₃)₂]^8? is found; the complex (NH₄)₁₁Cu(S₂O₃)₆ is 2(NH₄)₂(S₂O₃)·(NH₄)₇[Cu(SSO₃)₄]. A novel new hydrate of sodium thiosulfate is described, 4Na₄S₂O₃·5H₂O, largely describable as sheets of the salt, shrouded in water molecules to either side, together with a redetermination of the structure of 3K₂S₂O₃·H₂O.     

Differentiation of tautomers by ion cyclotron resonance spectrometry: \documentclass{article}\pagestyle{empty}\begin{document}${\rm (CH}_{\rm 3} {\rm)}_{\rm 2} \mathop {\rm N}\limits^{\rm + } {\rm = CH}_{\rm 2} {\rm vs H}_{\rm 3} {\rm C}\mathop {\rm N}\limits^{\rm + } {\rm H = CHCH}_{\rm 3}$\end{document}

Ion cyclotron resonance spectrometry and deuterium labeling have been used to determine that nondecomposing \documentclass{article}\pagestyle{empty}\begin{document}${\rm (CH}_{\rm 3} {\rm)}_{\rm 2} \mathop {\rm N}\limits^{\rm + } {\rm = CH}_{\rm 2}$\end{document} ions do not isomerize to \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} {\rm CH = }\mathop {\rm N}\limits^{\rm + } {\rm HCH}_{\rm 3}$\end{document}.     

Stable γ-distonic oxonium ions: R\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm O}\limits^ + $\end{document}HCHR′ĊH2CHR″ and their characteristic reaction

The γ-distonic radical ions R$ \mathop {\rm O}\limits^ + $CHR′CH₂?HR″ and their molecular ion counterparts R$ \mathop {\rm O}\limits^{{\rm + } \cdot } $CHR′CH₂CH₂R″ have been studied by isotopic labelling and collision-induced dissociation, applying a potential to the collision cell in order to separate activated from spontaneous decompositions. The stability of CH₃$ \mathop {\rm O}\limits^ + $HCH(CH₃)CH₂?HCH₃, C₂H₅$ \mathop {\rm O}\limits^ + $HCH(CH₃)CH₂?HCH₃, CH₃$ \mathop {\rm O}\limits^ + $HCH(CH₃)CH₂?H₂, CH₃$ \mathop {\rm O}\limits^ + $HCH₂CH₂?HCH₃ and C₂H₅$ \mathop {\rm O}\limits^ + $HCH₂CH₂?HCH₃, has been demonstrated and their characteristic decomposition, alcohol loss, identified. For all these γ-distonic ions, the 1,4-H abstraction leading to their molecular ion counterpart exhibits a primary isotope effect.     

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].     

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.     

Ab initio molecular orbital study on the structures and energetics of CH3OH\documentclass{article}\pagestyle{empty}\begin{document}$_{2}^{+}$\end{document}(H2O)n and CH3SH\documentclass{article}\pagestyle{empty}\begin{document}$_{2}^{+}$\end{document}(H2O)n in the gas phase

The purpose of this study was to calculate the structures and energetics of CH₃OH$_{2}^{+}$(H₂O)_n and CH₃SH$_{2}^{+}$(H₂O)_n in the gas phase: we asked how the CH₃OH$_{2}^{+}$ and CH₃SH$_{2}^{+}$ moieties of CH₃OH$_{2}^{+}$(H₂O)_n and CH₃SH$_{2}^{+}$(H₂O)_n change with an increase in n and how can we reproduce the experimental values ΔH°_n−1,n. For this purpose, we carried out full geometry optimizations with MP2/6‐31+G(d,p) for CH₃OH$_{2}^{+}$(H₂O)_n (n=0,1,2,3,4,5) and CH₃SH$_{2}^{+}$(H₂O)_n (n=0,1,2,3,4). We also performed a vibrational analysis for all clusters in the optimized structures to confirm that all vibrational frequencies are real. All of the vibrational frequencies of these clusters are real, and they correspond to equilibrium structures. For CH₃OH$_{2}^{+}$(H₂O)_n, when n increases, (1) the C O bond length decreases, (2) the C H bond lengths do not change, (3) the O H bond lengths increase, (4) the OCH bond angles increase, (5) the COH bond angles decrease, (6) the charge on CH₃ becomes less positive, and (7) these predicted values, except for the O H bond lengths of CH₃OH$_{2}^{+}$(H₂O)_n, approach the corresponding values in CH₃OH. The C O bond length in CH₃OH$_{2}^{+}$(H₂O)₅ is shorter than that in CH₃OH$_{2}^{+}$ in the gas phase by 0.061 Å at the MP2/6‐31+G(d,p) level. Except for the S H bond lengths in CH₃SH$_{2}^{+}$(H₂O)_n, however, the structure of the CH₃SH$_{2}^{+}$ moiety does not change with an increase in n. © 2000 John Wiley & Sons, Inc. J Comput Chem 22: 125–131, 2001     

On the Interchange Ability of the N‐donor Position in the Rare Earth Coordination Polymers $^{1}_{\infty}\rm [Ln(Btz)_{3}(L)]$, L = BtzH,Ph(NH2)2, NH3, and Pyridine

Benzotriazolates of the rare earth elements form chain like coordination polymers of the formula . An additional neutral ligand L saturates the coordination spheres of the trivalent lanthanide ions and, depending on the reaction conditions, can be a varying donor (L = BtzH, Ph(NH₂)₂, NH₃ and Py). Reactions in the BtzH (1H‐benzotriazole) melt result in coordination of benzotriazole and its thermal decomposition products as L. We have now investigated if the site occupied by L can be exchanged with other N donor ligands. Pyridine can substitute BtzH, Ph(NH₂)₂ and NH₃ under solvothermal conditions giving the coordination polymer even for the biggest Ln^III cation lanthanum without changing the overall strand structure. Chains proof to be the chemically favoured and stable structure fragment with the L position being the chemically variable site.     

Gas phase isomerization of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 10}} {\rm H}_{{\rm 14}} } \right]_{}^{_.^ + } $\end{document} ions generated from adamantanoid compounds

\documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 10}} {\rm H}_{{\rm 14}} } \right]_{}^{_.^ + } $\end{document} ions have been generated from a number of adamantanoid compounds, both by ionization and ionization followed-by fragmentation. Metastable ion abundance ratios of competitive reactions indicate the decomposition of these ions from common structures in all cases.     

$^{1}_{\infty}\rm [Ho_{2}Cl_{6}\{1,3-Ph(CN)_{2}\}_{3}]$ – Eine zu Doppelsträngen kondensierte Variante der PaCl5‐Struktur in einem Selten‐Erd‐Benzodinitril‐Koordinationspolymer

– A Variant of the PaCl₅ Structure Condensed to Double Strands in a Rare Earth Benzodinitrile Coordination Polymer Single crystalline transparent pink (1,3‐Ph(CN)₂ = 1,3‐benzodinitrile, C₆H₄(CN)₂) was obtained by the reaction of anhydrous holmium trichloride with a melt of 1,3‐benzodinitrile at 175 °C. The trichloride structure is broken up by the dinitrile ligands and re‐arranged to double strands of edge connected pentagonal bipyramids of chlorine and nitrogen atoms. The structure can be deduced from the PaCl₅ structure type by condensation of two PaCl₅ strands and exchange of two chlorine atoms with nitrile groups. The double strands exhibit ligand free cavities of 600–800 pm diameter.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

On an Unexpected 2D‐linked Rare Earth 1,2,4‐Triazolate Network: Synthesis,Crystal Structure,Spectroscopic and Thermal Properties of $_{\infty}^{2}\rm [Ho(Tz)_{3}(TzH)_{2}]TzH$

The network compound , (Tz^? = 1,2,4‐triazolate anion, C₂H₂N₃^?, TzH = 1,2,4‐1H‐triazole, C₂H₃N₃), was obtained as pink single crystals by the reaction of the holmium metal with a melt of the amine 1,2,4‐1H‐triazole. No additional solvent was used. The compound is an unexpected example of a 2D‐linked network structure as other lanthanides give 3D‐frameworks and MOFs with 1,2,4‐1H‐triazole instead. This illustrates that the series of lanthanides yields very different results in attempts to create MOF structures. In the triazolate ligands Tz^? function both as μ‐η¹:η² linkers as well as η¹ end on ligands. The latter coordination mode is also found for additional triazole molecules. C.N. is nine for holmium(III). The layers exhibit a system of intra and inter layer hydrogen bonding and to triazole molecules from the melt reaction intercalated in‐between the layers. The product was investigated by X‐ray single crystal analysis, Mid IR, Far IR and Raman spectroscopy, and with DTA/TG regarding its thermal behaviour.     

Unexpected Kinetics in the Polymerization of Ethene by Cp$\rm{ {_{2}^{{\ast}}}}$ZrCl2/MAO

A sterically hindered metallocene catalyst, Cp ZrCl₂ activated with methylaluminoxane (MAO), is found to polymerize ethene at temperatures up to 60° with a good propagation rate constant but low number of active sites, and with negligible β‐hydride elimination or β‐hydride transfer to monomer. Moreover, transmetalation to Al is found to be effectively irreversible for alkyl groups larger than Me. With the major mechanisms for chain transfer and termination suppressed, one might expect a living polymerization. The bulk polymerization of ethene was indeed found to be quasi‐living even when performed at well above room temperature, and furthermore provided rate constants which agreed remarkably well with those from the mass‐spectrometric study.     

Electrochemiluminescence Sensor Based on Multiwalled Carbon Nanotubes Doped Polyvinyl Butyral Film Containing Ru(bpy)$\rm{ {_{3}^{2+}}}$ as Chemiluminescence Reagent

An effective electrochemiluminescence (ECL) sensor was developed by combining Ru(bpy) with multiwalled carbon nanotubes(MWNTs) doped polyvinyl butyral (PVB) film. The doped film can prevent the leakage of Ru(bpy) efficiently and the immobilized Ru(bpy) kept its electrocatalytic activity toward the electrooxidation of tripropylamine (TPA), suggesting PVB and MWNTs were proper matrix to immobilize Ru(bpy) by hydrophobic interaction. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and electrochemiluminescent characterization were employed to study the presented sensor. A wide linear dynamic range of 6 orders of magnitude between ECL intensity and concentration of TPA was found from 1×10^?8 M to 5×10^?2 M, with a detection limit of 3.5×10^?9 M.