Normal Vibrations of Water in 1:1 Complexes

IR spectra of water in 1:1 complexes (HOH…B) show a characteristic change of the vibration frequencies v₁, v₂ and v₃ for differently strong bases (B). The normal vibrations in different complexes are calculated from the frequencies and the force constants f_OH, f_α, f_OH,OH. The normal vibrations show that v₃ (1:1) becomes the “free” and v₁ (1:1) the “bonded” OH vibration. The degree of coupling in these systems can be deduced directly from the observed band separation. For a base like water the degree of coupling in 1:1 complexes is about 40%.     

1,4-Bis(phosphine)-2,5-difluoro-3,6-dihydroxybenzenes and their P-oxides: Syntheses, structures, ligating and electronic properties

Reactions of 1,4-difluoro-2,5-dimethoxybenzene with LDA (1:2) at low temperatures generated organodilithio intermediates; quenching the reaction mixtures with chlorophosphines ClPR₂ produced 1,4-bis(phosphino)-2,5-difluoro-3,6-dimethoxybenzenes 1a (R = Ph) and 1b (R = iPr). Demethylation of 1a–b was accomplished by BBr₃, yielding bis(phosphino)hydroquinones 2a–b. Treating 2a–b with excess hydrogen peroxide produced bis(phosphinyl)hydroquinones 3a–b. The binucleating properties of 2a were established by the formation of a bimetallic nickel complex upon reaction with Ph₂Ni(PMe₃)₂. Electrochemical activity of hydroquinones 2a–b and 3a–b was examined by cyclic voltammetry. In addition, compounds 2a, 3a and 3b were obtained in crystalline form and characterized by single-crystal X-ray diffraction. The influence of the fluorine substituents on the composition of the frontier orbitals of 2a and 3a was examined by computational methods.     

Regioselective reactivity of an asymmetric tetravalent di[dihydroxotin(IV)] bis-porphyrin host driven by hydrogen-bond templation

Local molecular environment effects on the rates of ligand exchange at an asymmetric di[dihydroxotin(IV)] bis-porphyrin 5 are examined. The host 5 possesses four non-equivalent tin(IV)-ligand binding sites that are distinguished by their position relative to a shallow cavity, by the steric environment at each binding site and by electronic-structure differences between the constituent porphyrin and quinoxalinoporphyrin macrocycles. These design features of the asymmetric host are confirmed by X-ray crystal structure analysis. Binding experiments with monodentate carboxylic acids and bidentate dicarboxylic acids show significant differences in the rate of ligand exchange at each of the four tin(IV) binding sites. For monodentate carboxylic acids, binding preferentially occurs at the exterior porphyrin site. Further addition of carboxylic acid results in sequential binding at the quinoxalinoporphyrin sites and lastly at the interior site on the porphyrin, with high regioselectivity. These selective binding outcomes are immediately apparent by NMR spectroscopy. A series of 2D NMR spectroscopy experiments allowed identification of the preferred binding sites at the host. This positively identifies that steric hindrance and electron-withdrawing functionality on the porphyrin macrocycle impede ligand exchange. However, these effects are overcome by dicarboxylic acid guests, which form ditopic hydrogen-bond interactions between the intracavity hydroxo ligands in the initial stage of ligand exchange, leading to regioselective binding between the tin(IV) sites within the cavity. It is envisaged that the factors identified herein that define regioselective ligand exchange at host 5 will find wider application in supramolecular systems incorporating tin(IV) porphyrins.     

The Effects of Structural Alterations in the Polyamine and Amino Acid Moieties of Philanthotoxins on Nicotinic Acetylcholine Receptor Inhibition in the Locust,Schistocerca gregaria

Alterations in the polyamine and amino acid (tyrosine) moieties of philanthotoxin-343 (PhTX-343) were investigated for their effects on the antagonism of nicotinic acetylcholine receptors (nAChRs) isolated from the locust (Schistocerca gregaria) mushroom body. Through whole-cell patch-clamp recordings, the philanthotoxin analogues in this study were shown to cause inhibition of the inward current when co-applied with acetylcholine (ACh). PhTX-343 (IC₅₀ = 0.80 μM at −75 mV) antagonised locust nAChRs in a use-dependent manner, suggesting that it acts as an open-channel blocker. The analogue in which both the secondary amine functionalities were replaced with methylene groups (i.e., PhTX-12) was ~6-fold more potent (IC₅₀ (half-maximal inhibitory concentration) = 0.13 μM at −75 mV) than PhTX-343. The analogue containing cyclohexylalanine as a substitute for the tyrosine moiety of PhTX-343 (i.e., Cha-PhTX-343) was also more potent (IC₅₀ = 0.44 μM at −75 mV). A combination of both alterations to PhTX-343 generated the most potent analogue, i.e., Cha-PhTX-12 (IC₅₀ = 1.71 nM at −75 mV). Modulation by PhTX-343 and Cha-PhTX-343 fell into two distinct groups, indicating the presence of two pharmacologically distinct nAChR groups in the locust mushroom body. In the first group, all concentrations of PhTX-343 and Cha-PhTX-343 inhibited responses to ACh. In the second group, application of PhTX-343 or Cha-PhTX-343 at concentrations ≤100 nM caused potentiation, while concentrations ≥ 1 μM inhibited responses to ACh. Cha-PhTX-12 may have potential to be developed into insecticidal compounds with a novel mode of action.     

Synthesis and catalytic epoxidation activity with TBHP and H2O2 of dioxo-, oxoperoxo-, and oxodiperoxo molybdenum(VI) and tungsten(VI) compounds containing monodentate or bidentate phosphine oxide ligands: crystal structures of WCl2(O)2(OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2.C4H10O, WCl2(O)2dppmO2, Mo(O)(O2)2dppmO2, and W(O)(O2)2dppmO2

The dioxo tungsten(VI) and molybdenum(VI) complexes WCl2(O)2(OPMePh2)2, WCl2(O)2dppmO2, and MoCl2(O)2dppmO2, the oxoperoxo compounds WCl2(O)(O2)(OPMePh2)2, WCl2(O)(O2)dppmO2, and MoCl2(O)(O2)dppmO2, and the oxodiperoxo complexes, W(O)(O2)2dppmO2 and Mo(O)(O2)2dppmO2 have been prepared and characterized by IR spectroscopy, 31P NMR spectroscopy, elemental analysis, and X-ray crystallography. The structural and X-ray crystallographic data of compounds WCl2(O)2(OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2.4H10O, WCl2(O)2dppmO2, Mo(O)(O2)2dppmO2, and W(O)(O2)2dppmO2 are also detailed. All complexes were studied as catalysts for cis-cyclooctene epoxidation in the presence of tert-butyl hydroperoxide (TBHP) or H2O2 as an oxidant. The Mo-based catalysts showed a superior reactivity over W-based catalysts in the TBHP system. On the other hand, in the H2O2 system, the W-based catalysts (accomplishing nearly 100% epoxidation of cyclooctene in 6 h) are more reactive than the Mo catalysts (<45% under some conditions). Various solvent systems have been investigated, and ethanol is the most suitable solvent for the H2O2 system.     

Nonequilibrium dynamics of the zeta urn model

We consider a mean-field dynamical urn model, defined by rules which give the rate at which a ball is drawn from an urn and put in another one, chosen amongst an assembly. At equilibrium, this model possesses a fluid and a condensed phase, separated by a critical line. We present an analytical study of the nonequilibrium properties of the fluctuating number of balls in a given urn, considering successively the temporal evolution of its distribution, of its two-time correlation and response functions, and of the associated fluctuation-dissipation ratio, both along the critical line and in the condensed phase. For well separated times the fluctuation-dissipation ratio admits non-trivial limit values, both at criticality and in the condensed phase, which are universal quantities depending continuously on temperature.     

Tetra­ammonium benzene‐1,2,4,5‐tetra­carboxyl­ate tetrahydrate

The anions in the title compound, 4NH₄⁺·C₁₀H₂O₈^4?·4H₂O, are held together by regular hydrogen bonds from the carboxyl­ate O atoms to the ammonium cations and water mol­ecules, forming a three‐dimensional network.     

Scaling properties of a structure intermediate between quasiperiodic and random

We consider a one-dimensional structure obtained by stringing two types of beads (short and long bonds) on a line according to a quasiperiodic rule. This model exhibits a new kind of order, intermediate between quasiperiodic and random, with a singular continuous Fourier transform (i.e., neither Dirac peaks nor a smooth structure factor). By means of an exact renormalization transformation acting on the two-parameter family of circle maps that defines the model, we study in a quantitative way the local scaling properties of its Fourier spectrum. We show that it exhibits power-law singularities around a dense set of wavevectorsq, with a local exponent(q) varying continuously with the ratio of both bond lengths. Our construction also sheds some new light on the interplay between three characteristic properties of deterministic structures, namely: (1) a bounded fluctuation of the atomic positions with respect to their average lattice; (2) a quasiperiodic Fourier transform, i.e., made of Dirac peaks; and (3) for sequences generated by a substitution, the number-theoretic properties of the eigenvalue spectrum of the substitution.