Reductive nitrosylation of tetraoxometallates—XVII. Molybdate-hydroxylamine-cyanide reaction, and synthesis and characterization of K2[Mo(NO)(CN)5] and (NMe4)2[Mo(NO)(CN)4]

A reaction condition is established which determines the nature of the products in the molybdate-hydroxylamine-cyanide reaction. With hydroxylamine always used in excess, it is the hydroxyl ion concentration of the reaction mixture which plays a vital role in determining whether K₄[Mo(NO)(CN)₅] or K₂[Mo(NO)(CN)₅] is obtained exclusively. The latter product is hereby reported for the first time. Its powder diffractogram being typical of a cubic system, a gross structural characterization has been made possible. The former under aqueous, aerobic conditions yields a new product, (NMe₄)₂[Mo(NO)(CN)₄].     

Photopolymerization of methyl methacrylate with the use of bromine as photoinitiator

Low concentrations of bromine (0.008–0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol. Polymerization in bulk follows usual free-radical kinetics. Inert solvents (benzene, toluene) as well as the other solvents used enhance the rate of polymerization MMA even when used in the range of catalytic concentrations (0.04–0.4M). An initiation mechanism involving solvent molecules appears to be predominant in diluted systems.     

Intermolecular force constants of hcn in the condensed phase

A simple theory of linear lattice is applied to the hydrogen bonded linear chain system of HCN to calculate the intermolecular force constants at different temperatures in the condensed phase. The strong CN bond is assumed to remain unperturbed in the hydrogen bond formation. The sharp change in intermolecular force constant while passing from the crystalline to the liquid phase is interpreted as a characteristic of this phase transition (fusion).     

Partitioning of quencher ions in the micellar microenvironment of polyoxyethylene nonyl phenol

This paper has explored the quenching of fluorescence of the dye safranine T (ST) by the inorganic cations viz Cu2+, Co2+, Ni2+ and Mn2+ in micellar solutions of the surfactant dioxyethylene nonyl phenol (Igepal CO-210), pentaoxyethylene nonyl phenol (Igepal CO-520) and dodecaoxyethylene nonyl phenol (Igepal CO-720). The quenching results have been calculated in light of stern volmer equation (SV) to evaluate the extent of interaction between the fluorophore (ST) and quencher. The average concentration of the quencher ions in the micelle have been determined. The quenching efficiency of ST by inorganic ions in micellar medium is lower than that in aqueous medium. The results show that the ions get partitioned in the micellar medium. The values of the partition coefficient of the ions decrease with increase in HLB value and number of oxyethylene groups in Igepal.     

Metal-organic framework H-bonded like a polycatenane: coexistence of acyclic water trimer and nonamer

Pyridine-2,6-dicarboxylic acid and 1,2-di-4-pyridylethylene react hydrothermally with nickel(II) nitrate, forming a metal-organic framework that forms a polycatenane-like structure through H-bonding interactions between water molecules and carboxylate O atoms with void spaces. Discrete acyclic trimeric and nonameric water clusters occupy the voids in the structures. X-ray powder diffraction and X-ray structure analysis have been used to characterize this compound. Crystal data for 1 {(3dpeH(2))[Ni(pdc)(2)](3).15H(2)O}: monoclinic space group P2(1)/c, a = 24.730(5) Angstroms, b = 19.895(2) Angstroms, c = 17.257(4) Angstroms, beta = 104.832(5) degrees, V = 8208(4) Angstroms(3), Z = 4, R1 = 0.0429, wR2 = 0.1072, and S = 1.051.     

Synthesis of azahelicenes through Mallory reaction of imine precursors: corannulene substrates provide an exception to the rule in oxidative photocyclizations of diarylethenes

Typically, the synthesis of phenanthrene-based polycyclic aromatic hydrocarbons relies on the Mallory reaction. In this approach, stilbene (PhCH CHPh)-based precursors undergo an oxidative photocyclization reaction to join the two adjacent aromatic rings into an extended aromatic structure. However, if one C C carbon atom is replaced by a nitrogen atom (C N), the synthesis becomes practically infeasible. Here, we show the very first examples of a successful Mallory reaction on stilbene-like imine precursors involving the molecularly curved corannulene nucleus. The isolated yields exceed 90% and the resulting single and double aza[4]helicenes exhibit adjustable high affinity for electrons.

First azahelicene synthesis from corannulene-based imine precursors is presented.     

Determination of critical micelle concentration by hyper-rayleigh scattering

The critical micelle concentration (CMC) of several surfactants that contain an NLO chromophore, either at the hydrocarbon tail, or at the hydrophilic headgroup, or even as a counterion, was determined by hyper-Rayleigh scattering (HRS). In all cases, the HRS signal exhibited a similar variation with surfactant concentration, wherein the CMC is inferred from a rather unprecedented drop in the signal intensity. This drop is attributed to the formation of small pre-micellar aggregates, whose concentrations become negligible above CMC. In addition, a probe molecule, which upon protonation yielded a species with significantly enhanced HRS intensity, was developed and its utility for the determination of the CMC of simple fatty acids was demonstrated.     

Studies of vulcanization with tetramethylthiuram disulfide and sulfur vulcanization accelerated by tetramethylthiuram disulfide of styrene–butadiene rubber in presence and absence of dicumyl peroxide

The salient features of nonelemental sulfur vulcanization by tetramethylthiuram disulfide (TMTD) and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. In stock containing TMTD, a higher rate constant value for dicumyl peroxide (DCP) decomposition was observed. TMTD decreases the crosslinking density due to DCP depending on its concentration. An entirely radical mechanism has been advanced in the absence of ZnO. ZnO or ZnO–stearic acid seems to alter the entire course of reaction. The rate of crosslinking increases in the presence of ZnO or ZnO–stearic acid. Moreover, crosslinks are formed additively (further supported from the activation energy data), and mixed crosslink formation has been confirmed by the methyl iodide test of the vulcanizates. Stearic acid has no effect on crosslink formation. An ionic chain mechanism has been postulated in the presence of ZnO, as suggested by British authors.