Factors contributing to phantom bonds in inorganic molecules: Interpretations and predictions

The validity of various qualitative proposals for interpreting and predicting the existence of short contacts between formally non-bonded atoms, as in cyclodisiloxane and related inorganic ring systems, is critically evaluated. The models range from simple considerations of geometric constraints, lone pair repulsions and pi-complex formation to proposals such as the unsupported pi-bond model and the sigma-bridged-pi bond concept. It is pointed out that a unified description based on a combination of closed and open 3-centre 2-electron bonds is possible. The role of hybridisation is emphasized in the short phantom bond computed in an earlier model system. These insights are used to predict structures with exceptionally short Si..Si and B..B phantom bonds. The proposals are confirmed by ab initio calculations.

Modulation of vesicular properties by variation of shapes of bolaform counter ions in hybrid-ion paired surfactants

Four new vesicle-forming bolaphile/amphiphile ion pairs are synthesized; the bolaphile shapes in such hybrid systems strongly control their vesicular properties.

First-order hyperpolarizabilities and pKa of weak organic acids in protic solvents are lineraly related

Second-order nonlinearities (beta) of five weak organic acids in protic solvents have been measured by the double-quantum Rayleigh scattering (DRS) technique. beta is found to bear a linear relationship to the pK(a) of these compounds in those solvents. A direct implication of this observation is that the DRS technique can be used to determine the pK(a) of weak organic acids in any solvent.

Dissociation constants of weak organic acids in protic solvents obtained from their first hyperpolarizabilities in solution

The first hyperpolarizabilities (beta) of some weak aromatic organic acids have been measured in protic solvents by the hyper-Rayleigh scattering (HRS) technique at low concentrations. The measured hyperpolarizability (beta(m)) varies between the two extreme limits: the hyperpolarizability of the acid form (beta(HA)) at the lower side and that of the basic form (beta(A-)) at the higher side. The degree of dissociation (alpha) of the acid in a solvent is related to the measured hyperpolarizability, beta(m), by the following relationship: beta(m)(2)=(1-alpha)beta(HA)(2)+alpha beta(A-)(2). The calculated beta's including solvent effects in terms of an Onsager field do not reproduce the experimentally measured hyperpolarizabilities. Other solvent-induced effects like hydrogen bonding and van der Waals interactions seem to influence the first hyperpolarizability and, thus, indirectly the extent of dissociation of these weak acids in these protic solvents.

Spatial confinement of exciton transfer and the role of conformational order in organic nanoparticles

Organic nanoparticles consisting of single conjugated polymer chains were investigated as a function of degree of conjugation by means of single-molecule spectroscopy. The degree of conjugation was synthetically controlled. For highly conjugated chains, singlet excitons are efficiently funneled over nanometer distances to a small number of sites. In contrast, chains with less conjugation and a high number of saturated bonds do not exhibit energy funneling due to a highly disordered conformation.

Sulfates of organic diamines: hydrogen-bonded structures and properties

In order to investigate the supramolecular hydrogen-bonded networks and other structural features exhibited by compounds containing an organic cation and an inorganic anion, sulfates of the organic diamines, ethylenediamine (I), 1,3-diaminopropane (II), piperazine (III), and 1,4-diazabicyclo[2.2.2]octane (DABCO) (IV) have been prepared investigated by X-ray crystallography. While II, III, and IV crystallize in the centrosymmetric space group, Pbca, P2(1)/n, Pbcn, respectively, I crystallizes in the non-centrosymmetric space group, P4(1) exhibiting chirality and weak NLO properties. I-IV exhibit different types of supramolecular H-bonded networks involving the organic cation and the SO42- anion. The nature and strength of the H-bonding network vary from one compound to another, with the strongest network found in piperazinium sulfate, III, and the weakest in II. While in III, water molecules form part of the H-bonded network, they are present as guest molecules in the channels of IV. Thermal stability of the compounds as well as the infrared spectra reflect the stabilities of these H-bonded solids. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Phase transitions in the anchored organic bilayers of long-chain alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4; n=12, 16, 18

The single perovskite slab alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4, n = 12, 16, 18, display two phase transitions, just above room temperature, associated with changes in the alkylammonium chains. We have followed these two phase transitions using scanning calorimetry, X-ray powder diffraction, and IR and Raman spectroscopies. We find the first phase transition to be associated with symmetry changes arising from a dynamic rotational disordering of the ammonium headgroup of the chain whereas the second transition, the melting of the chains in two dimensions, is characterized by an increased conformational disorder of the methylene units of the alkyl chains. We examine these phase transitions in light of the interesting optical properties of these materials, as well as the relevance of these systems as models for phase transitions in lipid bilayers.

Synthesis of electrically conducting copolymers of o-/m-toluidines and o-/m-amino benzoic acid in an organic peroxide system and their characterization

Copolymers of o-lm-toluidine with o-lm-amino benzoic acid have been synthesized by chemical polymerization using inverse emulsion pathway and characterized by a number of techniques including UV-Vis, FT-IR, FT Raman, EPR and NMR spectroscopies, thermal analysis and conductivity. The solubility of the copolymers in organic solvents increases with increase in the amount of amino benzoic acid in the feed. The copolymers synthesized at room temperature show relatively higher conductivity and are obtained in higher yield compared to those synthesized at 0 and 60 degreesC. The spectral studies have revealed restricted conjugation along the polymer chain. The effect of -COOH substituent on the copolymer structure is discussed. (C) 2003 Elsevier Science B.V All rights reserved.

Electroluminescence from GaN-polymer heterojunction

Inorganic and organic semiconductor devices are generally viewed as distinct and separate technologies. Herein we report a hybrid inorganic-organic light-emitting device employing the use of an air stable polymer, Poly (9,9-dioctylfluorene-alt-benzothiadiazole) as a p-type layer to create a heterojunction, avoiding the use of p-type GaN, which is difficult to grow, being prone to the complex and expensive fabrication techniques that characterises it. I-V characteristics of the GaN-polymer heterojunction fabricated by us exhibits excellent rectification. The luminescence onset voltage is typically about 8-10 V. The device emits yellowish white electroluminescence with CIE coordinates (0.42, 0.44). (C) 2011 Elsevier B.V. All rights reserved.

Fluorescent metal-organic framework for selective sensing of nitroaromatic explosives

Highly luminescent micrometre-sized fine particles of a Zn(II) metal-organic framework (MOF) of a new pi-electron rich tricarboxylate dispersed in ethanol is demonstrated as a selective sensory material for the detection of nitroaromatic explosives via a fluorescence quenching mechanism.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Magnetic and Mechanical Anisotropy in a Manganese 2-Methylsuccinate Framework Structure

Hybrid inorganic-organic framework materials exhibit unique properties that can be advantageously tuned through choice of the inorganic and organic components and by control of the crystal structure. We present a new hydrothermally prepared 3D hybrid framework, [Mn(2-methylsuccinate)](n) (1), comprising alternating 2D manganese oxide sheets and isolated MnO(6) octahedra, pillared via syn, anti-syn carboxylates. Powder magnetic characterization shows that the compound is a homospin Mn(II) ferrimagnet below 2.4 K. The easy-axis is revealed by single-crystal magnetic susceptibility studies and a magnetic structure is proposed. Anisotropic elastic moduli and hardness, observed through nanoindentation on differing crystal facets, were correlated with specific structural features. Such measurements of anisotropy are not commonly undertaken, yet allow for a more comprehensive understanding of structure-property relationships.