DSC study of charge-transfer complexes of polynuclear aromatic hydrocarbons with nitroaromatic acceptors

Charge-transfer, crystalline complexes of 1,3,5-trinitrobenzene (TNB), 2,4,7- trinitro-9-fluorenone (TNF). and 2,4,5,7-tetranitro-9-fluorenone (TENF) with eleven polynuclear aromatic hydrocarbons were compared for thermal stability, ΔH and ΔS of melting. Factors possibly influencing the above parameters are discussed.Melting does not induce separation of the components; these complexes can be repeatedly crystallized and melted without variation of the ΔH of melting, thereby indicating high thermal stability.With a few exceptions, melting temperatures of the complexes increase in the order TNB<TNF<TENF: so do ΔH and ΔS of melting. A number of crystal transitions were observed.     

Formation of Se0 Nanoparticles in an Aqueous Cationic Polyelectrolyte

The nanostructures formed by reduction of Se(IV) in the selenite-ascorbate redox system in an aqueous solution of supermacromolecular polycation, poly[trimethyl(methacryloyloxyethyl)ammonium] methyl sulfate, were studied by static and dynamic optical scattering and flow birefringence.     

Rißbildung,Nachgiebigkeit und Bruch in Polycarbonat und Polyäthylenterephthalat bei tiefen Temperaturen

Ohne Zusammenfassung     

S=N versus S+-N-: an experimental and theoretical charge density study

To elucidate the bonding situation in the widely discussed hypervalent sulfur nitrogen species, the charge density distributions rho(r) and related properties of four representative compounds, methyl(diimido)sulfinic acid H(NtBu)(2)SMe (1), methylene-bis(triimido)sulfonic acid H(2)C[S(NtBu)(2) (NHtBu)](2) (2), sulfurdiimide S(NtBu)(2) (3), and sulfurtriimide S(NtBu)(3) (4), were determined experimentally by high-resolution low-temperature X-ray diffraction experiments (T = 100 K). This set of molecules represents an ideal frame of reference for the comparison of SN bonding modes, because they contain short formal S=N double bonds as well as long S-N single bonds, some of them influenced by inter- or intramolecular hydrogen bonds. For comparison, the gas-phase ab initio calculations of the four model compounds, H(NMe)(2)SMe, H(2)C[S(NMe)(2)(NHMe)](2), S(NMe)(2), and S(NMe)(3), were performed. The topological features were found to be not particularly sensitive with respect to different substituents R (R = H, Me, tBu). In this paper, it is documented that theory and experiment differ in the eigenvalues of the Hessian matrix because of systematically differing positions of the bond critical points but agree very well concerning the spatial Laplacian distribution and the distinct polarization of all investigated sulfur-nitrogen bonds. Both recommend the S(+)-N(-) formulation of sulfur nitrogen bonds in 1 and 2 since all nitrogen atoms are found to be sp(3) hybridized. The planar SNx (x = 2, 3) units in the diimide 3 and the triimide 4 reveal characteristics of m-center-n-electron systems. For none of the investigated S-N bonds, a classical double bond formulation can be supported. This is further substantiated by the NBO/NRT approach. Valence expansion to more than eight electrons at the sulfur atom can definitely be excluded to explain the bonding.     

Low-dimensional chainlike assemblies of TiO2 nanorod-stabilized Au nanoparticles

A simple and versatile light-based strategy to grow low-dimensional gold superstructures is presented; prolonged UV-irradiation of TiO2 nanorod-stabilized Au nanoparticles in organic media promotes the progressive formation of distinctive chainlike metal assemblies, namely segments of a few gold particles, 2D or quasi-1D large structures composed of interlacing lines of hundreds of metal units over areas of about 500 nm2.     

Coordination of aza heterocycles with macroheterocyclic metal complexes in amphiprotic media: III. Kinetics and mechanism of inner-sphere ligand exchange in (tetraphenylporphyrinato)chromium(III)

Inner-sphere replacement of alcohols by imidazole and its derivatives in the complex (acetato)-(tetraphenylporphyrinato)chromium(III) was studied by electronic absorption spectroscopy. The rate constants and activation parameters of the process were calculated. The entering ligand structure was shown to affect the reaction rate, while the alcohol nature (departing ligand) does not influence the kinetic parameters of the process to an appreciable extent. Regression analysis revealed participation of imidazole and ethanol in the rate-determining stages. The kinetic equation for the inner-sphere axial substitution implies interaction of a free alcohol molecule with that coordinated to chromium, followed by replacement of the associate by the heteroring. Mathematical processing of the kinetic data in terms of the proposed solvolytic association-dissociation mechanism gave the rate constants for particular stages of the process and showed an extremal relation between the rate constant and composition of the solvent.     

Analytical mass spectrometry

A review is made of the basic theory, instrumentation and application of mass spectrometry, with special reference to the development of the equipment and its impact on the scope of application.