X-ray structure analysis and the intervalent electron transfer in organic mixed-valence crystals with bridged aromatic cation radicals

X-ray crystallography identifies the aromatic donor group D = 2,5-dimethoxy-4-methylphenyl to be a suitable redox center for the construction of organic mixed-valence crystals owing to its large structural change attendant upon 1e oxidation to the cation-radical (D*(+)). The combination of cyclic voltammetry, dynamic ESR line broadening, and electronic (NIR) spectroscopy allows the intervalence electron transfer between the redox centers in the mixed-valence system D-br-D*(+) [where br can be an aliphatic trimethylene or an aromatic (poly)phenylene bridge] to be probed quantitatively. Independent measures of the electronic coupling matrix element (H) for D/D*(+) electron exchange via Mulliken-Hush theory accord with the X-ray crystallographic data-both sufficient to consistently identify the various D-br-D*(+) according to the Robin-Day classification. Thus, the directly coupled biaryl D-D*(+) is a completely delocalized cation in class III with the charge distributed equally over both redox centers. The trimethylene- and biphenylene-bridged cations D(CH(2))(3)D*(+) and D(ph)(2)D*(+) with highly localized charge distributions are prototypical class II systems involving moderately coupled redox centers with H approximately equal to 400 cm(-1). The borderline region between class II/III is occupied by the phenylene-bridged cation D(ph)D*(+); and the X-ray, CV, and NIR analyses yield ambivalent H values (which we believe to be) largely a result of an unusually asymmetric (20/80) charge distribution that is polarized between the D/D*(+) redox centers.     

Electron Diffraction Analysis of the Fracture Zone of Fe–0.45C–17Mn–3Al Steel Subjected to Multicyclic Fatigue Tests

The methods of transmission electron microscopy are used to investigate the structure and phase content of Fe–0.45C–17Mn–3Al steel subjected to multicyclic fatigue tests to failure after intermediate electrostimulation. It is demonstrated that electrostimulation does not change the mechanism of steel failure. An increase in the operating life time of samples after electrostimulation in the intermediate test stage is connected with the hindered -martensitic transformation, the relaxation of stress concentrators, and the reduction of the volume fraction of the critical dislocation (network) substructure in which -martensite is mainly developed.     

Simulation of the Processes of Irreversible Aggregation in the Systems of Molecular Chains with Different Distribution of Associating Groups

The processes of the irreversible aggregation of chain molecules with various numbers of associating groups are studied by the Monte Carlo method using the Eden model. Three-dimensional lattice systems are considered. The model developed qualitatively reproduces the main structural (morphological) characteristics that are observed experimentally for the aggregates composed of macromolecules of ionic polymers under the conditions of strong segregation. It is established that the chains with one associating terminal group form tree-like coral-shaped aggregates; associating groups form the skeleton with a large number of branches at the periphery. It is shown that the chains with the number n _s 2 of associating groups form aggregates whose structures correspond to a three-dimensional network. Integral characteristics of a system are scale-invariant; molecular parameters, such as the chain length N and the number of associating groups n _s, enter into corresponding scaling dependences in the form of scaling multipliers N and n _s . Critical indices and , as well as main index determining the dependence of the mean aggregate sizes on the number n of constituting molecules, are estimated. It is established that an increase in the number of associating groups in a chain results in the formation of more compact aggregates with smaller characteristic size of a network cell. For the model considered, such an effective compression is explained by the intensification of branching, i.e., by the dispersal of growth points, rather than by the folding of chains (on the contrary, their substantial fraction is attached to the cluster in greatly extended conformations). The important role of intra- and interchain screening effects arising during the formation of local morphology of aggregates is demonstrated. As a result of such screening, the sizes of lattice nodes composed of associating groups seem to be the nonmonotonic function of the number of these groups in the chain.     

Electronic absorption spectra or carbonium and dicarbonium ions containing heterocyclic rings with a biphenylene base

An analysis has been made of -^* -electronic excitations of carbonium and dicarbonium ions obtained by the interaction of concentrated sulfuric or fluoboric acid with alcohols or glycols containing a heterocyclic bridge structure, i.e., nuclei of dibenzofuran, dibenzothiophene, carbazole, and N-methylcarbazole; this analysis has been aimed at establishing a correlation of their structure and spectral characteristics. From an analysis of experimental data, calculated results, and indexes quantitatively characterizing the structure of the -^* -electronic excitations, it has been established that there are four electronic transitions in the visible region of the electronic absorption spectrum of the carbonium ions. The long-wave, intense band of the spectrum is due to superposition of intense (p-type) and weak (-type) transitions proceeding from corresponding excitations of the heterocyclic fragment. In the electronic spectra of the dicarbonium ions, a doublet of p-transitions is clearly manifested. It has been shown that the interaction of chromophores through the bridge structure increases by a factor of approximately 1.8 when the change is made from dibenzofuran to dibenzothiophene, carbazole, and Nmethylcarbazole; in comparison with the corresponding dihydroxycarbonium ions, the degree of interaction of the chromophores is greater by a factor of approximately 1.5.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 3, pp. 284–291, May–June, 1990.