Spiro[4.4]nonatetraene and its Positive and Negative Radical Ions: Molectronic Structure Investigations

The electronic structure of spiro[4.4]nonatetraene 1 as well as that of its radical anion and cation were studied by different spectroscopies. The electron‐energy‐loss spectrum in the gas phase revealed the lowest triplet state at 2.98 eV and a group of three overlapping triplet states in the 4.5 – 5.0 eV range, as well as a number of valence and Rydberg singlet excited states. Electron‐impact excitation functions of pure vibrational and triplet states identified various states of the negative ion, in particular the ground state with an attachment energy of 0.8 eV, an excited state corresponding to a temporary electron attachment to the 2b₁ MO at an attachment energy of 2.7 eV, and a core excited state at 4.0 eV. Electronic‐absorption spectroscopy in cryogenic matrices revealed several states of the positive ion, in particular a richly structured first band at 1.27 eV, and the first electronic transition of the radical anion. Vibrations of the ground state of the cation were probed by IR spectroscopy in a cryogenic matrix. The results are discussed on the basis of density‐functional and CASSCF/CASPT2 quantum‐chemical calculations. In their various forms, the calculations successfully rationalized the triplet and the singlet (valence and Rydberg) excitation energies of the neutral molecule, the excitation energies of the radical cation, its IR spectrum, the vibrations excited in the first electronic absorption band, and the energies of the ground and the first excited states of the anion. The difference of the anion excitation energies in the gas and condensed phases was rationalized by a calculation of the Jahn‐Teller distortion of the anion ground state. Contrary to expectations based on a single‐configuration model for the electronic states of 1 , it is found that the gap between the first two excited states is different in the singlet and the triplet manifold. This finding can be traced to the different importance of configuration interaction in the two multiplicity manifolds.     

Synthesis of highly sulfonated poly(arylene ether sulfone) random (statistical) copolymers via direct polymerization

Novel biphenol‐based wholly aromatic poly (arylene ether sulfones) containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenyl sulfone (SDCDPS), 4,4′‐dichlorodiphenylsulfone (DCDPS) and biphenol. Copolymerization proceeded quantitatively to high molecular weight in N‐methyl‐2‐pyrrolidinone at 190°C in the presence of anhydrous potassium carbonate. Tough membranes were successfully cast from the control and the copolymers, which had a SDCDPS/DCDPS mole ratio of either 40:60 or 60:40 using N,N‐dimethylactamide; the 100% SDCDPS homopolymer was water soluble. Short‐term aging (30 min) indicates that the desired acid form membranes are stable to 220°C in air and conductivity values at 25°C of 0.110 (40%) and 0.170 S/cm (60%) were measured, which are comparable to or higher than the state‐of‐the art fluorinated copolymer Nafion 1135 control. The new copolymers, which contain ion conductivity sites on deactivated rings, are candidates as new polymeric electrolyte materials for proton exchange membrane (PEM) fuel cells. Further research comparing their membrane behavior to post‐sulfonated systems is in progress.     

INHIBITION OF NUCLEIC ACID SYNTHESIS IN CELLS EXPOSED TO 200 MICROMETER RADIATION FROM THE FREE ELECTRON LASER

Vertebrate tissue culture cells were exposed to 200 um wavelength radiation (1CO W/cm²) from a free electron laser (FEL) of the electrostatic generator type. Cell cultures demonstrated no morphological alterations but a statistically significant (P .05) proportion of the cells exhibited inhibition of DNA synthesis. This study demonstrates the first biological effects of the FEL and the feasibility of performing biological investigations with this device.     

Synthesis of 1,3,4-oxadiazol-2-ones with aliphatic groups at N-3

A series of 3-substituted-5-methoxy-1,3,4-oxadiazol-2-ones were prepared from aldehydes, ketones, phenylacetic acids, and 1,2- and 1,3-diketones. Conditions for the formation of these oxadiazolones from the precursor N-carbamoyl chlorides depended on the structure, and varied from spontaneous ring closure to those requiring bases. Variation in the N-3 substituents sometimes produced mixtures of isomers which were separated and identified. These molecules were prepared in order to study the effect of the N-3 substituent variation on the biological properties of oxadiazolones.     

Unsaturated Molecules Containing Main Group Metals

Molecules in which there are neighboring electrophilic and nucleophilic centers are unusually reactive. Oligomerization can be prevented only by bulky groups attached to the main group metal atom that would act as electron pair acceptor, or to the basic non-metal atom. The basic and the acid centers behave as a single unit in chemical reactions; the system is similar to a “double bond” whose π-electron density is largely concentrated at one atom. The unsaturated nature of these molecules can be seen in (for example) their addition reactions with hydrogen compounds of non-metals, or in reactions that are distantly related to cycloadditions at homopolar double bonds. The selection of suitable reaction partners leads to polycyclic, cage-like molecules containing metal atoms. If these atoms possess lone pairs (as is usual in the lower oxidation states of the third and fourth main groups), these can be utilized to form bonds to further (Lewis acid) metal centers. In some cases large assemblies can be built up from polycyclic systems in this way; a characteristic of these assemblies is a one-dimensional array of metal atoms. Commonly occurring structural features of the polycyclic species are tetrahedra, trigonal bipyramids and cubes.     

A powerful truncated Newton method for potential energy minimization

With advances in computer architecture and software, Newton methods are becoming not only feasible for large-scale nonlinear optimization problems, but also reliable, fast and efficient. Truncated Newton methods, in particular, are emerging as a versatile subclass. In this article we present a truncated Newton algorithm specifically developed for potential energy minimization. The method is globally convergent with local quadratic convergence. Its key ingredients are: (1) approximation of the Newton direction far away from local minima, (2) solution of the Newton equation iteratively by the linear Conjugate Gradient method, and (3) preconditioning of the Newton equation by the analytic second-derivative components of the “local” chemical interactions: bond length, bond angle and torsional potentials. Relaxation of the required accuracy of the Newton search direction diverts the minimization search away from regions where the function is nonconvex and towards physically interesting regions. The preconditioning strategy significantly accelerates the iterative solution for the Newton search direction, and therefore reduces the computation time for each iteration. With algorithmic variations, the truncated Newton method can be formulated so that storage and computational requirements are comparable to those of the nonlinear Conjugate Gradient method. As the convergence rate of nonlinear Conjugate Gradient methods is linear and performance less predictable, the application of the truncated Newton code to potential energy functions is promising.