Studies on photochemical reactions of air pollutants. XV. Photoreactivity of heptachloro-3'-cyclopentenyldioxy heptachloro-2-cyclopentene formed by exposure of hexachlorocyclopentadiene to ultraviolet light in air.

Hexachlorocyclopentadiene (HCCP, 1), one of the starting materials in the synthesis of aldrin (3), was found to be able to epoxidize aldrin (3) to give dieldrin (4) when exposed to artificial light at wavelengths longer than 290 nm. In this photochemical reaction, heptachloro-3'-cyclopentenyldioxy heptachloro-2-cyclopentene (2) was isolated as a key intermediate, which appears to be derived from the interaction between the triplet state of photo-excited HCCP (1) and triplet oxygen (3sigma(g)-), but not from that between the ground state of HCCP (1) and singlet oxygen (1delta(g)). The peroxide (2) plays an important role in the formation of dieldrin (4), because it utilized oxygen atom derived from oxygen in air for the epoxidation.

Physicochemical and crystallographic characterization of mefenamic acid complexes with alkanolamines.

The preparation of mefenamic acid (MH)-alkanolamine (propanolamine, diethanolamine, triethanolamine) complexes was attempted to increase the transdermal flux of MH. Differential scanning calorimetry, Fourier transform infrared spectroscopy, and X-ray crystallographic studies demonstrated that MH and each alkanolamine formed an ion pair complex. The series of amine complexes had a lower melting point and higher solubility in water compared with pure MH.

Tuning of Spin Density Wave Strengths in Quasi-One-Dimensional Halogen-Bridged Ni(III) Complexes with Strong Electron Correlations, [Ni(III)(chxn)(2)X]Y(2).

A series of quasi-one-dimensional halogen-bridged Ni(III) complexes, [Ni(chxn)(2)X]Y(2) (chxn = 1R,2R-diaminocyclohexane; X = Cl, Br, and mixed halides; Y = Cl, Br, mixed halides, NO(3), BF(4), and ClO(4)) have been synthesized in order to investigate the effect of the bridging halogens and counteranions on their crystal, electronic structures, and moreover the spin density wave strengths. In the crystal structures, the [Ni(chxn)(2)] moieties are symmetrically bridged by halogen ions, forming linear-chain Ni(III)-X-Ni(III) structures. The hydrogen bonds between the aminohydrogens of chxn and the counteranions are constructed not only along the chains but also over the chains, forming the two-dimensional hydrogen-bond networks. While the Ni(III)-X-Ni(III) distances or b axes are almost constant in the compounds with the same bridging halogens, the c axes which correspond to the interchain distances in the directions of the interchain hydrogen bonds are remarkably lengthened with the increase of the ionic radius of the counterions; X < NO(3) < BF(4) < ClO(4). These compounds show the very strong antiferromagnetic interactions among spins on Ni 3d(z)2 orbitals through the superexchange mechanisms via the bridging halogen ions. Judging from the results of X-ray photoelectron spectra (XPS), Auger spectra, and single-crystal reflectance spectra, these Ni compounds are not Mott-insulators but charge-transfer-insulators. Their electronic structures or the spin density wave strengths are found to be tuned by the combinations of the counteranions and the bridging halogens.