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Quenched calcium-doped lanthanum cuprate (La 2 CuO 4 ) samples were examined at room temperature using extended X-ray absorption fine structure (EXAFS) analysis and X-ray absorption near-edge spectroscopy (XANES) near the CaK edge, and via atomic-and electronicstructure modeling. Calculations and experiments show that the Ca atom, in a manner similar to that of Sr and Ba atoms, replaces the La atom and maintains its nine-fold coordination above the center of a CuO 4 square, which is the nominal position of the La atom. In contrast to the Sr and Ba atoms, the distances from Ca to its nearest neighbors are similar to the size of the La 3؉ cation. The distances that are obtained from the simulation are in reasonable agreement with the experimental results for calcium, as well as previous studies that involved strontium and barium. The binding of a calcium dopant to vacancies on the O(1) sites is stable, but only slightly; therefore, there are probably many different types of such clusters. This calculated binding also is supported by the EXAFS data. The overall electronic structure is similar to that observed in calculations for pure La 2 CuO 4 : the LaO planes remain ionic, even with the presence of the calcium dopant, and the Cu−O(1) bond is covalent. The calcium is ionic in character, with a net charge of 1.6, and the narrow Ca 3d band lies ∼6 eV above the Fermi energy level.

Metal-free and copper porphyrazines, [H(2)pz] and [Cu pz], have been fused at the periphery with molybdocene dithiolene, [Cp(2)Mo]. The optical, magnetic, and electronic properties of the resulting neutral and cationic complexes are studied, using first-principles density functional theory implemented by the discrete variational method. Analysis of the charge and spin distribution shows that the porphyrazine core is strongly coupled with the peripheral complex. The calculated optical absorption is found to be in reasonable agreement with experimental spectra, lending support to our theoretical model. Under appropriate circumstances one observes interaction of unpaired spins localized in the vicinity of both metal sites. The calculated spin distribution shows that [Cp(2)Mo][Cu pz] and [Cp(2)Mo][H(2)pz](+) have a magnetic moment of 1 micro(B) while [Cp(2)Mo][Cu pz](+) and [Cp(2)Mo][H(2)pz] have no moment, in good agreement with the results of X-band EPR spectra. The Cu-Mo magnetic interaction is antiferromagnetic, being mediated by pyrrol nitrogens, meso nitrogens, carbons, and sulfurs.

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