THE ORIGIN OF THE 321-nm ABSORPTION OBSERVED IN THE CRYSTAL SPECTRA OF Ba[Pd($CN_{4})]\cdot4H_{2}O$.

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1981

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Ohio State University

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A number of planner $d^{8}$ transition-mental complexes form crystals in which the complexes show columnar stacking and relatively short metal-metal distances. These crystals typically have a strong electronic absorption in a region where the solution spectrum of the complex involved shows no comparable absorption. In order to establish the ``single-molecule’’ origin of such absorptions observed in the barium salts of the Pt(II), Pd(II), and Ni(II) tetracyanides, polarized single-crystal absorption spectra of Ba[Pd$(CN)_{4}]\cdot 4H_{2}O$ and a series of salts obtained from it via the replacement of $Ba^{2+}$ with other cations have been determined. This series shows a variety of intercomplex spacings, and thus allows one to relate the ``crystal’‘ band to an absorption found in the solution spectrum of $Pd(CN)_{4}^{2-}$. These results will be presented and discussed in terms of similar studies on related systems.

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