Abstract
The two-dimensional silicon backbone structure of planar polysilane and W\"ohler siloxene is responsible for their exciting luminescing properties. We have prepared single crystals of siloxene by a topotactic reaction from crystalline CaSi${}_{2}$. The chemical composition was determined as [Si${}_{6}$H${}_{3}$(OH)${}_{3}$]${}_{n}.$ The x-ray crystal structure analysis identifies the so-called W\"ohler siloxene as 2D-poly[1,3,5-trihydroxocyclohexasilane]. Polysilane exhibits the same structural properties but with a chemical composition [Si${}_{6}$H${}_{6}$]${}_{n}.$ The optical properties (infrared transmission, photoluminescence, excitation spectroscopy) of these well-defined materials are presented. A heat treatment above $350\ifmmode^\circ\else\textdegree\fi{}$C in vacuum of W\"ohler siloxene results in a destruction of the planar ${}_{\ensuremath{\infty}}^{2}$ [Si${}^{\ensuremath{-}}$] structure by internal rearrangements, which is evidenced by the x-ray-diffraction pattern and characteristic changes in the optical spectra. The involvement of W\"ohler siloxene in the optical properties of porous Si is critically reviewed.
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