In situ transformations of selenidostannate frameworks in ionic liquids (ILs) were initiated by treatment of the starting phase K2[Sn2Se5] and the consecutive reaction products by means of temperature increase and/or amine addition. Along the reaction pathway, the framework dimensionalities of the five involved selenidostannate anions develop from 3D to 1D and back, both in top-down and bottom-up style. Addition of ethane-1,2-diamine (en) led to the reversion of the 2D→1D step from 2D-{[Sn24Se56](16-)} to 1D-{[Sn6Se14](4-)}. As rationalized by DFT investigations, the 2D anion is thermodynamically favored. Photoconductivity measurements reveal that all samples show Schottky contact behavior with absolute thresholds below 10 V. One of the samples exhibits conductive states within the energy range of visible photons.
Changes in the Structural Dimensionality of Selenidostannates in Ionic Liquids:Formation, Structures, Stability, and Photoconductivity. -The new selenidostannate compounds (II), (III), and (IV) are formed in ionic liquids, following unprecedented transformation pathways that include dimensionality changes of the anionic Sn/Se substructures. A temperature-induced deconstruction of the three-dimensional framework of (I) through the layered phase of (II) to an infinite double-chain motif in (III) or (IV) is observed. DFT calculations suggest that the transformations are provoked by competing influences of temperature and amine addition. Yields of the compounds are given in g. Products are characterized by single crystal XRD and UV/VIS spectroscopy. (II) crystallizes in the trigonal space group P32 with Z = 3, (III) in the monoclinic space group P2 1 /c with Z = 4, and (IV) in the triclinic space group P1 with Z = 2. Photoconductivity measurements show Schottky contact behavior with absolute thresholds below 10 V for all the samples. -(LIN, Y.; XIE, D.; MASSA, W.; MAYRHOFER, L.; LIPPERT, S.; EWERS, B.; CHERNIKOV, A.; KOCH, M.; DEHNEN*, S.; Chem. -Eur. J. 19 (2013) 27, 8806-8813, http://dx.
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