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?:abstract
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We report about the successful extension of the class of organogtetrel sulfide clusters by further examples of the still rare silicon-based species, synthesized from RSiCl 3 with R = phenyl (Ph, I ), naphthyl (Np, II ), and styryl (Sty, III ) with Na 2 S. Besides known [(PhSi) 4 S 6 ] ( IV ), new compounds [(NpSi) 4 S 6 ] ( 1 ) and [(StySi) 4 S 6 ] ( 2 ) were obtained, the first two of which underwent follow-up reactions with [AuCl(PPh 3 )] to form ternary complexes. Density functional theory (DFT) studies of cluster dimers helped to understand fundamental differences between the habitus of {Si 4 S 6 }-based vs. {Sn 4 S 6 }-based compounds. Investigations of the optical properties of crystalline compound 1 and intrinsically amorphous 2 indicated the former to show a pronounced nonlinear optical response, i.e. , second-harmonic generation, while for the latter, the chemical damage threshold seems to inhibit a corresponding observation that can be clearly put down to nonlinear optical effects. Calculations within the independent particle approximation (IPA) served to rationalize and compare electronic and optical excitations of [(RSi) 4 S 6 ] clusters (R = Ph, Np). The calculations reproduced the measured data and allowed for the interpretation of the main spectroscopic features.
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