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Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters.


ABSTRACT: We report the extension of the class of organotetrel sulfide clusters with further examples of the still rare silicon-based species, synthesized from RSiCl3 with R=phenyl (Ph, I), naphthyl (Np, II), and styryl (Sty, III) with Na2 S. Besides known [(PhSi)4 S6 ] (IV), new compounds [(NpSi)4 S6 ] (1) and [(StySi)4 S6 ] (2) were obtained, the first two of which underwent reactions with [AuCl(PPh3 )] to form ternary complexes. DFT studies of cluster dimers helped us understand the differences between the habit of {Si4 S6 }- and {Sn4 S6 }-based compounds. Crystalline 1 showed a pronounced nonlinear optical response, while for intrinsically amorphous 2, the chemical damage threshold seems to inhibit a corresponding observation. Calculations within the independent particle approximation served to rationalize and compare electronic and optical excitations of [(RSi)4 S6 ] clusters (R=Ph, Np). The calculations reproduced the measured data and allowed for the interpretation of the main spectroscopic features.

SUBMITTER: Hanau K 

PROVIDER: S-EPMC7839700 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters.

Hanau Katharina K   Schwan Sebastian S   Schäfer Moritz R MR   Müller Marius J MJ   Dues Christof C   Rinn Niklas N   Sanna Simone S   Chatterjee Sangam S   Mollenhauer Doreen D   Dehnen Stefanie S  

Angewandte Chemie (International ed. in English) 20201215 3


We report the extension of the class of organotetrel sulfide clusters with further examples of the still rare silicon-based species, synthesized from RSiCl<sub>3</sub> with R=phenyl (Ph, I), naphthyl (Np, II), and styryl (Sty, III) with Na<sub>2</sub> S. Besides known [(PhSi)<sub>4</sub> S<sub>6</sub> ] (IV), new compounds [(NpSi)<sub>4</sub> S<sub>6</sub> ] (1) and [(StySi)<sub>4</sub> S<sub>6</sub> ] (2) were obtained, the first two of which underwent reactions with [AuCl(PPh<sub>3</sub> )] to  ...[more]

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