We report the extension of the class of organotetrel sulfide clusters with 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 reactions with [AuCl(PPh
3
)] to form ternary complexes. DFT studies of cluster dimers helped us understand the differences between the habit of {Si
4
S
6
}‐ and {Sn
4
S
6
}‐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
S
6
] clusters (R=Ph, Np). The calculations reproduced the measured data and allowed for the interpretation of the main spectroscopic features.
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 Na2S. Besides known [(PhSi)4S6] (IV), new compounds [(NpSi)4S6] (1) and [(StySi)4S6] (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 {Si4S6}‐ and {Sn4S6}‐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)4S6] clusters (R=Ph, Np). The calculations reproduced the measured data and allowed for the interpretation of the main spectroscopic features.
Clusterchemie. Im Forschungsartikel auf S. 1196 berichten Simone Sanna, Sangam Chatterjee, Doreen Mollenhauer, Stefanie Dehnen et al. über Untersuchungen der weitgehend unerforschten Siliciumchalkogenid‐Cluster [(RSi)4S6] und deren Reaktion mit [AuCl(PPh3)].
Clusters. In their Research Article on page 1176, Simone Sanna, Sangam Chatterjee, Doreen Mollenhauer, Stefanie Dehnen et al. report on studies of the largely unexplored silicon chalcogenide clusters [(RSi)4S6] and their reactions with [AuCl(PPh3)].
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