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.

Amorphous materials are integral part of today´s technology, they commonly are performant and versatile in integration. Consequently, future applications increasingly aim to harvest the potential of the amorphous state. Establishing its structure-property relationship, however, is inherently challenging using diffraction-based techniques yet is extremely desirable for developing advanced functionalities. In this article, we introduce a set of transmission electron microscopy-based techniques to locally quantify the structure of a material. This unique approach allows to clearly identify the spatial distribution of amorphous and crystalline regions and to quantify atomic arrangements of amorphous regions of a representative model system. We study an ensemble of well-defined, functionalized adamantane-type cluster molecules exhibiting exceptionally promising nonlinear optical properties of unclear origin. The nanoscopic structure for three model compounds ([(PhSn)4S6], [(NpSn)4S6], [(CpSn)4S6]) correlates with their characteristic optical responses. These results highlight the advantageous properties of amorphous molecular materials when understanding the microscopic origin.

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)].

The family of group 14 tetra-aryl tetrels with cemical formula X(C 6 H 5 ) 4 and X = C, Si, Ge, Sn, Pb is investigated both theoretically and experimentally. Calculations in the framework of the density functional theory are employed to model the structural, vibrational, electronic and optical properties of the clusters, both as single molecules and in their crystalline form.