Katharina Hanau1, Sebastian Schwan2,3, Moritz R Schäfer2,3, Marius J Müller4, Christof Dues5, Niklas Rinn1, Simone Sanna5, Sangam Chatterjee4, Doreen Mollenhauer2,3, Stefanie Dehnen1. 1. Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35043, Marburg, Germany. 2. Institute of Physical Chemistry, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392, Giessen, Germany. 3. Center for Materials Research (LaMa), Justus Liebig University Giessen, Heinrich-Buff-Ring 16, 35392, Giessen, Germany. 4. Institute of Experimental Physics I and Center for Materials Research (LaMa), Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392, Giessen, Germany. 5. Institute of Theoretical Physics and Center for Materials Research (LaMa), Justus Liebig University Giessen, Heinrich-Buff-Ring 16, 35392, Giessen, Germany.
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.
We report the extension of the class of pan class="Chemical">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.