Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

Hanau, Katharina; Schwan, Sebastian; Schäfer, Moritz; Müller, Marius J.; Dues, Christof; Rinn, Niklas; Sanna, Simone; Chatterjee, Sangam; Mollenhauer, Doreen; Dehnen, Stefanie

doi:10.1002/anie.202011370

Cited by 18 publications

(45 citation statements)

References 40 publications

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“…[15] (2). [15] Angewandte Chemie Forschungsartikel [(StySi) 4 S 6 ]( 2). However,o nly the crude product could be isolated upon evaporation of the solvent in form of acolorless "solid" with the consistencyo fc otton candy or honeydepending on the duration of the reaction and drying process.…”

Section: Resultsmentioning

confidence: 99%

“…4:S i ÀS2.095(2)-2.1589(3), SÀAu 2.297(2), AuÀP2.256(2), SiÀC1.865( 8), SiÀSÀSi 82.58( 10), SÀSiÀS97.42( 10)-115.64( 10), SiÀSÀ Au 103.57( 9), SÀAuÀP173.35 (7). [15] Tabelle 1: 29 Si NMR shifts of compounds I-IV, 1, 2,and 4 reported in this work. Angewandte Chemie…”

Section: Quantum Chemical Investigation Of Structural Featuresmentioning

confidence: 99%

“…Hatoms omitted for clarity; pstacking and CH/p-interactions are indicated as dashed lines. Selected distances and angles [, 8 8]: SiÀCl 2.0313(7)-2.0385(7)), SiÀC1 .8426(18); ClÀSiÀCl 106.42(3)-107.58(3), ClÀSiÀC1 11.42(6)-112.56(6), C Np •••p (red) 3.4397(18), C Np -H•••p (blue) 2.9371(1) [15].…”

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confidence: 99%

“…Molecular structure of 1 (top) and visualization of the two different orientationsofthe organic substituents in the two individuals within the asymmetric unit (bottom);t he structure at the top refers to the bottom right individual.E llipsoids drawn at 50 %probability level. Hatoms omitted for clarity.S elected distances and angles [, 8 8]: SiÀS 2.111(3)-2.153(3), SiÀC1.837(8)-1.876(8);Si ÀSÀSi 103.42(11)-105.64(13), SÀSiÀS110.31(12)-113.28(12), SÀSiÀC104.1(3)-110.1-(2) [15].…”

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confidence: 99%

“…Hatoms and P-bound phenyl groups omitted for clarity.Selected distances and angles [, 8 8]: 3:Si ÀS2.091(2)-2.144(2), SÀAu 2.3136(16), AuÀP2.2534(16), SiÀC1 .870(7);Si ÀSÀSi 82.40(9), SÀSiÀS97.60(9)-115.54(10),S i ÀSÀAu 90.97(7), SÀAuÀP 178.03(6). 4:S i ÀS2.095(2)-2.1589(3), SÀAu 2.297(2), AuÀP2.256(2), SiÀC1.865(8), SiÀSÀSi 82.58(10), SÀSiÀS97.42(10)-115.64(10), SiÀSÀ Au 103.57(9), SÀAuÀP173.35(7) [15].…”

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Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

et al. 2020

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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.

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Section: Quantum Chemical Investigation Of Structural Featuresmentioning

confidence: 99%

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Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

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Cluster‐Glass for Low‐Cost White‐Light Emission

et al. 2022

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The term "supercontinuum generation" describes an extreme spectral broadening of an originally monochromatic light beam upon propagating through a nonlinear medium, [8,10] as an alternative to the conventional generation of white light by means of inorganic phosphors or inorganic as well as organic semiconductors. [14][15][16] The broad spectrum obtained may cover the entire visible spectral range; in these cases, the observed emission resembles white light and the process is therefore referred to as WLG. The physical mechanisms underlying supercontinuum generation can be diverseand can also occur as a combination of nonlinear optical effects, like self-phase and cross-phase modulation, four-wave mixing, or solitonic phenomena. [17][18][19][20] While in most cases pulsed-laser sources are required for such processes, WLG upon irradiation of a material with a near-infrared continuous-wave (NIR CW) laser of significantly lower costs (by a factor of ≈10 3 …10 4 as compared to the pulsed lasers) has been reported for (doped) oxides or oxidic hybrid compounds, for complexes of rare-earth metals, and for carbon-based solids. [1] Given the complexity of the processes, different compounds exhibiting WLG can show the extreme nonlinear effects owing to different reasons or different combinations of mechanisms, which in many cases have not yet been fully elucidated to date.The development of efficient and high-brilliance white-light sources is an essential contribution to innovative emission technologies. Materials exhibiting strong nonlinear optical properties, in particular second-harmonic generation (SHG) or white-light generation (WLG), have therefore been investigated with great activity in recent times. While many new approaches have been reported until now, the processability of the compounds remains a challenge. Here, a new class of materials, denoted as "cluster-glass", which do not only show superior white-light emission properties upon irradiation by an inexpensive continuous-wave infrared laser diode, but can be easily accommodated in size and shape by formation of robust glassy solids, is introduced. The cluster-glass materials are fabricated by mild heating from crystalline powders of adamantane-type clusters exhibiting a quaternary, inorganic-organic hybrid cluster core [(PhSi)(CH 2 ) 3 (PhSn)E 3 ] (E = S, Se, Te). The process is fully reversible and preserves the integrity of the clusters in the glass, as proven by solution spectroscopy and recrystallization. Theoretical studies corroborate the importance of the quaternary nature of the cluster cores for the observed structural and optical phenomena. Thanks to these findings, high-brilliance white-light sources can be synthesized in form of stable, robust glass of any shape, which ultimately renders them suitable for everyday's applications.

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Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

Stellhorn

Hayakawa

Klee

et al. 2022

Advanced Optical Materials

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The local structure of four amorphous organotin sulfide compounds is investigated by X‐ray absorption spectroscopy. These compounds exhibit a nonlinear optical (NLO) response upon irradiation with a continuous‐wave near‐infrared laser. Their basic structural motif is a hetero‐adamantane cluster with different organic substituent, but depending on the morphology of the compound and the choice of the organic substituent, the nature of the NLO response changes to either a second harmonic generation or the generation of a supercontinuum, potentially appearing as white light. The structural results provide an experimental evidence that the nature of the NLO properties is tied to distortions occurring at the cluster core, with almost ideal clusters in compounds that show second harmonic generation, and strongly distorted clusters in the case of compounds that generate a supercontinuum. These distortions may enable a closer proximity of the cluster cores, altering the intermolecular order, and thereby influencing the NLO response.

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Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

Cited by 18 publications

References 40 publications

Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

Cluster‐Glass for Low‐Cost White‐Light Emission

Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

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