Disilanes are organosilicon compounds that contain saturated Si-Si bonds. The structural characteristics of Si-Si single bonds resemble those of C-C single bonds, but their electronic structure is more similar to that of C[double bond, length as m-dash]C double bonds, as Si-Si bonds have a higher HOMO energy level. These organosilicon compounds feature unique intramolecular σ electron delocalization, low ionization potentials, polarizable electronic structure, and σ-π interaction. It has been demonstrated that the employment of disilane units (Si-Si) is a versatile and effective approach for finely adjusting the photophysical properties of organic materials in both solution and solid states. In this review, we present and discuss the structure, properties, and relationships of novel σ-π-conjugated hybrid architectures with saturated Si-Si σ bonds. The application of disilane-bridged σ-conjugated compounds as optoelectronic materials, multifunctional solid-state emitters, CPL, and non-linear optical and stimuli-responsive materials is also reviewed.
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http://dx.doi.org/10.1039/d3sc02690f | DOI Listing |
Phys Chem Chem Phys
January 2025
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
We present first-principles molecular dynamics simulations of oxygen difluoride impinging upon the monohydrogenated Si{001}(2 × 1) surface. Adsorption occurred in fewer than 10% of our computed trajectories, but in each reactive case the initial step involved partial dissociation to yield an adsorbed fluorine atom and a free oxygen monofluoride radical. In one trajectory, the adsorbed fluorine atom displaced a hydrogen atom into an unusual Si-H-Si bridge position, consistent with three-centre two-electron bonding.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
State Key Laboratory of Elemento-Organic Chemistry and Frontiers Science Center of New Organic Matter, Nankai University, Tianjin 300071, People's Republic of China.
Controlled oxidation of NHB-stabilized disilyne (NHB)Si ≡ Si(NHB) (, NHB = [ArN(CMe)NAr]B, Ar = 2,6-PrCH) with one equivalent of trimethylamine N-oxide (MeN─O) in dry -hexane gave oxo-bridged bis-silepin in high yields. DFT calculations disclosed that silepin is only more stable by 13.4 kcal/mol than the corresponding oxo-bridged bis-silylene intermediate (NHB)Si(μ-O)Si(NHB), and was very likely to be formed by the insertion of the two divalent Si atoms into the pendant aryl rings in bis-silylene intermediate .
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 115, Sekr. C2, 10623, Berlin, Germany.
The facile reaction of the SiPh-bridged bis-silylene (LSi:)SiPh (L=PhC(NBu)) with diphenylacetylene affords the unprecedented 1,2,3-trisilacyclopentadiene (LSi)(PhC)SiPh 1 with a hypercoordinate λSi-λSi double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert NO to form the bicyclic oxygenation product 2 through O-atom insertion in the Si=Si and Si-Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3-disilacyclopentadiene 3, representing the first hypercoordinate example of a cyclosilene with a λSi-λC double bond.
View Article and Find Full Text PDFInorg Chem
September 2024
School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, Xi'an Jiaotong University, Xi'an 710049, China.
The construction of the unsymmetrical 1,2-bis(silylene) pentacarbonyl chromium(0) complex was achieved through the reaction of chlorosilylene with half an equivalent of KCr(CO). X-ray diffraction analysis of confirms the formation of the Si-Si bond and the coordination of one of the silicon atoms to the Cr center. Density functional theory (DFT) calculations disclose that highest occupied molecular orbital (HOMO) mainly corresponds to the lone pair of electrons on the silicon atom and the σ-bonding interaction between two Si atoms.
View Article and Find Full Text PDFJ Hazard Mater
October 2024
State Key Laboratory of Earth Surface Processes and Resource Ecology, Faculty of Geographical Science, Beijing Normal University, Beijing 100875, China.
In this study, a high-Si (Si) adsorbent (APR@Sam) was prepared by acid leaching slag (APR) from lead-zinc (Pb-Zn) tailings based on high-temperature alkali melting technology. The synthesized Si-based materials were applied to aqueous solutions contaminated with Pb and cadmium (Cd) to investigate the crucial role of active Si in sequestering heavy metals. The adsorption capacities of APR@Sam and the Si-depleted material (APR@Sam-NSi) were studied under different pH and temperature conditions.
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