研究目的
To develop an atomically precise protocol for the expansion of unsaturated silicon clusters from six to seven and eight vertices using specific reagents.
研究成果
The study successfully demonstrates a stepwise and atomically precise expansion of silicon clusters from Si6 to Si7 and Si8 vertices using decamethylsilicocene as an electrophile, with potential for infinite repetition and application to heteroatom-doped clusters beyond silicon.
研究不足
The protocol may have limitations in yield and reproducibility for larger clusters; the use of specific ligands (Tip and Cp*) might restrict generality; computational methods may not fully capture all electronic effects.
1：Experimental Design and Method Selection:
The study involves the use of lithium/naphthalene as a reducing agent and decamethylsilicocene (SiCp*2) as an electrophilic silicon source to expand silicon clusters. Theoretical calculations (B3LYP/def2-TZVP and OLYP/def2-TZVP levels) are employed to predict and confirm structures and NMR chemical shifts.
2：Sample Selection and Data Sources:
The anionic siliconoid Si6R5- (12, R = Tip) is used as the starting material. Samples are synthesized and characterized.
3：List of Experimental Equipment and Materials:
Key materials include lithium, naphthalene, tetrahydrofuran (thf), decamethylsilicocene, and solvents like C6D6 and pentane. Equipment includes NMR spectrometers for 1H and 29Si NMR, and X-ray diffractometers for structural analysis.
4：Experimental Procedures and Operational Workflow:
- Reduction of siliconoid 12 with lithium/naphthalene in thf at -100°C to form anionic species. - Reaction with SiCp*2 to expand the cluster to Si7 and Si8 species. - Characterization using NMR spectroscopy and X-ray crystallography. - Hydrolysis experiments with H2O to form adducts.
5：Data Analysis Methods:
NMR data are analyzed to assign chemical shifts and confirm structures. X-ray diffraction data are used to determine molecular structures. Computational methods (B3LYP and OLYP functionals with def2-TZVP basis set) are used for geometry optimization and NMR shift calculations.
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