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Lead Oxychloride Borates Obtained under Extreme Conditions
Oleg I Siidra1, Houria Kabbour2, Olivier Mentre2
1Department of Crystallography, Saint-Petersburg State University , University emb. 7/9, 199034 St. Petersburg, Russia.
Inorganic Chemistry
|August 26, 2016
Summary
New lead oxyhalide compounds were synthesized under high temperature and pressure. These complex structures feature unique oxocentered lead units and demonstrate varied stereochemical activity of lead lone pairs.
Area of Science:
- Solid-state chemistry
- Inorganic materials science
- Crystal structure analysis
Background:
- Tetragonal α-PbO exhibits an ideal [OPb] layer structure.
- Understanding complex lead oxyhalides is crucial for materials development.
Purpose of the Study:
- Synthesize novel lead oxyhalide compounds using high-temperature, high-pressure methods.
- Characterize the crystal structures and electronic properties of the synthesized materials.
- Investigate the stereochemical activity of lead(II) lone pairs in these complex structures.
Main Methods:
- High-temperature, high-pressure synthesis experiments.
- Single-crystal X-ray diffraction for structural determination.
- Charge calculations and density of states (DOS) analysis.
- First-principle calculations to analyze lone pair behavior.
Main Results:
- Two new compounds, [Pb10O4]Pb2(B2O5)Cl12 (1) and [Pb18O12]Pb(BO2OH)2Cl10 (2), were successfully synthesized.
- Compound 2 features incorporated {Pb(10)Cl4(BO2OH)2} clusters within alternating PbO and chloride layers.
- Compound 1 exhibits [O4Pb10](12+) tetramers integrated into a 3D halogen matrix.
- Pb(II) lone pair activity varies, being stereochemically active on most Pb sites in compound 2 but inert on one site.
- Coordination environments of Pb atoms in compound 2 were classified into three groups based on ECCv and DOS.
Conclusions:
- The study presents the first analysis of unusual lead lone pair behavior in complex oxyhalide materials.
- The findings highlight the diverse structural motifs and electronic properties achievable in lead oxyhalides.
- This research provides insights into structure-property relationships in materials containing stereochemically active lone pairs.
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