Pressure-induced polymerization of P(CN)3.

Area of Science:

• Materials Science
• Solid-State Chemistry
• High-Pressure Physics

Background:

• Investigating novel extended carbon-nitrogen solids is crucial for developing advanced materials.
• Molecular precursor pathways offer controlled synthesis routes for complex structures.
• Phosphorous tricyanide (P(CN)3) is a potential precursor for new materials.

Purpose of the Study:

• To explore the chemical reactivity of pure phosphorous tricyanide (P(CN)3) under high pressure.
• To investigate the formation of novel extended phosphorous carbon nitride (PCN) solids.
• To characterize the structural and vibrational properties of P(CN)3 under compression.

Main Methods:

• High-pressure experiments using Raman and infrared (IR) spectroscopy.
• Synchrotron powder X-ray diffraction (XRD) for structural analysis.
• First-principles molecular-dynamics simulations for theoretical insights.

Main Results:

• Phase transformations observed in P(CN)3 below 10 GPa.
• P(CN)3 exhibits high compressibility (bulk modulus of 10.0 ± 0.3 GPa).
• Amorphization and polymerization into a novel PCN phase occurs above ~10.0 GPa, characterized by sp(2) hybridized CN bonds.

Conclusions:

• A novel, recoverable phosphorous carbon nitride (PCN) polymeric phase is formed from P(CN)3 under high pressure.
• The amorphization transition involves polymerization of cyanide groups, yielding a material analogous to known carbon nitrides.
• This study demonstrates a viable molecular precursor pathway for synthesizing novel PCN materials.