A structural study of a three-membered linear metal chain compound at elevated pressure

Area of Science:

• Solid-state chemistry
• Materials science
• Crystallography

Background:

• Molecular wires are compounds with potential applications in molecular electronics.
• Understanding their structural response to external stimuli like pressure is crucial for device design.

Purpose of the Study:

• To investigate the structural changes of Co3(dpa)4Cl2·(dcm) under high pressure.
• To elucidate the relationship between pressure, electronic states, and molecular packing.

Main Methods:

• Single crystal X-ray diffraction up to 3.6 GPa using synchrotron and conventional sources.
• Extensive theoretical calculations.
• Analysis of void spaces and Hirshfeld surfaces.

Main Results:

• The terminal Co-Cl bond distance initially increases then decreases with pressure.
• A thermally excited state with increased Co-Cl anti-bonding character is proposed at 0.32 GPa.
• Significant changes in solvent molecule occupancy and approaching metal chains with H···H interactions observed at high pressure.

Conclusions:

• Pressure induces complex structural and electronic rearrangements in Co3(dpa)4Cl2·(dcm).
• Hirshfeld surface analysis provides insights into intermolecular interactions and packing under pressure.
• Findings contribute to understanding the mechanical and electronic properties of molecular wires.