Interdigitated Pt-Br chains with π-stacking: an approach toward Robin-Day class I mixed valency in MX-chain complexes

Area of Science:

• Coordination Chemistry
• Materials Science
• Solid-State Chemistry

Background:

• MX chain complexes are studied for their unique electronic and optical properties.
• Achieving specific mixed valence states, like the Robin-Day class I, is key for material applications.
• Controlling intermolecular interactions, such as π-stacking, is vital for tuning material properties.

Purpose of the Study:

• To synthesize the first interdigitated MX-type chain complex featuring infinite π-stacked arrays.
• To investigate the relationship between Pt-Br⋯ chain synchronization and π-stacking periodicities.
• To achieve and characterize the Robin-Day class I mixed valence state in these novel MX chains.

Main Methods:

• Synthesis of a novel interdigitated MX-type chain complex.
• Single-crystal X-ray diffraction analysis to determine structural parameters.
• Spectroscopic methods to evaluate intervalence charge transfer (ICT).

Main Results:

• Successful synthesis of the first interdigitated MX-type chain complex with infinite π-stacked arrays.
• Observed synchronization between the Pt-Br⋯ chain and π-stacking periodicities.
• Achieved the longest M-X-M distance to date (6.6978(15) Å).
• Demonstrated nil or negligible intervalence charge transfer, indicative of a class I mixed valence state.

Conclusions:

• The synthesized complex represents a significant advancement in MX chain materials.
• The synchronization of structural features is critical for achieving desired electronic states.
• This work provides a pathway for designing advanced materials with tailored mixed valence properties.