Electrically conductive charge-segregated pseudo-polymorphs comprising highly planar expanded π-electronic cations

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Organic Electronics

Background:

• Charge-segregated columnar structures are crucial for desirable electronic properties.
• Benzoporphyrin derivatives are typically insoluble, limiting their applications.

Purpose of the Study:

• To synthesize soluble benzoporphyrin Au^III complexes for charge-segregated assemblies.
• To investigate the impact of counteranions on assembly structure and properties.
• To explore the electric conductivity of these novel materials.

Main Methods:

• Synthesis of benzoporphyrin Au^III complex ion pairs with bulky counteranions.
• X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (NMR) for structural analysis.
• Molecular dynamics (MD) simulations to understand ion arrangement.
• Electric conductivity measurements.

Main Results:

• Synthesized soluble ion pairs of benzoporphyrin Au^III complex.
• Identified two pseudo-polymorphs: single-crystal and less-crystalline (LeC) states.
• LeC states arise from less-ordered ion arrangements due to bulky counteranions.
• Observed electric conductivity in both assembly states.

Conclusions:

• Bulky counteranions enhance solubility and influence the self-assembly of benzoporphyrin Au^III complexes.
• Charge-segregated assemblies, even in less-ordered states, exhibit electric conductivity.
• These findings offer potential for developing new organic electronic materials.