Redox-Active Ruthenium-Organic Polyhedra with Tunable Surface Functionality and Porosities

Area of Science:

• Materials Science
• Coordination Chemistry
• Electrochemistry

Background:

• Dinuclear ruthenium paddlewheel complexes offer high stability in redox reactions.
• Ruthenium metal-organic polyhedra (RuMOPs) are promising redox-active porous materials.
• Synthesis of RuMOPs is challenging due to difficulties in controlling ligand-exchange assembly.

Purpose of the Study:

• To synthesize novel cuboctahedral RuMOPs using Ru2(II/III)-paddlewheel units.
• To investigate the impact of alkyl functionalization on RuMOP properties.
• To explore the redox behavior and tunability of functionalized RuMOPs.

Main Methods:

• Synthesis of three novel cuboctahedral RuMOPs with varying alkyl functionalizations.
• Characterization of molecular packing, porosity, and redox properties.
• Electrochemical measurements to analyze electron transfer processes.

Main Results:

• Successfully synthesized three new RuMOPs with controlled structures.
• Demonstrated that external functionalization influences molecular packing and porosity.
• Electrochemical studies revealed multielectron redox processes controllable by functional groups.

Conclusions:

• Novel RuMOPs with tunable redox properties were synthesized.
• External functionalization is a key strategy for controlling RuMOP characteristics.
• These findings pave the way for designing advanced redox-active porous materials.