Cu(iii)triarylcorroles with asymmetric push-pull meso-substitutions: tunable molecular electrochemically catalyzed...

Area of Science:

• Coordination Chemistry
• Catalysis
• Materials Science

Background:

• Corrole complexes, particularly those of copper, are of interest due to their unique electronic structures and catalytic potential.
• Tuning the electronic properties of ligands is crucial for optimizing catalyst performance in various chemical transformations.

Purpose of the Study:

• To synthesize and characterize novel low symmetry A2B type copper(III) triarylcorroles.
• To investigate the structure-property relationships concerning optical and redox characteristics.
• To evaluate the catalytic efficiency of these corroles in electrocatalyzed hydrogen evolution reactions (HERs).

Main Methods:

• Synthesis of four A2B type Cu(III) triarylcorroles with varying meso-aryl substituents.
• Structural characterization using NMR spectroscopy and X-ray crystallography.
• Analysis of optical and redox properties via UV-Vis spectroscopy, electrochemistry, and spectroelectrochemistry.
• Computational studies using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) for property prediction.

Main Results:

• Successful synthesis and full structural characterization of the target Cu(III) triarylcorroles.
• Demonstrated correlation between meso-aryl substituent electronic nature (donating/withdrawing) and the optical/redox properties.
• Identified these A2B type Cu(III) triarylcorroles as highly efficient electrocatalysts for HERs.
• Showcased the ability to modulate catalytic reactivity by altering the B-position meso-substituent.

Conclusions:

• The synthesized A2B type Cu(III) triarylcorroles exhibit tunable electronic and optical properties.
• These complexes are effective catalysts for electrocatalyzed hydrogen evolution.
• The catalytic performance can be fine-tuned by strategic modification of the molecular structure, specifically the B-position substituent.