Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters

Porphyrin derivatives represent an emerging class of redox‐active materials for sustainable electrochemical energy storage. However, their structure–performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A(2)B(2)‐type porphyrin 5,15‐bis(ethynyl)‐10,20‐diphenylporphyrin and its first‐row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource‐friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage.