π-Electronic ions with appropriate geometries and peripheral substituents provide assemblies through the interactions between charged building subunits, resulting in fascinating electronic properties. Structures and properties of the assemblies can be controlled by the combined positively and negatively charged species in the assemblies.[1–3] In fact, π-electronic ion pairs comprising porphyrin-based π-electronic anions have exhibited characteristic assembling modes via i π– i π interactions and resulting electronic properties such as solid-state absorption, which was correlated with the arrangement of constituent charged π-systems, and photoinduced electron transfer.[4] Among various combinations of the porphyrin anions with porphyrin–AuIIIcomplexes as π-electronic cations,[5] the “activated” ion pair of meso-EWG (electron-withdrawing group)-substituted cation and meso-EDG (electron-donating group)-substituted anion exhibited the electron transfer in the ground state, resulting in the production of the heterodiradical in a close stacking structure as revealed by the ESR.[6] Further modifications of charged porphyrins and analogs have been examined for the electronic properties that are derived from ion pairing.[1] Recent reviews: (a) Haketa, Y.; Yamasumi, K. et al. Chem. Soc. Rev. 2023, 52, 7170; (b) Haketa, Y. et al. Responsive Mater. 2023, 1, e20230018. [2] Recent reports on ion pairs and assemblies: (a) Yamasumi, K. et al. Angew. Chem. Int. Ed. 2023, 62, e202216013; (b)Sugiura, S. et al. J. Am. Chem. Soc. 2023, 144, 8122; (c) Haketa, Y. et al. Chem. Sci. 2024, 15, in press (DOI: 10.1039/d3sc04564a). [3] Selected reports on pyrrole-based π-electronic molecules: (a) Haketa, Y. et al. J. Am. Chem. Soc. 2020, 142, 16420; (b) Ishikawa, S. et al. under revision. [4] Sasano, Y.; Tanaka, H. et al. Chem. Sci. 2021, 12, 9645. [5](a) Haketa, Y. et al. iScience 2019, 14, 241; (b) Nakajima, R. et al. to be submitted; (c) Maruyama, Y. et al. to be submitted. [6](a) Tanaka, H. et al. J. Am. Chem. Soc. 2022, 144, 21710; (b) Tanaka, H. et al. Chem. Eur. J. 2023, 29, e202203957.