Alonso-Navarro, Matías J.Suárez-Blas, FátimaMartínez, jose IgnacioRamos, M. MarSegura Castedo, José Luis2025-09-082025-09-082025-08-08Org. Lett, 20025, published online 25 August 2025, https://doi.org/10.1021/acs.orglett.5c0265510.1021/acs.orglett.5c02655https://hdl.handle.net/20.500.14352/123763In this work, we report the synthesis and comprehensive characterization of a new series of fully fused three-dimensional rylenimide-based derivatives featuring extended π-conjugation through core-fusion strategies and tailored side-chain engineering at the imide nitrogen, resulting in molecular architectures with up to 19 fused rings. The effects of π-extension and alkyl/aryl imide substituents on the optical and electrochemical behavior were systematically studied using UV–vis spectroscopy, cyclic voltammetry, and density functional theory calculations. The results demonstrate that combining π-extension with bulky solubilizing groups effectively suppresses undesired π–π interactions, enhances electronic delocalization, and improves device-relevant properties. This molecular design strategy offers a promising platform for the development of next-generation functional n-type organic semiconductors.engjournal articlehttps://pubs.acs.org/doi/10.1021/acs.orglett.5c02655open access547AggregationOrganic SemiconductorRylenimideOptoelectrochemicalQuímica orgánica (Química)2306 Química Orgánica