biostudies-literatureAlonso-Navarro MJMinisterio de Ciencia, Innovaci?n y UniversidadesComunidad de MadridUniversidad Rey Juan CarlosUniversidad Complutense de MadridNextGenerationEU9613-9618https://www.ebi.ac.uk/biostudies/studies/S-EPMC12418488biostudies-literatureUnknown27(35)In 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 <i>n-</i>type organic semiconductors.Organic lettersGiant Fully Fused Tetrapodal Rylenimides: Design, Synthesis and Optoelectrochemical Characterization via Alkyl Chain and Core Engineering Strategies.PMC12418488PLEC2021-007906PID2022-138908NB-C33TEC-2024/TEC-459PID2023-149077OB-C31INV.GR.00.1819.107592024/SOLCON-138169TED2021-12941A-I00TEC-2024/ECO-332TED2021-129886BC43Ramos MMSegura JLMartinez JISuarez-Blas FAlonso-Navarro MJfalseGiant Fully Fused Tetrapodal Rylenimides: Design, Synthesis and Optoelectrochemical Characterization via Alkyl Chain and Core Engineering Strategies.In 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 <i>n-</i>type organic semiconductors.2025-01-01T00:00:00Z2025 Sep2026-06-02T17:41:30.345Z2026-04-18T03:11:35.441ZS-EPMC124184884085141610.1021/acs.orglett.5c02655