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Porphyrins are π-conjugated materials with exceptional optical and electronic properties that have garnered considerable interest in the field of organic photovoltaics. Their well-established synthetic accessibility enables the construction of diverse molecular geometries through relatively few synthetic steps. This review highlights recent progress over the past decade in the rational design of porphyrin-based donor–acceptor architectures for third-generation organic photovoltaic devices. Emphasis is placed on the roles of molecular symmetry, π-extension, and donor–acceptor energy level alignment. Key structural features, including metal centers, side chains, and π-bridges, are examined in relation to their impact on device efficiency and operational stability. The influence of structural modifications on HOMO–LUMO energy levels, active layer morphology, and overall photovoltaic performance is critically assessed. • The properties of porphyrins make them good semiconductors in organic solar cells. • Molecular engineering in porphyrins, enable fine-tuning of energy levels. • Active layer morphology can be optimized by chemical functionalization. • Porphyrin-based semiconductors have evolved to multifunctional components in OSC. • The use of β-functionalized and n-type porphyrins for OSC is still challenging.
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Caballero et al. (2025) studied this question.
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