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We have synthesized a new series of 2,4,6-triaryl-λ 5 -phosphinines containing different substituents both at the carbon-backbone and the phosphorus atom of the six-membered heterocycle. Their optical and redox properties were studied in detail, supported by in-depth theoretical calculations. The modularity of the synthetic strategy allowed us to establish structure-property relationships for this class of compounds and an OLED based on a blue phosphinine emitter could be developed for the first time. © 2020 WILEY-VCH Verlag GmbH &