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In this study, we report a rigid nitrogen\u2010rich donor, 3N, featuring the first fused framework constructed from two anti\u2010aromatic phenazine units. This unique architecture ensures 3N has good planarity and an exceptionally shallow highest occupied molecular orbital (HOMO) energy level of \u22124.88\u00a0eV. Meanwhile, the effective suppression of structural relaxation by its rigid scaffold contributes to a narrow emission at 456\u00a0nm. By pairing 3N with planar boron\u2010containing acceptors through strong intermolecular interactions, highly efficient exciplex emissions ranging from green to orange\u2010red were successfully achieved. Two representative exciplex systems reached outstanding photoluminescence quantum yields of 92% at 557\u00a0nm and 78% at 604\u00a0nm, respectively. Correspondingly, organic light\u2010emitting diodes based on these exciplexes delivered maximum external quantum efficiencies of 25.6% at 556\u00a0nm and 24.7% at 586\u00a0nm, respectively. To the best of our knowledge, these values rank among the highest performance metrics reported for long\u2010wavelength exciplexes. These results demonstrate that fusing multiple phenazine units could significantly raise the HOMO level and enhances structural rigidity, thereby enabling highly efficient long\u2010wavelength exciplex electroluminescence.<\/jats:p>","DOI":"10.1002\/anie.2974644","type":"journal-article","created":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T08:58:30Z","timestamp":1791968310000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Dibenzophenazine\u2010Fused Heterocyclic Luminophores: Decoding High\u2010Performance Organic Light\u2010Emitting Diodes Based on Long\u2010Wavelength Exciplex"],"prefix":"10.1002","author":[{"given":"Yu","family":"Fu","sequence":"first","affiliation":[{"name":"Guangdong Basic Research Center of Excellence for Energy and Information Polymer Materials State Key Laboratory of Luminescent Materials and Devices and Institute of Polymer Optoelectronic Materials and Devices South China University of Technology  Guangzhou P. 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