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While the development of wide\u2010energy\u2010gap exciplexes for deep\u2010blue OLEDs remains challenging, this work presents a unique approach to generating a blue exciplex and using it as a sensitizer in HF\u2010OLEDs. Considering the benefits of efficient triplet confinement in sensitizer\u2010based OLEDs, we developed a new \u201c\n                    <jats:italic>hot\u2010exciplex<\/jats:italic>\n                    \u201d system that leverages higher\u2010lying triplet states, confirmed by ultrafast picosecond and nanosecond transient absorption studies. To achieve this system, a simple bispyrimidine motif, BisPMD, and a carbazole derivative, CCP, are used as the acceptor and donor, respectively, owing to their similar high triplet energy levels. This design enables access to the hot excitonic states, reducing the singlet\u2010triplet energy gap (\u0394\n                    <jats:italic>E<\/jats:italic>\n                    <jats:sub>ST<\/jats:sub>\n                    ) and enhancing the upper\u2010level reverse intersystem crossing (RISC) rate (\n                    <jats:italic>k<\/jats:italic>\n                    <jats:sub>hRISC<\/jats:sub>\n                    ). The \u201c\n                    <jats:italic>hot\u2010exciplex<\/jats:italic>\n                    \u201d system proves to be an effective sensitizer for blue TADF and narrowband multi\u2010resonance (MR) emitters, enabling efficient F\u00f6rster energy transfer (FRET) and improving rolloff and color purity at high efficiency. This advanced exciplex\u2010driven HF\u2010OLED is expected to enhance device performance and open further opportunities.\n                  <\/jats:p>","DOI":"10.1002\/anie.8297276","type":"journal-article","created":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T05:36:01Z","timestamp":1789104961000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Hot\u2010Exciplex: A New Regime of Triplet Harvesting Beyond Conventional TADF Advancing Hyperfluorescence"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9085-1105","authenticated-orcid":false,"given":"Debasish","family":"Barman","sequence":"first","affiliation":[{"name":"Center For Organic Photonics and Electronics Research (OPERA) and Organic Photonics and Electronics International Laboratory (OPHELIA), Applied Chemistry Kyushu University  Fukuoka 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