High‐Efficiency Deep Blue Single‐Gaussian Europium(II) Emitters and Their Emitter‐Host Interactions

Eu(II) complexes are attractive emitters for deep‐blue organic light‐emitting diodes (OLEDs) due to their narrow, parity‐allowed 4 f –5 d emission; however, their implementation in vacuum‐processed OLEDs has remained limited. Here, we introduce a new molecular design concept for Eu(II) emitters, in which crown‐ether ligands are combined with carborate anions to define the coordination environment and improve steric shielding of the europium center. Based on this design, we present two emitters that combine narrow deep‐blue photoluminescence with quantum yields approaching 90% and sufficient thermal stability for vacuum deposition. As the excited‐state dynamics of this emitter class are different from most conventional OLED emitters and the pathway to maximum luminescence efficiency in thin films is not fully established, we study interactions between Eu(II) complexes and the host environment, based on density functional theory and time‐resolved experiments. We identify steric shielding of the Eu(II) core and energetic confinement of the excited 5 d electron, defined by molecular design as key factors governing efficient luminescence, providing a roadmap for rational design of Eu(II) emitters. Together, these results establish a basis for higher‐efficiency and deeper‐blue OLEDs incorporating Eu(II) emitters.