Luminescence clusters composed of organic ligands and metals have gained significant interests as scintillators owing to their great potential in high X-ray absorption, customizable radioluminescence, and solution processability at low temperatures. However, X-ray luminescence efficiency in clusters is primarily governed by the competition between radiative states from organic ligands and nonradiative cluster-centered charge transfer. Here we report that a class of Cu₄I₄ cubes exhibit highly emissive radioluminescence in response to X-ray irradiation through functionalizing biphosphine ligands with acridine. Mechanistic studies show that these clusters can efficiently absorb radiation ionization to generate electron-hole pairs and transfer them to ligands during thermalization for efficient radioluminescence through precise control over intramolecular charge transfer. Our experimental results indicate that copper/iodine-to-ligand and intraligand charge transfer states are predominant in radiative processes. We demonstrate that photoluminescence and electroluminescence quantum efficiencies of the clusters reach 95% and 25.6%, with the assistance of external triplet-to-singlet conversion by a thermally activated delayed fluorescence matrix. We further show the utility of the Cu₄I₄ scintillators in achieving a lowest X-ray detection limit of 77 nGy s⁻¹ and a high X-ray imaging resolution of 12 line pairs per millimeter. Our study offers insights into universal luminescent mechanism and ligand engineering of cluster scintillators.

Development of white organic light-emitting diodes based on purely thermally activated delayed fluorescence with a single-emissive-layer configuration has been a formidable challenge. Here, we report the rational design of a donor-acceptor energy-relaying exciplex and its utility in fabricating single-emissive-layer, thermally activated delayed fluorescence-based white organic light-emitting diodes that exhibit 100% internal quantum efficiency, 108.2 lm W⁻¹ power efficiency, and 32.7% external quantum efficiency. This strategy enables thin-film fabrication of an 8 cm × 8 cm thermally activated delayed fluorescence white organic light-emitting diodes (10 inch²) prototype with 82.7 lm W⁻¹ power efficiency and 25.0% external quantum efficiency. Introduction of a phosphine oxide-based acceptor with a steric group to the exciplex limits donor-acceptor triplet coupling, providing dual levels of high-lying and low-lying triplet energy. Transient spectroscopic characterizations confirm that a ladder-like energy relaying occurs from the high-lying triplet level of the exciplex to a blue emitter, then to the low-lying triplet level of the phosphine oxide acceptor, and ultimately to the yellow emitter. Our results demonstrate the broad applicability of energy relaying in multicomponent systems for exciton harvesting, providing opportunities for the development of third-generation white organic light-emitting diode light sources.

Developing efficient red thermally activated delayed fluorescence (TADF) emitters is a real challenge due to the serious nonradiation of their low-band-gap singlet charge transfer state. Dipyridophenazine (DPPZ) (weak electron-withdrawing pyridines fused with strong electron-withdrawing phenazine) is used as an acceptor to overcome this issue. The gradient multi-inductive effect of different heterocyclic units simultaneously enhances the intramolecular charge transfer for red emission of the TADF molecule oTPA-DPPZ, and facilitates the radiative transition of its singlet charge transfer state by increasing frontier molecular orbital overlap on the electron-deficient pyrazine moiety. The 10-fold increased oscillator strength of its singlet transition results in its excellent photoluminescence and electroluminescence quantum efficiencies of ∼75% and ∼19%, accompanied by red emission peaked around 600 nm.

Organic ultralong room-temperature phosphorescence (RTP) usually emerges instantly and immediately decays after excitation removal. Here we report a new delayed RTP that is postponed by dozens of milliseconds after excitation removal and decays in two steps including an initial increase in intensity followed by subsequent decrease in intensity. The delayed RTP is achieved through introduction of phosphines into carbazole emitters. In contrast to the rapid energy transfer from single-molecular triplet states (T₁) to stabilized triplet states (T_n*) of instant RTP systems, phosphine groups insert their intermediate states (T_M) between carbazole-originated T₁ and T_n* of carbazole-phosphine hybrids. In addition to markedly increasing emission lifetimes by ten folds, since T_M → T_n* transition require >30 milliseconds, RTP is thereby postponed by dozens of milliseconds. The emission character of carbazole-phosphine hybrids can be used to reveal information through combining instant and delayed RTP, realizing multi-level time resolution for advanced information, biological and optoelectronic applications.

Lanthanide nanocrystals offer unique advantages for electroluminescence (EL) applications, including narrow-band emission, high colour purity and compositionally tunable output^1,2,3,4. However, their insulating nature poses a challenge for carrier transport and injection, impeding their application in electrically driven optoelectronic devices⁵. Here we demonstrate efficient EL from insulating lanthanide fluoride nanocrystals (4 nm; NaGdF₄:X; X = Tb³⁺, Eu³⁺ or Nd³⁺) coated with a series of functionalized 2-(diphenylphosphoryl)benzoic acids (ArPPOA). These ligands, featuring donor–phosphine oxide acceptor hybrids with carboxyl and P=O coordination sites, effectively sensitize the luminescence of lanthanide nanocrystals by modulating the intraligand charge transfer characteristics. Ultrafast spectroscopic investigations reveal that strong coupling between ArPPOA and lanthanide nanocrystals facilitates intersystem crossing (ISC; <1 ns) and highly efficient triplet energy transfer to nanocrystals (up to 96.7%). Through careful control of dopant composition and concentration in nanocrystals, we also achieve wide-ranging multicolour EL without altering the device architecture, reaching an external quantum efficiency exceeding 5.9% for Tb³⁺. This ligand-functionalized nanocrystal platform provides a modular strategy for exciton control in insulating nanocrystal systems, offering a pathway for spectrally precise electroluminescent materials.