In an organic electroluminescent (EL) device, the recombination of injected holes and electrons produces what appears to be an ion‐pair or charge‐transfer (CT) exciton, and this CT exciton decays to produce one photon directly, or relaxes to a low‐lying local exciton (LE). Thus the full utilization of both the energy of the CT exciton and the LE should be a pathway for obtaining high‐efficiency EL. Here, a twisting donor‐acceptor (D‐A) triphenylamine‐imidazol molecule, TPA‐PPI, is reported: its synthesis, photophysics, and EL performance. Prepared by a manageable, one‐pot cyclizing reaction, TPA‐PPI exhibits deep‐blue emission with high quantum yields (90%) both in solution and in the solid state. Fluorescent solvatochromic experiments for TPA‐PPI solutions show a red‐shift of 57 nm (3032 cm−1) from low‐polarity hexane (406 nm) to high‐polarity acetonitrile (463 nm), accompanied by the gradual disappearance of the vibrational band in the spectra with increased solvent polarity. The photophysical investigation and DFT analysis suggest an intercrossed CT and LE excited state of the TPA‐PPI, originating from its twisting D‐A configuration. This is a rare instance that a CT‐state material shows highly efficient deep‐blue emission. EL characterization demonstrates that, as a deep‐blue emitter with CIE coordinates of (0.15, 0.11), the performance of a TPA‐PPI‐based device is rather excellent, displaying a maximum current efficiency of >5.0 cd A−1, and a maximum external quantum efficiency of >5.0%, corresponding to a maximum internal quantum efficiency of >25%. The effective utilization of the excitation energy arising from materials with intercrossed‐excited‐state (LE and CT) characters is thought to be beneficial for the improved efficiency of EL devices.

In principle, the ratio (Φ) of the maximum quantum efficiencies for electroluminescence (EL) to photoluminescence (PL) can be expected to approach unity, if the exciton (bound electron–hole pair) generated from the recombination of injected electrons and holes in OLEDs has a sufficiently weak binding energy. However, seldom are examples of Φ > 25% reported in OLEDs because of the strongly bound excitons for most organic semiconductors in nature. Here, a twisting donor–acceptor triphenylamine‐thiadiazol molecule (TPA‐NZP) exhibits fluorescent emission through a hybridized local and charge‐transfer excited state (HLCT), which is demonstrated from both fluorescent solvatochromic experiment and quantum chemical calculations. The HLCT state possesses two combined and compatible characteristics: a large transition moment from a local excited (LE) state and a weakly bound exciton from a charge transfer (CT) state. The former contributes to a high‐efficiency radiation of fluorescence, while the latter is responsible for the generation of a high fraction of singlet excitons. Using TPA‐NZP as the light‐emitting layer in an OLED, high Φ values of 93% (at low brightness) and 50% (at high brightness) are achieved, reflecting sufficient employment of the excitons in the OLED. Characterization of the EL device shows a saturated deep‐red emission with CIE coordinates of (0.67, 0.32), accompanied by a rather excellent performance with a maximum luminance of 4574 cd m−2 and a maximum external quantum efficiency (ηext) of ∼2.8%. The HLCT state is a new way to realize high‐efficiency of EL devices.

The development of near-infrared (NIR) organic light-emitting diodes (OLEDs) is of growing interest. Donor-acceptor (D-A) chromophores have served as an important class of NIR materials for NIR OLED applications. However, the external quantum efficiencies (EQEs) of NIR OLEDs based on conventional D-A chromophores are typically below 1 %. Reported herein is a butterfly-shaped D-A compound, PTZ-BZP. A PTZ-BZP film displayed strong NIR fluorescence with an emission peak at 700 nm, and the corresponding quantum efficiency reached 16 %. Remarkably, the EQE of the NIR OLED based on PTZ-BZP was 1.54 %, and a low efficiency roll-off was observed, as well as a high radiative exciton ratio of 48 %, which breaks through the limit of 25 % in conventional fluorescent OLEDs. Experimental and theoretical investigations were carried out to understand the excited-state properties of PTZ-BZP.

For a donor–acceptor (D–A) molecule, there are three possible cases for its low‐lying excited state (S1): a π–π* state (a localized electronic state), a charge‐transfer (CT) state (a delocalized electronic state), and a mixed or hybridized state of π–π* and CT (named here as the hybridized local and charge transfer (HLCT) state). The HLCT state is an important excited state for the design of next‐generation organic light‐emitting diode (OLED) materials with both high photoluminescence (PL) efficiency and a large fraction of singlet exciton generation in electroluminescence (EL). According to the principle of state mixing in quantum chemistry, a series of twisting D–A molecules are designed and synthesized, and their HLCT state characters are verified by both fluorescent solvatochromic experiments and quantum chemical calculations. The CT components in the HLCT state, which greatly affect the molecular optical properties, are found to be enhanced with a decrease of the twist angle of the D–A segment or an increase of the D–A intensity in these twisting D–A molecules. In OLEDs, using these HLCT compounds as the emitting layer, the maximum exciton utilization efficiency is harvested up to 93%. Surprisingly, an exception of Kasha's rule is revealed in some HLCT compounds: restricted internal‐conversion (IC) from the high‐lying triplet state (T2) to the low‐lying triplet T1, and a reopened path of reverse intersystem crossing (RISC) from T2 to S1 or S2, based on the analysis of the excited‐state energy levels and the measurement of the low‐temperature spectrum. RISC from T2 to S1 (S2) as a “hot exciton” channel is believed to contribute to the large proportion of the radiative singlet excitons.

Strong supramolecular interactions, which induced tight packing and rigid molecules in crystals of cyano substituent oligo(para-phenylene vinylene) (CN-DPDSB), are the key factor for the high luminescence efficiency of its crystals; opposite to its isolated molecules in solution which have very low luminescence efficiency.