Thermally Activated Delayed Fluorescent Binuclear Copper(I) Alkynyl Complexes with Cuprophilic Interactions.

Copper(I)-based thermally activated delayed fluorescence (TADF) emitters have been conceived to be promising candidates for display and lighting applications because of their multifarious structures and strong photoluminescence. Herein a string of binuclear Cu(I) complexes bearing pronounced cuprophilic interactions have been designed and synthesized. [Cu2(dppb)2(µ2-η1-C≡C-Ph)2] (1 a) and [Cu2(dppb)2(µ2-η1-C≡C-PPXZ)2] (1 b) display photoluminescence quantum yields of up to 67 % in doped films and solid states via TADF and exhibit reversible bicolor luminescence switching upon mechanical stimuli. Computational studies manifest that the metal-to-ligand charge transfer predominant transitions ensure a small energy splitting (ΔEST) between the lowest singlet (S1) and triplet (T1) excited states and cuprophilic interactions promote the spin-orbit coupling (SOC), favoring the reverse intersystem crossing (RISC) process. This study provides a new strategy for the construction of stimuli-responsive metal-based TADF materials.

Highly Efficient Au(I) Alkynyl Emitters: Thermally Activated Delayed Fluorescence and Solution-Processed OLEDs.

Two-coordinate donor-metal-acceptor type coinage metal complexes displaying efficient thermally activated delayed fluorescence (TADF) have been unveiled to be highly appealing candidates as emitters for organic light-emitting diodes (OLEDs). Herein a series of green to yellow TADF gold(I) complexes with alkynyl ligands has been developed for the first time. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.76 in doped films (5 wt % in PMMA) at room temperature. The modifications of alkynyl ligands with electron-donating amino groups together with the use of electron-deficient carbene ligands induce ligand-to-ligand charge transfer excited states that give rise to TADF emission. Spectroscopic and density functional theory (DFT) calculations reveal the roles of electron-donating capability of the alkynyl ligand in tuning the excited-state properties. Solution-processed organic light-emitting diodes (OLEDs) using the present complexes as emitters achieve maximum external quantum efficiency (EQE) of up to 20 %.

Highly Efficient Thermally Activated Delayed Fluorescence from Pyrazine-Fused Carbene Au(I) Emitters.

Metal-based thermally activated delayed fluorescence (TADF) is conceived to inherit the advantages of both phosphorescent metal complexes and purely organic TADF compounds for high-performance electroluminescence. Herein a panel of new TADF Au(I) emitters has been designed and synthesized by using carbazole and pyrazine-fused nitrogen-heterocyclic carbene (NHC) as the donor and acceptor ligands, respectively. Single-crystal X-ray structures show linear molecular shape and coplanar arrangement of the donor and acceptor with small dihedral angles of <6.5°. The coplanar orientation and appropriate separation of the HOMO and LUMO in this type of molecules favour the formation of charge-transfer excited state with appreciable oscillator strength. Together with a minor but essential heavy atom effect of Au ion, the complexes in doped films exhibit highly efficient (Φ∼0.9) and short-lived (<1 µs) green emissions via TADF. Computational studies on this class of emitters have been performed to decipher the key reverse intersystem crossing (RISC) pathway. In addition to a small energy splitting between the lowest singlet and triplet excited states (ΔEST ), the spin-orbit coupling (SOC) effect is found to be larger at a specific torsion angle between the donor and acceptor planes which favours the RISC process the most. This work provides an alternative molecular design to TADF Au(I) carbene emitters for OLED application.

Recent Progress in Blue Thermally Activated Delayed Fluorescence Emitters and Their Applications in OLEDs: Beyond Pure Organic Molecules with Twist D-π-A Structures.

Thermally activated delayed fluorescence (TADF) materials, which can harvest all excitons and emit light without the use of noble metals, are an appealing class of functional materials emerging as next-generation organic electroluminescent materials. Triplet excitons can be upconverted to the singlet state with the aid of ambient thermal energy under the reverse inter-system crossing owing to the small singlet-triplet splitting energy (ΔEST). This results from a specific molecular design consisting of minimal overlap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, due to the spatial separation of the electron-donating and electron-releasing part. When a well-designed device structure is applied, high-performance blue-emitting TADF organic light-emitting diodes can be realized with an appropriate molecular design. Unlike the previous literature that has reviewed general blue-emitting TADF materials, in this paper, we focus on materials other than pure organic molecules with twist D-π-A structures, including multi-resonance TADF, through-space charge transfer TADF, and metal-TADF materials. Cutting-edge molecules with extremely small and even negative ΔEST values are also introduced as candidates for next-generation TADF materials. In addition, OLED structures used to exploit the merits of the abovementioned TADF emitters are also described in this review.

Conformational Engineering of Two-Coordinate Gold(I) Complexes: Regulation of Excited-State Dynamics for Efficient Delayed Fluorescence.

Carbene-Au-amide (CMA) type complexes, in which the amide and carbene ligands act as an electron donor (D) and acceptor (A), respectively, can exhibit strong delayed fluorescence (DF) from a ligand to ligand charge transfer (LLCT) excited state. Although the coplanar donor-acceptor (D-A) conformation has been suggested to be a crucial factor favoring radiative decay of the charge-transfer excited state, the geometric structural factor underpinning the excited-state mechanism of CMA complexes remains an open question. We herein develop a new class of carbene-Au-carbazolate complexes by introducing large aromatic substituents onto the carbazolate ligand, the presence of which are conceived to restrict the rotation of the Au-N bond and thus confine a twisted D-A conformation in both ground and excited states. A highly twisted D-A orientation is found for the complexes in their crystal structures. Photophysical studies reveal that the twisted conformation induces a decrease in the gap (ΔEST) between the lowest singlet excited state (S1) and the triplet manifold (T1) and thus a faster reverse intersystem crossing (RISC) from T1 to S1 at the expense of oscillator strength for an S1 radiative transition. In comparison with the coplanar analogue, the twisted complexes exhibit comparable or improved DF with quantum yields of up to 94% and short emission lifetimes down to sub-microseconds. The tuning of excited-state dynamics has been well interpreted by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, which unveil much faster RISC rates for twisted complexes. Solution-processed organic light-emitting diodes (OLEDs) based on the new CMA complexes show promising performances with almost negligible efficiency rolloff at a brightness of 1000 cd m-2. This work implies that neither a coplanar ground-state D-A conformation nor a dynamic rotation of the M-N bond is the key to the realization of efficient DF for CMA complexes.