No abstract

The practical use of luminescent mononuclear gold(I) complexes as optoelectronic materials has been limited by their inferior stability. Herein we demonstrate a strategy to improve the stability of gold(I) complexes which display thermally activated delayed fluorescence (TADF). A highly rigid and groove‐like σ‐donating aryl ligand has been used to form dual Au⋅⋅⋅H−C hydrogen bonds. The secondary metal‐ligand interactions have been authenticated by single‐crystal structure, NMR spectroscopy and theoretical simulations. The TADF AuI complex exhibits appealing emission properties (photoluminescence quantum yield=76 %; delayed fluorescence lifetime=1.2 μs) and much improved thermal and photo‐stability. Vacuum‐deposited organic light‐emitting diodes (OLEDs) show promising electroluminescence with a maximum external quantum efficiency (EQE) over 23 % and negligible efficiency roll‐off even at 10 000 cd m−2. An estimated LT50 longer than 77 000 h with initial luminance of 100 cd m−2 reveals good operational stability. This work suggests a way for design of stable luminescent gold(I) complexes.

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 (ΔE ST ) between the lowest singlet excited state (S 1 ) and the triplet manifold (T 1 ) and thus a faster reverse intersystem crossing (RISC) from T 1 to S 1 at the expense of oscillator strength for an S 1 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.

No abstract

Recently we have witnessed the rise of Artificial Intelligence of Things (AIoT) and the shift of sensing paradigm from cloud-centric to the edge-centric, which effectively improves the sensing capability of intelligence transportation systems. To improve the real-time sensing performance, in this work we propose an ensemble sensing based scheme to solve the time-constraint synchronized inference problem and achieve robust inference with heterogeneous IoT devices in intelligence transportation systems. We design and implement Ensen, which incorporates various novel techniques such as customized DNN model design, KD-based model training, and dynamic deep ensemble management, etc., to achieve improved accuracy and maximize the computational resource usage of the whole sensing group. Extensive evaluations on different types of common IoT devices have shown that Ensen achieves a robust performance and can be easily extended to different types of convolutional neural networks.