Tian Wei-Dong, Zhang Chengkai, Paul Sayan, Si Wei-Dan, Wang Zhi, Sun Pan-Pan, Anoop Anakuthil, Tung Chen-Ho, Sun Di
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan, 250100, People's Republic of China.
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721302.
Angew Chem Int Ed Engl. 2025 Mar 10;64(11):e202421656. doi: 10.1002/anie.202421656. Epub 2025 Jan 3.
Developing thermally activated delayed fluorescence (TADF)-active silver clusters with near-unity quantum efficiency is of practical importance in cutting-edge optoelectronic devices, but remains a tremendous challenge due to the difficulty of de novo synthesis and uncertainty of properties. Herein, we demonstrate a lattice modulation on parent TADF- active silver cluster, achieving TADF-driven photoluminescence quantum yield (PLQY) from 12 % to near-unity. Systematic experimental and calculated results reveal that the lattice modulation effectively lowers the singlet-triplet splitting (ΔE) from 718 to 549 cm, thereby facilitating thermally activated reverse intersystem crossing: T→S, leading to extremely efficient TADF by surpassing both phosphorescence and non-radiative decay, thus boosting the near-unity PLQY. Such high PLQY is extremely rare in the TADF-active silver clusters and even in the whole noble-metal clusters. This research showcases an unparalleled example of lattice modulation to realize near unity PLQY of TADF-active silver clusters.
开发具有接近单位量子效率的热激活延迟荧光（TADF）活性银簇在前沿光电器件中具有实际重要性，但由于从头合成的困难和性质的不确定性，仍然是一个巨大的挑战。在此，我们展示了对母体TADF活性银簇的晶格调制，实现了从12%到接近单位的TADF驱动的光致发光量子产率（PLQY）。系统的实验和计算结果表明，晶格调制有效地将单重态-三重态分裂（ΔE）从718 cm降低到549 cm，从而促进热激活反向系间窜越：T→S，通过超越磷光和非辐射衰减实现极其高效的TADF，从而提高接近单位的PLQY。这种高PLQY在TADF活性银簇中甚至在整个贵金属簇中都极为罕见。本研究展示了一个无与伦比的晶格调制实例，以实现TADF活性银簇接近单位的PLQY。
