Zheng Haoyue, Cao Peisheng, Wang Yanying, Lu Xiaomei, Wu Peng
State Key Laboratory of Hydraulics and Mountain River Engineering, Analytical & Testing Center, Sichuan University, Chengdu, 610064, China.
Key Laboratory of Green Chemistry and Technology of MOE, College of Chemistry, Sichuan University, Chengdu, 610064, China.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9500-9506. doi: 10.1002/anie.202101923. Epub 2021 Mar 15.
For a long time, phosphors with long-lived emission are dominated by rare earth/transition metal ion-doped sulfides and oxides. Recently, organic materials capable of emitting long-lived room-temperature phosphorescence (RTP) are reported, carbon skeletons are almost the exclusive structural feature of the conjugated luminophores. Herein, we reported that boric acid, a non-metal and C-free material, could emit RTP with lifetime up to 0.3 s. Detailed investigations indicated the weak conjugation between the n electrons of the O atoms in the B-O confined space was the possible origin of RTP. Similar RTP was also found in electron-rich N/F systems, namely, BN and BF (BF ). Importantly, the vacant orbital of B was found to contribute to the relevant unoccupied molecular orbitals involved in excitation, which is different from previous reports on phosphorescence from arylboronic acids. The results confirm the unique role of B as a versatile structure motif for construction of new RTP materials.
长期以来,具有长寿命发射的磷光体主要是稀土/过渡金属离子掺杂的硫化物和氧化物。最近,有报道称有机材料能够发射长寿命室温磷光(RTP),共轭发光体的碳骨架几乎是唯一的结构特征。在此,我们报道了硼酸这种不含金属和碳的材料能够发射寿命长达0.3秒的RTP。详细研究表明,B-O受限空间中O原子的n电子之间的弱共轭可能是RTP的起源。在富电子的N/F体系中,即BN和BF(BF )中也发现了类似的RTP。重要的是,发现B的空轨道有助于激发过程中涉及的相关未占据分子轨道,这与之前关于芳基硼酸磷光的报道不同。结果证实了B作为构建新型RTP材料的通用结构基序的独特作用。