Tunable Ultralong Organic Phosphorescence Modulated by Main-Group Elements with Different Lewis Acidity and Basicity
Tunable Ultralong Organic Phosphorescence Modulated by Main-Group Elements with Different Lewis Acidity and Basicity
复制标题
不同路易斯酸碱度主族元素调控的可调谐超长有机磷光
DOI：
10.1039/d0tc02953j
复制
发表时间：
2020
影响因子：
6.4
通讯作者：
He Gang
中科院分区：
文献类型：
--
作者：
Xu Letian;Zhou Kun;Qiu Xinyu;Rao Bin;Pei D;an;Zhou Kun;Li Ang;An Zhongfu;He Gang
报道了一系列咔唑（Cz-Cm/Lab，X = B，C，N，S）与刘易斯酸性或刘易斯碱性主族元素的配合物，合成了一系列具有可调UOP颜色和寿命的超长有机磷光材料（XCz-Cm/Lab，X = B，C，N，S）。随着支架中刘易斯碱性从硼到碳、氮和硫的增加，XCz相应的最低三重激发态能级逐渐降低，XCz-Cm的UOP颜色从黄绿色（λ 534 nm）向橙红色（λ 580 nm）红移。相反，XCz分子的π-π相互作用距离和从最低三重激发态到基态的辐射衰减逐渐增加，赋予XCz-Cm可调谐的UOP寿命（0.068-0.555 s）。XCz-Lab具有与XCz-Cm类似的光致发光行为，XCz-Cm与XCz-Lab的差异归因于Cz-Cm的异构体。由于CCz-Cm纳米粒子具有长寿命的三重激发态，因此成功地将其应用于体内静脉注射的实时淋巴结余辉成像。这一贡献不仅为通过引入刘易斯酸/碱主族元素来调节UOP性质提供了一种新的通用策略，而且扩展了它们在余辉成像中的应用。
A series of ultralong organic phosphorescence (UOP) materials (XCz-Cm/Lab, X = B, C, N, and S) with tunable UOP colors and lifetimes through the combination of commercial/lab-synthesized carbazole (Cz-Cm/Lab) with the Lewis acidic or Lewis basic main-group elements is reported. With the increasing Lewis basicity from boron to carbon, nitrogen and sulfur in scaffolds, the corresponding lowest triplet excited state energy levels of the XCz gradually decreased, and the UOP colors of XCz-Cm showed a bathochromic shift from yellow-green (∼534 nm) to orange-red (∼580 nm). Conversely, the distances of π–π interaction of the XCz molecules and the radiative decay from the lowest triplet excited state to the ground state gradually increased, endowing the XCz-Cm with tunable UOP lifetimes (0.068–0.555 s). The XCz-Lab exhibited similar photoluminescence behavior as XCz-Cm, and the difference between XCz-Cm and XCz-Lab was attributed to the isomer of Cz-Cm. Owing to the long-lived triplet excited states, the CCz-Cm nanoparticles were applied in real-time lymph node afterglow imaging through intravenous injection in vivo successfully. This contribution not only presents a new versatile strategy for modulating UOP properties by introducing Lewis acidic/basic main-group elements but also extends their applications in afterglow imaging.