Wu Liangliang, Fang Yu, Zuo Wanlong, Wang Juanjuan, Wang Ju, Wang Shufeng, Cui Zhifeng, Fang Weihai, Sun Hao-Ling, Li Yunliang, Chen Xuebo
Key Laboratory of Theoretical and Computational Photochemistry of the Ministry of Education, Department of Chemistry, Beijing Normal University, Xin-wai-da-jie No. 19, Beijing 100875, China.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, No.8, 3rd South Street, Zhongguancun, Haidian District, Beijing 100190, China.
JACS Au. 2022 Mar 16;2(4):853-864. doi: 10.1021/jacsau.1c00584. eCollection 2022 Apr 25.
Photosensitized energy transfer (EnT) phenomena occur frequently in a variety of photophysical and photochemical processes and have traditionally been treated with the donor-acceptor distance-dependent Förster and Dexter models. However, incorrect arguments and formulae were employed by ignoring energy resonance conditions and the selection rules of the state-to-state transition in special cases, especially for the sensitive intramolecular EnT of lanthanide complexes. Herein, we proposed an innovative model of energy-degeneracy-crossing-controlled EnT, which can be experimentally confirmed by time-resolved two-dimensional photoluminescence measurements. The computationally determined energy resonance region provides the most effective channel to achieve metal-to-ligand EnT beyond the distance-dependent model and sensitively bifurcates into symmetry-allowed or -forbidden channels for some representative europium antenna complexes. The outcomes of the multidisciplinary treatment contribute to a complementary EnT model that can be tuned by introducing a phosphorescence modulator and altering the antenna-related parameters of the ligand-centered energy level of the ππ* state and its spin-orbit coupling for the ππ* → S transition through mechanism-guided crystal engineering and should motivate further development of mechanistic models and applications.
光敏能量转移（EnT）现象在各种光物理和光化学过程中频繁出现，传统上一直用供体-受体距离依赖的福斯特和德克斯特模型来处理。然而，在特殊情况下，尤其是对于镧系配合物敏感的分子内EnT，由于忽略了能量共振条件和态-态跃迁的选择规则，采用了不正确的论点和公式。在此，我们提出了一种创新的能量简并交叉控制的EnT模型，该模型可以通过时间分辨二维光致发光测量进行实验验证。计算确定的能量共振区域提供了最有效的通道，以实现超越距离依赖模型的金属到配体的EnT，并敏感地分为一些代表性铕天线配合物的对称允许或禁止通道。多学科处理的结果有助于形成一个互补的EnT模型，该模型可以通过引入磷光调制器并通过机理引导的晶体工程改变ππ态的配体中心能级及其ππ→S跃迁的自旋-轨道耦合的天线相关参数来进行调整，这应该会推动机理模型和应用的进一步发展。
