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具有不同电子供体和受体相互取向的紧凑型BDP-咔唑二元体系中的电子耦合和自旋轨道电荷转移系间窜越(SOCT-ISC)

Electronic coupling and spin-orbit charge transfer intersystem crossing (SOCT-ISC) in compact BDP-carbazole dyads with different mutual orientations of the electron donor and acceptor.

作者信息

Hou Yuqi, Kurganskii Ivan, Elmali Ayhan, Zhang Huimin, Gao Yuting, Lv Lingling, Zhao Jianzhang, Karatay Ahmet, Luo Liang, Fedin Matvey

机构信息

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-208 West Campus, 2 Ling Gong Rd., Dalian 116024, People's Republic of China.

International Tomography Center, SB RAS, and Novosibirsk State University, 630090 Novosibirsk, Russia.

出版信息

J Chem Phys. 2020 Mar 21;152(11):114701. doi: 10.1063/1.5145052.

Abstract

In order to study the spin-orbit charge transfer induced intersystem crossing (SOCT-ISC), Bodipy (BDP)-carbazole (Cz) compact electron donor/acceptor dyads were prepared. Charge transfer (CT) emission bands were observed for dyads showing strong electronic coupling between the donor and the acceptor (coupling matrix elements V, 0.06 eV-0.18 eV). Depending on the coupling magnitude, the CT state of the dyads can be either dark or emissive. Equilibrium between the LE (locally excited) state and the CT state was confirmed by temperature-dependent fluorescence studies. Efficient ISC was observed for the dyads with Cz connected at the meso-position of the BDP. Interestingly, the dyad with non-orthogonal geometry shows the highest ISC efficiency (Φ = 58%), which is different from the previous conclusion. The photo-induced charge separation (CS, time constant: 0.7 ps) and charge recombination (CR, ∼3.9 ns) were studied by femtosecond transient absorption spectroscopy. Nanosecond transient absorption spectroscopy indicated that the BDP-localized triplet state was exceptionally long-lived (602 µs). Using pulsed laser excited time-resolved electron paramagnetic resonance spectroscopy, the SOCT-ISC mechanism was confirmed, and we show that the electron spin polarization of the triplet state is highly dependent on the mutual orientation of the donor and acceptor. The dyads were used as triplet photosensitizers for triplet-triplet-annihilation (TTA) upconversion, and the quantum yield is up to 6.7%. TTA-based delayed fluorescence was observed for the dyads (τ = 41.5 µs). The dyads were also used as potent photodynamic therapy reagents (light toxicity of IC = 0.1 µM and dark toxicity of IC = 70.8 µM).

摘要

为了研究自旋 - 轨道电荷转移诱导的系间窜越(SOCT - ISC),制备了硼二吡咯(BDP)-咔唑(Cz)紧密电子供体/受体二元体系。对于供体和受体之间显示出强电子耦合(耦合矩阵元V,0.06 eV - 0.18 eV)的二元体系,观察到了电荷转移(CT)发射带。根据耦合强度,二元体系的CT态可以是暗态或发光态。通过温度依赖的荧光研究证实了局域激发(LE)态和CT态之间的平衡。对于在BDP的中位连接Cz的二元体系,观察到了高效的ISC。有趣的是,具有非正交几何结构的二元体系显示出最高的ISC效率(Φ = 58%),这与先前的结论不同。通过飞秒瞬态吸收光谱研究了光诱导电荷分离(CS,时间常数:0.7 ps)和电荷复合(CR,~3.9 ns)。纳秒瞬态吸收光谱表明,BDP局域的三重态寿命极长(602 µs)。使用脉冲激光激发的时间分辨电子顺磁共振光谱,证实了SOCT - ISC机制,并且我们表明三重态的电子自旋极化高度依赖于供体和受体的相互取向。二元体系用作三重态 - 三重态湮灭(TTA)上转换的三重态光敏剂,量子产率高达6.7%。观察到二元体系基于TTA的延迟荧光(τ = 41.5 µs)。二元体系还用作有效的光动力治疗试剂(光毒性IC = 0.1 µM,暗毒性IC = 70.8 µM)。

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