Bodipy 三重态激发态：形成、调控及应用。
The triplet excited state of Bodipy: formation, modulation and application.
机构信息
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E 208 Western Campus, 2 Ling-Gong Road, Dalian 116012, P. R. China.
出版信息
Chem Soc Rev. 2015 Dec 21;44(24):8904-39. doi: 10.1039/c5cs00364d. Epub 2015 Oct 14.
Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet-triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Förster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were briefly discussed.
硼二吡咯亚甲基（Bodipy）是研究最广泛的有机发色团之一。大多数研究都集中在 Bodipy 的单重激发态上，例如荧光。与此形成鲜明对比的是，Bodipy 的三重激发态的研究受到限制，但它是一个新兴领域，因为 Bodipy 的三重态对于几个领域非常重要，例如基础光化学研究、光动力疗法（PDT）、光催化和三重态-三重态湮灭（TTA）上转换。本文讨论了 Bodipy 三重激发态的产生、调制和应用方面的最新进展。Bodipy 三重态的形成是通过光激发，通常采用众所周知的方法，如重原子效应（包括 I、Br、Ru、Ir 等），以及新方法，如使用自旋转换器（如 C60）、电荷复合、激子耦合和双取代激发态。所有基于 Bodipy 的三重态光敏剂都显示出对可见光或近红外光的强吸收和长寿命的三重态激发态，这对于 PDT 或光催化中三重态激发态的应用非常重要。此外，还讨论了 Bodipy 三重态的切换（或调制）方法，例如基于光诱导电子转移（PET）的方法，通过控制竞争的Förster 共振能量转移（FRET）或分子间电荷转移（ICT）。控制三重态激发态将赋予功能性分子，例如可激活的 PDT 试剂或分子器件。值得注意的是，Bodipy 的单重激发态和三重态的切换可能遵循不同的原则。还讨论了 Bodipy 三重态在 PDT、氢气（H2）产生、光还原催化有机反应和 TTA 上转换中的应用。简要讨论了这些领域的挑战和机遇。
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