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Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2021-09-23 , DOI: 10.1039/c9cs00828d Wai-Lun Chan 1, 2 , Chen Xie 1 , Wai-Sum Lo 2 , Jean-Claude G Bünzli 1, 3 , Wai-Kwok Wong 1 , Ka-Leung Wong 1
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2021-09-23 , DOI: 10.1039/c9cs00828d Wai-Lun Chan 1, 2 , Chen Xie 1 , Wai-Sum Lo 2 , Jean-Claude G Bünzli 1, 3 , Wai-Kwok Wong 1 , Ka-Leung Wong 1
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Tetrapyrrole derivatives such as porphyrins, phthalocyanines, naphthalocyanines, and porpholactones, are highly stable macrocyclic compounds that play important roles in many phenomena linked to the development of life. Their complexes with lanthanides are known for more than 60 years and present breath-taking properties such as a range of easily accessible redox states leading to photo- and electro-chromism, paramagnetism, large non-linear optical parameters, and remarkable light emission in the visible and near-infrared (NIR) ranges. They are at the centre of many applications with an increasing focus on their ability to generate singlet oxygen for photodynamic therapy coupled with bioimaging and biosensing properties. This review first describes the synthetic paths leading to lanthanide–tetrapyrrole complexes together with their structures. The initial synthetic protocols were plagued by low yields and long reaction times; they have now been replaced with much more efficient and faster routes, thanks to the stunning advances in synthetic organic chemistry, so that quite complex multinuclear edifices are presently routinely obtained. Aspects such as redox properties, sensitization of NIR-emitting lanthanide ions, and non-linear optical properties are then presented. The spectacular improvements in the quantum yield and brightness of YbIII-containing tetrapyrrole complexes achieved in the past five years are representative of the vitality of the field and open welcome opportunities for the bio-applications described in the last section. Perspectives for the field are vast and exciting as new derivatizations of the macrocycles may lead to sensitization of other LnIII NIR-emitting ions with luminescence in the NIR-II and NIR-III biological windows, while conjugation with peptides and aptamers opens the way for lanthanide–tetrapyrrole theranostics.
中文翻译：
镧系元素-四吡咯配合物：合成、氧化还原化学、光物理特性和光子应用
卟啉、酞菁、萘酞菁和卟啉内酯等四吡咯衍生物是高度稳定的大环化合物，在与生命发展相关的许多现象中发挥着重要作用。它们与镧系元素的配合物已为人所知 60 多年，并具有令人叹为观止的特性，例如一系列易于获得的氧化还原状态，导致光致变色和电致变色、顺磁性、大的非线性光学参数以及显着的光发射。可见光和近红外 (NIR) 范围。它们处于许多应用的中心，越来越关注它们为光动力疗法产生单线态氧的能力以及生物成像和生物传感特性。本综述首先描述了导致镧系元素-四吡咯配合物及其结构的合成路径。最初的合成方案受到产量低和反应时间长的困扰；由于合成有机化学的惊人进步，它们现在已被更有效和更快的路线所取代，因此目前可以常规获得相当复杂的多核建筑物。然后介绍了诸如氧化还原特性、发射 NIR 的镧系元素离子的敏化和非线性光学特性等方面。Yb 的量子产率和亮度的惊人改进 然后介绍了 NIR 发射镧系元素离子的敏化和非线性光学特性。Yb 的量子产率和亮度的惊人改进 然后介绍了 NIR 发射镧系元素离子的敏化和非线性光学特性。Yb 的量子产率和亮度的惊人改进在过去五年中获得的含III的四吡咯配合物代表了该领域的活力，并为上一节所述的生物应用提供了欢迎机会。该领域的前景广阔而令人兴奋，因为大环的新衍生化可能会导致其他 Ln III NIR 发射离子在 NIR-II 和 NIR-III 生物窗口中发光，而与肽和适体的共轭为镧系元素-四吡咯治疗诊断学。
更新日期：2021-09-23
中文翻译：
镧系元素-四吡咯配合物：合成、氧化还原化学、光物理特性和光子应用
卟啉、酞菁、萘酞菁和卟啉内酯等四吡咯衍生物是高度稳定的大环化合物，在与生命发展相关的许多现象中发挥着重要作用。它们与镧系元素的配合物已为人所知 60 多年，并具有令人叹为观止的特性，例如一系列易于获得的氧化还原状态，导致光致变色和电致变色、顺磁性、大的非线性光学参数以及显着的光发射。可见光和近红外 (NIR) 范围。它们处于许多应用的中心，越来越关注它们为光动力疗法产生单线态氧的能力以及生物成像和生物传感特性。本综述首先描述了导致镧系元素-四吡咯配合物及其结构的合成路径。最初的合成方案受到产量低和反应时间长的困扰；由于合成有机化学的惊人进步，它们现在已被更有效和更快的路线所取代，因此目前可以常规获得相当复杂的多核建筑物。然后介绍了诸如氧化还原特性、发射 NIR 的镧系元素离子的敏化和非线性光学特性等方面。Yb 的量子产率和亮度的惊人改进 然后介绍了 NIR 发射镧系元素离子的敏化和非线性光学特性。Yb 的量子产率和亮度的惊人改进 然后介绍了 NIR 发射镧系元素离子的敏化和非线性光学特性。Yb 的量子产率和亮度的惊人改进在过去五年中获得的含III的四吡咯配合物代表了该领域的活力，并为上一节所述的生物应用提供了欢迎机会。该领域的前景广阔而令人兴奋，因为大环的新衍生化可能会导致其他 Ln III NIR 发射离子在 NIR-II 和 NIR-III 生物窗口中发光，而与肽和适体的共轭为镧系元素-四吡咯治疗诊断学。
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