“Chemistry-on-the-complex”: functional RuII polypyridyl-type sensitizers as divergent building blocks,Chemical Society Reviews

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“Chemistry-on-the-complex”: functional RuII polypyridyl-type sensitizers as divergent building blocks
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2018-09-24 00:00:00 , DOI: 10.1039/c8cs00096d
Tina Mede _{1,

2,

3,

4} , Michael Jäger _{1,

2,

3,

4,

5} , Ulrich S. Schubert _{1,

2,

3,

4,

5}

Affiliation

Ruthenium polypyridyl type complexes are potent photoactive compounds, and have found – among others – a broad range of important applications in the fields of biomedical diagnosis and phototherapy, energy conversion schemes such as dye-sensitized solar cells (DSSCs) and molecular assemblies for tailored photo-initiated processes. In this regard, the linkage of Ru^II polypyridyl-type complexes with specific functional moieties is highly desirable to enhance their inherent photophysical properties, e.g., with a targeting function to achieve cell selectivity, or with a dye or redox-active subunits for energy- and electron-transfer. However, the classical approach of performing ligand syntheses first and the formation of Ru complexes in the last steps imposes synthetic limitations with regard to tolerating functional groups or moieties as well as requiring lengthy convergent routes. Alternatively, the diversification of Ru complexes after coordination (termed “chemistry-on-the-complex”) provides an elegant complementary approach. In addition to the Click chemistry concept, the rapidly developing synthesis and purification methodologies permit the preparation of Ru conjugates via amidation, alkylation and cross-coupling reactions. In this regard, recent developments in chromatography shifted the limits of purification, e.g., by using new commercialized surface-modified silica gels and automated instrumentation. This review provides detailed insights into applying the “chemistry-on-the-complex” concept, which is believed to stimulate the modular preparation of unpreceded molecular assemblies as well as functional materials based on Ru-based building blocks, including combinatorial approaches.

中文翻译：

“复杂化学”：功能性Ru ^II聚吡啶基型敏化剂作为不同的构建基块

钌多吡啶基型配合物是有效的光活性化合物，除其他外，已在生物医学诊断和光疗，能量转换方案（例如染料敏化太阳能电池（DSSC）和用于定制照片的分子组装）领域中找到了广泛的重要应用。启动的过程。在这方面，非常需要Ru ^II多吡啶基型复合物与特定功能部分的连接，以增强其固有的光物理性质，例如，具有实现细胞选择性的靶向功能，或具有用于能量和电子转移的染料或氧化还原活性亚基。然而，首先进行配体合成并在最后步骤中形成Ru配合物的经典方法在耐受官能团或部分以及要求漫长的收敛途径方面强加了合成限制。或者，配位后Ru配合物的多样化（称为“复杂化学”）提供了一种优雅的补充方法。除了点击化学概念外，快速发展的合成和纯化方法还允许通过酰胺化，烷基化和交叉偶联反应。在这方面，色谱的最新发展改变了纯化的极限，例如，通过使用新型的商业化的表面改性硅胶和自动化仪器。这篇综述提供了“复杂化学”概念的应用的详细见解，该概念被认为可以促进无序分子组装的模块化制备以及基于钌基结构单元的功能材料，包括组合方法。

更新日期：2018-09-24

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