State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
Chem Soc Rev. 2013 Feb 21;42(4):1568-600. doi: 10.1039/c2cs35363f. Epub 2013 Jan 18.
Coordination chemistry plays an essential role in the design of photoluminescent probes for metal ions. Metal coordination to organic dyes induces distinct optical responses which signal the presence of metal species of interest. Luminescent lanthanide (Ln(3+)) and transition metal complexes of d(6), d(8) and d(10) configurations often exhibit unique luminescence properties different from organic dyes, such as high quantum yield, large Stokes shift, long emission wavelength and emission lifetimes, low sensitivity to microenvironments, and can be explored as lumophores to construct probes for metal ions, anions and neutral species. In this review, the design principles and coordination chemistry of metal probes based on mechanisms of PeT, PCT, ESIPT, FRET, and excimer formation will be discussed in detail. Particular attention will be given to rationales for the design of turn-on and ratiometric probes. Moreover, phosphorescent probe design based on Ln(3+) and d(6), d(8) and d(10)-metal complexes are also presented via discussing certain factors affecting the phosphorescence of these metal complexes. A survey of the latest progress in photoluminescent probes for identification of essential metal cations in the human body or toxic metal cations in the environment will be presented focusing on their design rationales and sensing behaviors. Metal complex-based photoluminescent probes for biorelated anions such as PPi, and neutral biomolecules ATP, NO, and H(2)S will be discussed also in the context of their metal coordination-related sensing behaviors and design approaches.
配位化学在设计用于金属离子的光致发光探针中起着至关重要的作用。金属与有机染料的配位会引起明显的光学响应，从而表明感兴趣的金属物种的存在。镧系元素（Ln(3+)）和 d(6)、d(8)和 d(10)构型的过渡金属配合物通常表现出与有机染料不同的独特发光特性，例如高量子产率、大斯托克斯位移、长发射波长和发射寿命、对微环境的低灵敏度，并且可以作为发光体来构建用于金属离子、阴离子和中性物质的探针。在这篇综述中，将详细讨论基于 PeT、PCT、ESIPT、FRET 和激基缔合物形成机制的金属探针的设计原则和配位化学。特别关注设计开关键和比率探针的原理。此外，还将通过讨论影响这些金属配合物磷光的某些因素，介绍基于 Ln(3+)和 d(6)、d(8)和 d(10)-金属配合物的磷光探针设计。将重点介绍其设计原理和传感行为，介绍用于鉴定人体中必需金属阳离子或环境中有毒金属阳离子的光致发光探针的最新进展。还将讨论基于金属配合物的用于生物相关阴离子（如 PPi）和中性生物分子（如 ATP、NO 和 H(2)S）的光致发光探针，以及它们与金属配位相关的传感行为和设计方法。
