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Metal-Organic Frameworks with Multiple Luminescence Emissions: Designs and Applications.
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2020-01-30 , DOI: 10.1021/acs.accounts.9b00575 Hua-Qing Yin 1 , Xue-Bo Yin 1
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2020-01-30 , DOI: 10.1021/acs.accounts.9b00575 Hua-Qing Yin 1 , Xue-Bo Yin 1
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Emissive species are powerful for luminescent detection with high sensitivity and simple procedure and for light-emitting diode (LED) lighting because of their high efficiency, long lifetime, and low energy consumption. Here we propose the concept of multiple luminescence emissions from a single matrix or species under single-wavelength excitation. Multiemission not only realizes the high sensitivity of luminescence sensing but also possesses the capacity of self-reference for environment-free interferences. The color change is also convenient for visible detection. In multiemission species, every emissive center responds to a specific analyte to improve the efficiency for multiple-target detection. Multiemission also extends the applications to anticounterfeiting, colorful LEDs, and information storage. To date, it is still challenging to combine more than one type of emissive center in a single matrix or species. Obtaining multiemission under single-wavelength excitation also needs exquisite design. Metal-organic frameworks (MOFs) are porous hybrid assemblies prepared with metal ions and organic ligands. Metal nodes and ligands with large π-conjugated systems have the potential for the construction of luminescent MOFs. Abundant and diverse precursors provide the possibility to prepare MOFs with multiple luminescence emissions. The pores or channels of MOFs also act as hosts to encapsulate luminescent guest species as additional emissive sites. In this Account, we propose the concept of multiple-luminescence MOFs (ML-MOFs) and summarize the recent research progress on their designs, constructions, and applications reported by our group and others. ML-MOFs are MOFs that possess more than one emissive center under single-wavelength excitation. Six different kinds of construction strategies of ML-MOFs are introduced: (1) multiemission from both metal nodes and ligands in single MOFs; (2) use of mixed-metal nodes as multiemission centers in single MOFs; (3) combination of different emissive MOFs as a whole to achieve multiemission application; (4) host-guest emissions from emissive MOFs after encapsulation of luminescent guest species; (5) organization of different emissive ligands in a single MOF for multiemission; and (6) use of single ligands exhibiting dual emission to prepare ML-MOFs. We also discuss the mechanisms that realize multiple emissions from MOFs under single-wavelength excitation, such as the antenna effect and excited-state intramolecular proton transfer. The applications of ratiometric sensing, LED lighting, anticounterfeiting, and information storage are summarized. With this Account, we hope to spark new ideas and to inspire new endeavors in the design and construction of ML-MOFs, especially with postsynthetic techniques such as postsynthetic modification, postsynthetic exchange, and postsynthetic deprotection, to promote the applications of MOFs in sensing, lighting, information storage, and others.
中文翻译：
具有多种发光的金属有机框架：设计和应用。
发射物种具有高效率，长寿命和低能耗的特性，因此它们对于发光检测具有高灵敏度和简单的过程，以及对于发光二极管（LED）照明，具有强大的功能。在这里，我们提出了在单波长激发下从单个基质或物种发出多种发光的概念。多发射不仅实现了发光感测的高灵敏度，而且还具有针对无环境干扰的自参考能力。颜色变化也便于可见检测。在多发射物种中，每个发射中心都对特定的分析物做出响应，以提高多目标检测的效率。多重发射还将应用范围扩展到防伪，彩色LED和信息存储。至今，在单个矩阵或物种中组合不止一种类型的发射中心仍然具有挑战性。在单波长激发下获得多发射也需要精巧的设计。金属有机骨架（MOF）是用金属离子和有机配体制备的多孔杂化组件。具有大型π共轭体系的金属节点和配体具有构建发光MOF的潜力。丰富多样的前驱物为制备具有多种发光发射的MOF提供了可能性。MOF的孔或通道还充当宿主，封装发光的客体作为额外的发射位点。在此帐户中，我们提出了多发光MOF（ML-MOF）的概念，并总结了我们小组和其他组织报告的有关其设计，构造和应用的最新研究进展。ML-MOF是在单波长激发下拥有一个以上发射中心的MOF。介绍了六种不同类型的ML-MOF的构建策略：（1）单个MOF中金属节点和配体的多重发射；（2）在单个MOF中使用混合金属节点作为多发射中心；（3）结合不同的发射MOF整体实现多发射应用；（4）封装发光客体后，来自发射MOF的主客体发射；（5）在单个MOF中组织不同的发射配体进行多发射；（6）使用具有双重发射的单一配体制备ML-MOF。我们还讨论了在单波长激发下实现MOF多重发射的机制，例如天线效应和激发态分子内质子转移。总结了比率感测，LED照明，防伪和信息存储的应用。借助此帐户，我们希望在ML-MOF的设计和构建中激发新的想法并激发新的努力，尤其是利用合成后技术（例如合成后修饰，合成后交换和合成后去保护），以促进MOF在传感，照明，信息存储等。
更新日期：2020-01-31
中文翻译：
具有多种发光的金属有机框架：设计和应用。
发射物种具有高效率，长寿命和低能耗的特性，因此它们对于发光检测具有高灵敏度和简单的过程，以及对于发光二极管（LED）照明，具有强大的功能。在这里，我们提出了在单波长激发下从单个基质或物种发出多种发光的概念。多发射不仅实现了发光感测的高灵敏度，而且还具有针对无环境干扰的自参考能力。颜色变化也便于可见检测。在多发射物种中，每个发射中心都对特定的分析物做出响应，以提高多目标检测的效率。多重发射还将应用范围扩展到防伪，彩色LED和信息存储。至今，在单个矩阵或物种中组合不止一种类型的发射中心仍然具有挑战性。在单波长激发下获得多发射也需要精巧的设计。金属有机骨架（MOF）是用金属离子和有机配体制备的多孔杂化组件。具有大型π共轭体系的金属节点和配体具有构建发光MOF的潜力。丰富多样的前驱物为制备具有多种发光发射的MOF提供了可能性。MOF的孔或通道还充当宿主，封装发光的客体作为额外的发射位点。在此帐户中，我们提出了多发光MOF（ML-MOF）的概念，并总结了我们小组和其他组织报告的有关其设计，构造和应用的最新研究进展。ML-MOF是在单波长激发下拥有一个以上发射中心的MOF。介绍了六种不同类型的ML-MOF的构建策略：（1）单个MOF中金属节点和配体的多重发射；（2）在单个MOF中使用混合金属节点作为多发射中心；（3）结合不同的发射MOF整体实现多发射应用；（4）封装发光客体后，来自发射MOF的主客体发射；（5）在单个MOF中组织不同的发射配体进行多发射；（6）使用具有双重发射的单一配体制备ML-MOF。我们还讨论了在单波长激发下实现MOF多重发射的机制，例如天线效应和激发态分子内质子转移。总结了比率感测，LED照明，防伪和信息存储的应用。借助此帐户，我们希望在ML-MOF的设计和构建中激发新的想法并激发新的努力，尤其是利用合成后技术（例如合成后修饰，合成后交换和合成后去保护），以促进MOF在传感，照明，信息存储等。
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