灵活的发光MOF：诱捕旋转异构体的不稳定构型，原位客体响应性关断和开通发光及机理研究。,ACS Applied Materials & Interfaces

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灵活的发光MOF：诱捕旋转异构体的不稳定构型，原位客体响应性关断和开通发光及机理研究。
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-04-22 , DOI: 10.1021/acsami.0c02891
Sajal Khatua ₁ , Protap Biswas ₁

Affiliation

具有柔性和动态Cu ^I金属-有机骨架[Cu（I）-MOF（1）]，具有由柔性三联吡啶配体构建的定义明确的纳米孔通道，可为通过单晶或单晶形成不同种类的客体分子提供支架在环境条件下气相中的单晶（SCSC）转变具有可见的颜色变化。因此，Cu（I）-MOF（1）提供了一个潜在的分子识别平台，并经历了可由界面相互作用触发的客体响应性结构动力学。尽管具有旋转异构体的稳定构象，但它在SCSC过程中从其气相中选择性地将较不稳定的构象（偏色和薄纱状）封装到其腔中。所有来宾交换的过程都是可逆的。它显示了对一类中极性较小的客人的选择性。所有来宾交换过程的中间物以黑色材料（H ₂ O @ Cu（I）-MOF）（1z）的形式出现，然后通过SCSC方式封装每个来宾，随后进行来宾的替换高₂通过SCSC转换在环境条件下原位生成O。这证实了该过程是导致通用中间体的两步过程。MOF在H ₂ O去除原位晶格溶剂后失去了发光行为，并显示为黑色物质，并且在客体取代H ₂ O的情况下恢复了发光特性。因此，MOF既显示“关闭”又显示“分别在访客合并之前和之后“开启”，从而导致一种通用的关闭机制。荧光滴定实验表明苯及其衍生物对苯胺具有选择性。

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Flexible Luminescent MOF: Trapping of Less Stable Conformation of Rotational Isomers, In Situ Guest-Responsive Turn-Off and Turn-On Luminescence and Mechanistic Study.

Flexible and dynamic Cu^I metal–organic framework [Cu(I)-MOF (1)] with well-defined nanoporous channel built with flexible terpyridine ligand offers a scaffold for the inclusion of different classes of guest molecules through a single-crystal-to-single-crystal (SCSC) transformation in the vapor phase at ambient conditions with visual color change. Thus, Cu(I)-MOF (1) offers a potential platform for molecular recognition and undergoes guest-responsive structural dynamism that can be triggered by interfacial interactions. Despite having the stable conformation of the rotational isomers, it selectively encapsulates the less stable conformation (eclipsed and gauche) into its cavity from their vapor phases in the SCSC process. All of the guest-exchanged processes are reversible. It shows selectivity toward less polar guest in a class. The intermediate of all of the guest-exchanged processes appeared as a black material (H₂O@Cu(I)-MOF) (1z) prior to the encapsulation of each guest that happens through the SCSC manner followed by encapsulation of the guests replacing H₂O in situ at ambient conditions through SCSC transformation. This confirms that the process is a two-step process leading to a common intermediate. The MOF loses its luminescence behavior with H₂O removing lattice solvents in situ and appears as a black material, and it regains its luminescence property with the guests replacing H₂O. Thus, the MOF displays both luminescence “turn-off” and “turn-on” before and after incorporation of the guests, respectively, leading to a common turn-off mechanism. A fluorescence titration experiment shows selectivity toward aniline among benzene and its derivatives.

更新日期：2020-04-22

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