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基于咔唑的稳健稀土金属有机框架材料:用于温度和N,N-二甲基甲酰胺传感的可调谐白光发射

Robust Carbazole-Based Rare-Earth MOFs: Tunable White-Light Emission for Temperature and DMF Sensing.

作者信息

Hu Yuchen, Khoo Rebecca Shu Hui, Lu Jingzhi, Zhang Xu, Zhang Jian

机构信息

Department of Chemistry, University of Nebraska─Lincoln, Lincoln, Nebraska 68588, United States.

The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.

出版信息

ACS Appl Mater Interfaces. 2022 Sep 14;14(36):41178-41185. doi: 10.1021/acsami.2c09497. Epub 2022 Aug 29.

Abstract

Rare-earth metal-organic frameworks (RE-MOFs) are an attractive platform to construct luminescent materials for practical applications in lighting, optoelectronics, and sensing. By adjusting the metal composition in mixed RE-MOFs, one can not only realize tunable emission but also construct ratiometric luminescent sensors. As such, it is highly desirable to prepare robust RE-MOFs that display efficient, multifunctional sensing capability. In this work, we designed and synthesized a series of RE-MOFs that exhibit both excellent thermal and chemical stability due to the incorporation of a bulky butyl group on a new carbazole-based ligand. By rationally tuning the molar ratio of Eu/Tb/Y, a white-light-emitting MOF was developed as an excellent thermal sensor that exhibits a temperature-induced ratiometric luminescence response between 278 and 378 K. After removing the coordinated solvent molecules via thermal treatment, the desolvated MOF materials exhibit excellent turn-on or color change sensitivity to recognize dimethylformamide (DMF) molecules. Such high sensitivity is attributed to the DMF coordination that induces the framework structure change and shifts the ligand's excited-state energy level to facilitate the ligand-to-metal energy transfer process. Taking together, NPF-700-RE represents a new class of robust, tunable luminescent materials that have great potential in white-light emission and thermal- and DMF-sensing applications.

摘要

稀土金属有机框架材料(RE-MOFs)是构建发光材料的一个有吸引力的平台,可用于照明、光电子学和传感等实际应用。通过调整混合RE-MOFs中的金属组成,不仅可以实现可调谐发射,还可以构建比率型发光传感器。因此,制备具有高效、多功能传感能力的稳健RE-MOFs是非常有必要的。在这项工作中,我们设计并合成了一系列RE-MOFs,由于在一种新型咔唑基配体上引入了庞大的丁基基团,这些材料表现出优异的热稳定性和化学稳定性。通过合理调节Eu/Tb/Y的摩尔比,开发出一种白色发光的MOF作为一种优异的热传感器,在278至378K之间表现出温度诱导的比率型发光响应。通过热处理去除配位溶剂分子后,脱溶剂的MOF材料对识别二甲基甲酰胺(DMF)分子表现出优异的开启或颜色变化灵敏度。这种高灵敏度归因于DMF配位诱导框架结构变化并改变配体的激发态能级,从而促进配体到金属的能量转移过程。综上所述,NPF-700-RE代表了一类新型的稳健、可调谐发光材料,在白光发射以及热传感和DMF传感应用中具有巨大潜力。

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