Rosas Rivas Oswaldo, Hamer Mariana, Baldoni Héctor A, Boone Maya, Van Deun Rik, Gomez Germán E
Área de Química General e Inorgánica "Dr. G. F. Puelles", Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis, Ejército de los Andes 950, San Luis 5700, Argentina.
Instituto de Investigaciones en Tecnología Química (INTEQUI), Almirante Brown 1455, San Luis 5700, Argentina.
Polymers (Basel). 2025 Apr 22;17(9):1135. doi: 10.3390/polym17091135.
A set of three-dimensional metal-organic frameworks, named MOF-76, belonging to the tetragonal P422 space group, based on Y(BTC)(HO) (1,3,5-benzenetricarboxylate) doped with Eu, Tb, and Eu/Tb were obtained under solvothermal conditions and fully characterized by powder X-ray diffraction, thermal, and vibrational analyses. In addition, upon UV light excitation (280 nm), all the powdered samples exhibited fine 4f-4f transitions, of which the D → F (Eu) and D → F (Tb) were the most intense ones. All samples were photophysically analyzed by determining the luminescence lifetimes, and their emission colors were quantified by calculating their chromaticities and color purities. Moreover, the intrinsic quantum yield, radiative, and non-radiative constants were calculated and compared to establish a structure-property relationship. Specifically, the Eu/Tb co-doped sample was employed to monitor its hypersensitive emissions in the presence of small volatile organic compounds (VOCs), showing quenching or enhancement of emission in protic and non-protic solvents. Furthermore, DFT calculations were carried out to understand the energy transfer processes between the sensor and the respective analytes. These results are promising for the development of solid-state lighting devices and colorimetric chemical sensors for specific compounds.
获得了一组三维金属有机框架,命名为MOF-76,属于四方P422空间群,基于掺杂有Eu、Tb和Eu/Tb的Y(BTC)(HO)(1,3,5-苯三甲酸酯),在溶剂热条件下制备,并通过粉末X射线衍射、热分析和振动分析进行了全面表征。此外,在紫外光激发(280 nm)下,所有粉末样品均表现出良好的4f-4f跃迁,其中D→F(Eu)和D→F(Tb)跃迁最为强烈。通过测定发光寿命对所有样品进行了光物理分析,并通过计算色度和色纯度对其发射颜色进行了量化。此外,计算并比较了本征量子产率、辐射和非辐射常数,以建立结构-性能关系。具体而言,采用Eu/Tb共掺杂样品监测其在存在小挥发性有机化合物(VOCs)时的超灵敏发射,在质子性和非质子性溶剂中显示出发射的猝灭或增强。此外,进行了密度泛函理论(DFT)计算,以了解传感器与相应分析物之间的能量转移过程。这些结果对于固态照明器件和特定化合物的比色化学传感器的开发具有重要意义。