Caballero-Mancebo Elena, Cohen Boiko, Moreno José María, Corma Avelino, Díaz Urbano, Douhal Abderrazzak
Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La Mancha, Avenida Carlos III, S/N, 45071 Toledo, Spain.
Instituto de Tecnología Química, Universitat Politecnica de Valéncia-Consejo Superior de Investigaciones Científicas (UPV-CSIC), Av. de los Naranjos s/n, 46022 Valencia, Spain.
ACS Omega. 2018 Feb 7;3(2):1600-1608. doi: 10.1021/acsomega.7b01718. eCollection 2018 Feb 28.
In this work, we unravel the photodynamics of Nile Red (NR) interacting with Al-ITQ-HB nanostructure, a new layer-type metal-organic framework (MOF) with potential catalytic and photonic applications. Steady-state spectroscopy reveals the presence of NR monomers and aggregates when interacting with the MOF structure. Time-resolved experiments provide emission lifetimes of the interacting monomers, H- and J-type aggregates. We observed contributions from two monomer populations having different environments. One monomer species emits from the local-excited state and another from a photoproduced charge-separated state resulting from an ultrafast intramolecular charge transfer (ICT). Femtosecond fluorescence experiments reveal that the ICT process occurs in ∼1 ps. Fluorescence microscopy on single crystals and agglomerates of the composites shows a homogenous distribution of the dye lifetimes within the material. This study shows that the photobehavior of NR in Al-ITQ-HB MOF is dictated by its location within the material. The reported findings using a well-known polarity probe and a new two-dimensional MOF provide information on the microenvironment of this material, which may help for designing smart MOFs with potential applications in photonics and nanocatalysis.
在这项工作中,我们揭示了尼罗红(NR)与Al-ITQ-HB纳米结构相互作用的光动力学,Al-ITQ-HB是一种具有潜在催化和光子应用的新型层状金属有机框架(MOF)。稳态光谱显示,与MOF结构相互作用时存在NR单体和聚集体。时间分辨实验提供了相互作用的单体、H型和J型聚集体的发射寿命。我们观察到来自具有不同环境的两个单体群体的贡献。一种单体物种从局部激发态发射,另一种从超快分子内电荷转移(ICT)产生的光生电荷分离态发射。飞秒荧光实验表明,ICT过程在约1皮秒内发生。对复合材料单晶和团聚体的荧光显微镜观察显示,材料内染料寿命分布均匀。这项研究表明,NR在Al-ITQ-HB MOF中的光行为取决于其在材料中的位置。使用著名的极性探针和新型二维MOF所报告的研究结果提供了有关该材料微环境的信息,这可能有助于设计在光子学和纳米催化方面具有潜在应用的智能MOF。