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Temperature-dependent interchromophoric interaction in a fluorescent pyrene-based metal–organic framework

机译:荧光pyr基金属-有机骨架中温度相关的发色团间相互作用

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摘要

Compounds exhibiting tuneable fluorescence emission upon heating or cooling are considered smart materials as their optical properties can be exquisitely controlled by adjusting the external temperature. Herein, we report such a material, which is a porous pyrene-based metal–organic framework with a chemical formula of [Mg1.5(HTBAPy)(H2O)2]·3DMF (H4TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene), named >SION-7. The bulk solid material of >SION-7 can display either monomer or excimer fluorescence emission due to the temperature-dependent extent of interchromophoric interactions between the HTBAPy3– ligands within the framework. Consequently, the fluorescence emission colours gradually change from blue at low temperature (80 K) to yellow-green at high temperature (450 K). Interestingly, while kept in a relatively wide temperature range of 80–200 K, >SION-7 displays a structured monomer-like spectrum and its colour changes reversibly from deep to light blue. Ex situ variable-temperature (100–350 K) single-crystal X-ray diffractometry studies revealed the impact of solvent content on the optical properties of >SION-7, and illustrated the correlation between the position of the phenylene groups of the HTBAPy3– ligands at different temperatures and the interchromophoric interaction. Our study demonstrates a step forward towards the design of tuneable thermofluorochromic materials sought by optoelectronics.
机译:在加热或冷却时表现出可调节的荧光发射的化合物被认为是智能材料,因为可以通过调节外部温度来精确控制其光学性能。在这里,我们报道这种材料,它是一种具有化学式为[Mg1.5(HTBAPy)(H2O)2]·3DMF(H4TBAPy = 1,3,6,8-tetrakis)的多孔pyr基金属有机骨架(对-苯甲酸)py),名为> SION-7 。 > SION-7 的块状固体材料可以显示单体或受激准分子的荧光发射,这是由于框架内HTBAPy 3-配体之间发色团间相互作用的温度依赖性。因此,荧光发射颜色逐渐从低温(80 K)的蓝色变为高温(450 K)的黄绿色。有趣的是,> SION-7 保持在80–200 K的相对宽的温度范围内,显示出结构化的单体状光谱,其颜色从深蓝色到可逆蓝色变化。异位变温(100–350 K)单晶X射线衍射研究表明,溶剂含量对> SION-7 的光学性能有影响,并说明了位置之间的相关性。不同温度下HTBAPy 3 – 配体的亚苯基和发色团之间的相互作用。我们的研究表明,光子学向可调谐热致变色材料的设计迈出了一步。

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