机械发光MOF纳米片：方钠石骨架结构中发光客体的空间分子隔离
Mechanoluminescent MOF nanoplates: spatial molecular isolation of light-emitting guests in a sodalite framework structure
摘要：
机械发光材料在纳米技术中有着广泛的应用前景，如基于光子学的传感器和智能光电子学。然而，机械发光金属有机框架（MOF）材料的实例在文献中相对较少。在本文中，我们提出了一种先前未描述的Guest@M0F系统，其包含二萘嵌苯@ZIF-8纳米片，<->当经受中等水平的机械诱导压力（~ 10 s MPa）时，所述二萘嵌苯@ZIF-8纳米片将经历可逆的442 nm-502 nm光电发射切换。通过高浓度反应（HCR）策略在环境条件下合成纳米片，以产生容纳高度发光的二萘嵌苯客体的结晶ZIF-8框架;后者被限制在ZIF-8的多孔方钠石笼内。值得注意的是，我们表明，在固态条件下，它是空间隔离和纳米分区的发光客人，赋予一个独特的解决方案，如在主客体组装测量的光学性能。我们阐明了如何通过机械改性底层纳米片的纳米级包装来实现可见光发射的可切换的红移或蓝移。理论计算表明，主机方钠石笼的弹性加上分子间的弱相互作用的受限的客人是巩固观察到的独特的机械发光行为。
英文摘要：
Mechanoluminescent materials have a wide range of promising nanotechnological applications, such as photonics based sensors and smart optoelectronics. Examples of mechanoluminescent metal-organic framework (MOF) materials, however, are relatively scarce in the literature. Herein, we present a previously undescribed Guest@MOF system, comprising Perylene@ZIF-8 nanoplates which will undergo a reversible 442 nm <->502 nm photoemission switching when subject to a moderate level of mechanically induced pressure (~10s MPa). The nanoplates were synthesized via a high-concentration reaction (HCR) strategy at ambient conditions, to yield a crystalline ZIF-8 framework hosting the highly luminous Perylene guests; the latter confined within the porous sodalite cages of ZIF-8. Remarkably, we show that in a solid-state condition, it is the spatial isolation and nano-partitioning of the luminescent guests that bestow a unique solution-like optical properties measured in the host-guest assembly. We elucidate how the switchable red- or blue-shifts of the visible emission can be accomplished by mechanically modifying the nanoscale packing of the underlying nanoplates. Theoretical calculations suggest that the elasticity of the host sodalite cage coupled with the intermolecular weak interactions of the confined guest are underpinning the unique mechanoluminescent behavior observed.
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