The building of van der Waals heterostructures and the decoration of 2D materials with organic molecules share a common goal: to obtain ultrathin materials with tailored properties. Performing controlled chemistry on van der Waals heterostructures would add an extra level of complexity, providing a pathway towards 2D–2D–0D mixed-dimensional heterostructures. Here we show that thiol–ene-like “click” chemistry can be used to decorate franckeite, a naturally occurring van der Waals heterostructure with maleimide reagents. ATR-IR and NMR analyses corroborate the Michael addition mechanism via the formation of a S–C covalent bond, while Raman and HR-TEM show that the SnS₂–PbS alternating structure of franckeite is preserved, and suggest that SnS₂ reacts preferentially, which is confirmed through XPS. We illustrate how this methodology can be used to add functional molecular moieties by decorating franckeite with porphyrins. UV-vis-NIR spectroscopy confirms that the chromophore ground state remains operative, showing negligible ground-state interactions with the franckeite. Excited-state interactions across the hybrid interface are revealed. Time-resolved photoluminescence confirms the presence of excited-state deactivation in the linked porphyrin ascribed to energy transfer to the franckeite.

中文翻译：

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与马来酰亚胺对方沸石的共价修饰：连接分子和范德华结构

范德华异质结构的构建和有机分子对2D材料的装饰具有一个共同的目标：获得具有定制性能的超薄材料。在范德华异质结构上进行受控化学反应将增加额外的复杂性，为实现2D–2D–0D混合异质结构提供了一种途径。在这里，我们证明了可以使用硫醇-烯样的“喀哒”化学来装饰方锰矿，这是一种自然产生的范德华与马来酰亚胺试剂的异质结构。ATR-IR和NMR分析通过形成S–C共价键来证实Michael加成机理，而Raman和HR-TEM表明，方钠石的SnS ₂ -PbS交替结构得以保留，并暗示SnS ₂优先反应，这是通过XPS确认的。我们说明了如何通过用卟啉修饰方钠石来使用这种方法来添加功能分子部分。紫外可见近红外光谱证实了发色团的​​基态仍然有效，表明与方沸石的基态相互作用可忽略不计。揭示了跨混合接口的激发态相互作用。时间分辨的光致发光证实了连接的卟啉中存在激发态失活，这归因于能量转移至方沸石。