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Covalent Chemistry on a Van Der Waals Heterostructure

preprint
revised on 09.10.2019 and posted on 11.10.2019 by Julia Villalva, Sara Moreno, Palmira Villa, Luisa R. González, Cristina Navío, Andres Castellanos-Gomez, Emerson Giovanelli, Emilio Pérez
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 SnS2reacts 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 remains operative and shows negligible electronic interactions with franckeite in the ground state, while its fluorescence is strongly quenched upon photoexcitation.

History

Email Address of Submitting Author

emilio.perez@imdea.org

Institution

IMDEA Nanociencia

Country

Spain

ORCID For Submitting Author

0000-0002-8739-2777

Declaration of Conflict of Interest

No conflict of interest

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