Covalent Chemistry on a Van Der Waals Heterostructure

12 March 2021, Version 3


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 de-activation in the linked porphyrin ascribed to energy transfer to the franckeite.


van der Waals heterostructure
Thiol-ene click reaction
covalent modification
2D materials

Supplementary materials

JV CovalentChemFranckeite SI 10032021

Supplementary weblinks


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.