Controlled Covalent Functionalization of 2 H-MoS2 with Molecular or Polymeric Adlayers

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Authors

QUIROS-OVIES R. SULLEIRO M.V. VERA-HIDALGO M. PRIETO J. GOMEZ PEREZ Inmaculada Jennifer SEBASTIAN V. SANTAMARIA J. PEREZ E.M.

Year of publication 2020
Type Article in Periodical
Magazine / Source Chemistry - A European Journal
MU Faculty or unit

Central European Institute of Technology

Citation
web https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202000068
Doi http://dx.doi.org/10.1002/chem.202000068
Keywords click chemistry; 2D materials; covalent functionalization; maleimide; MoS2
Description Most air-stable 2D materials are relatively inert, which makes their chemical modification difficult. In particular, in the case of MoS2, the semiconducting 2 H-MoS2 is much less reactive than its metallic counterpart, 1T-MoS2. As a consequence, there are hardly any reliable methods for the covalent modification of 2 H-MoS2. An ideal method for the chemical functionalization of such materials should be both mild, not requiring the introduction of a large number of defects, and versatile, allowing for the decoration with as many different functional groups as possible. Herein, a comprehensive study on the covalent functionalization of 2 H-MoS2 with maleimides is presented. The use of a base (Et3N) leads to the in situ formation of a succinimide polymer layer, covalently connected to MoS2. In contrast, in the absence of base, functionalization stops at the molecular level. Moreover, the functionalization protocol is mild (occurs at room temperature), fast (nearly complete in 1 h), and very flexible (11 different solvents and 10 different maleimides tested). In practical terms, the procedures described here allow for the chemist to manipulate 2 H-MoS2 in a very flexible way, decorating it with polymers or molecules, and with a wide range of functional groups for subsequent modification. Conceptually, the spurious formation of an organic polymer might be general to other methods of functionalization of 2D materials, where a large excess of molecular reagents is typically used.
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