EXPLORING CHEMICAL TOOLS FOR CARBON NANOTUBES AND 2D MATERIALS Emilio M. Perez1; 1IMDEA NANOCIENCIA, Madrid, Spain; PAPER: 330/Nanomaterials/Invited (Oral) OS SCHEDULED: 18:15/Fri. 1 Dec. 2023/Dreams 3 ABSTRACT: In the last few years, the mechanical bond has been added to the chemistry toolbox for SWNT modification.[1] In this presentation, I will first discuss the characteristics of the mechanical bond that make it appealing for SWNTs. I will then describe the potential advantages of making mechanically-interlocked derivatives of SWNTs (MINTs), as compared to covalent or classic supramolecular derivatives of SWNTs, and go on to explain our approach for the synthesis of MINTs.[2,3] Finally, I will illustrate with examples how the making of MINTs can contribute to modifying the surface properties of SWNTs,[4] modulating their electronic properties,[5] and linking them to functional molecular fragments.[6,7] In the 2D materials field, I will describe the covalent grafting of 2H-MoS2 flakes on graphene monolayers embedded in field-effect transistors.[8] A bifunctional molecule was used that features a maleimide and a diazonium functional group, known to connect to sulfide- and carbon-based materials, respectively. MoS2 flakes were first exfoliated, functionalized by reaction with the maleimide moieties, then anchored to graphene through the diazonium groups. This approach enabled the simultaneous functionalization of several devices. The electronic properties of the resulting heterostructure are shown to be dominated by the MoS2–graphene molecular interface. I will also discuss the journey that has led to these results, including the development of a “click” chemistry reaction for transition metal-dichalcogenides,[9-11] and insights into the covalent patterning of graphene.[12-14] References: [1] A. López-Moreno, J. Villalva, E. M. Pérez, “Mechanically interlocked derivatives of carbon nanotubes: synthesis and potential applications” Chem. Soc. Rev. 2022, 51, 9433-9444. [2] A. de Juan, Y. Pouillon, L. Ruiz-González, A. Torres-Pardo, S. Casado, N. Martín, A. Rubio, E. M. Pérez, Angew. Chem., Int. Ed. 2014, 53, 5394-5400. [3] E. M. Pérez, Chem. Eur. J. 2017, 23, 12681-12689. [4] A. López-Moreno, B. Nieto-Ortega, M. Moffa, A. de Juan, M. M. Bernal, J. P. Fernández-Blázquez, J. J. Vilatela, D. Pisignano, E. M. Pérez, ACS Nano 2016, 10, 8012-8018. [5] M. Blanco, B. Nieto-Ortega, A. de Juan, M. Vera-Hidalgo, A. López-Moreno, S. Casado, L. R. González, H. Sawada, J. M. González-Calbet, and E. M. Pérez, Nat. Commun. 2018, 9, 2671. [6] S. Moreno-Da Silva, J. I. Martínez, A. Develioglu, B. Nieto-Ortega, L. de Juan-Fernández, L. Ruiz-Gonzalez, A. Picón, S. Oberli, P. J. Alonso, D. Moonshiram, E. M. Pérez, E. Burzurí, J. Am. Chem. Soc. 2021, 143, 21286-21293. [7] W. Zhang, M. Guillén-Soler, S. Moreno-Da Silva, A. López-Moreno, M. L. Ruiz-González, M. Giménez, E. M. Pérez Chem. Sci., 2022, 13, 9706-9712. [8] M. Vázquez Sulleiro, A. Develioglu, R. Quirós-Ovies, L. Martín-Pérez, N. Martín Sabanés, M. L. Gonzalez-Juarez, I. J. Gómez, M. Vera-Hidalgo, V. Sebastián, J. Santamaría, E. Burzurí, E. M. Pérez, Nat. Chem. 2022, 14, 695-700. [9] M. Vera-Hidalgo, E. Giovanelli, C. Navio, E. M. Pérez, J. Am. Chem. Soc. 2019, 141, 3767-3771. [10] R. Quirós-Ovies, M. Vázquez Sulleiro, M. Vera-Hidalgo, J. Prieto, I. J. Gómez, V. Sebastián, J. Santamaría, E. M. Pérez, Chem. Eur. J. 2020, 26, 6629-6634. [11] M. Vázquez Sulleiro, R. Quirós-Ovies, M. Vera-Hidalgo, I. J. Gómez, V. Sebastián, J. Santamaría, E. M. Pérez, Chem. Eur. J. 2021, 27, 2993. [12] J J Navarro, S Leret, F Calleja, D Stradi, A Black, R Bernardo-Gavito, M Garnica, D Granados, A L Vazquez de Parga, E M Pérez, and R Miranda, Nano Lett. 2016, 16, 355-361. [13] J. J. Navarro, F. Calleja, R. Miranda, E. M. Pérez, A. L. Vázquez de Parga, Chem. Commun. 2017, 53, 10418-10421. [14] A. Naranjo, N. Martín Sabanés, M. Vázquez Sulleiro, E. M. Pérez Chem. Commun. 2022, 58, 7813-7816. |