Direct Covalent Functionalization of H-Terminated 2D Germanane with Thiolated Molecules : Passivation and Tuning of Optoelectronic Properties
Campos Lendínez, Ángel (Universitat Autònoma de Barcelona. Departament de Química)
Faraudo, Jordi (Institut de Ciència de Materials de Barcelona)
García-Antón, Jordi (Universitat Autònoma de Barcelona. Departament de Química)
Sala Román, Xavier (Universitat Autònoma de Barcelona. Departament de Química)
Muñoz, Jose (Universitat Autònoma de Barcelona. Departament de Química)

Fecha:	2024
Resumen:	Covalent molecular functionalization allows the physicochemical properties of 2D materials to be precisely tuned and modulated on-demand. Nonetheless, research on the molecular functionalization of 2D monoelemental graphene-like materials─known as Xenes─remains scarce, being mainly restricted to a specific type of solid-state chemical reaction based on the topotactic transformation of bulkier Zintl phases. Herein, a robust and general chemical approach is reported for the direct functionalization of commercially available H-terminated 2D germanene (2D-GeH) with thiolated molecules (R-SH) via Ge-S bond formation. While the material characterization data provide direct experimental evidence of the Ge-S chemical bonding, density functional theory (DFT) calculations also predict its existence. Remarkably, the anchored thiolated molecules also favor the passivation of the 2D Xene against air oxidation, enlarging its benefits for real implementation. As a proof-of-principle, a redox-responsive molecular moiety such as 6-(ferrocenyl)hexanethiol (Fc6-SH) has been exploited to induce changes in the optoelectronic properties of the resulting 2D-GeFc6 heterostructure by simply modulating the external bias potential, making it possible to optically and electrically read out a molecular switch on 2D Xene via implanting molecular responsiveness. Remarkably, the ON/OFF ratio has been shown to be dependent on the distance between the redox-responsive Fc moiety and the 2D Xene surface through the alkyl chain length. Overall, the reported a-la-carte molecular engineering approach provides the basis toward the rapid development of stable 2D-GeR derivatives exhibiting molecule-programmable properties.
Ayudas:	Agencia Estatal de Investigación PID2019-104171RB-I00 Agencia Estatal de Investigación RYC2021-033820-I Ministerio de Ciencia e Innovación CEX2019-000917-S Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-01519
Nota:	Altres ajuts: acords transformatius de la UAB
Derechos:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Lengua:	Anglès
Documento:	Article ; recerca ; Versió publicada
Materia:	2D materials ; Electrodes ; Germanene ; Molecular switches ; Responsive materials
Publicado en:	ACS applied materials & interfaces, Vol. 16, Issue 48 (December 2024) , p. 66280-66289, ISSN 1944-8252

DOI: 10.1021/acsami.4c17152
PMID: 39561093

10 p, 3.9 MB

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