Molecularly “clicking” active moieties to germanium-based inorganic 2D materials

Abstract

Thiol–ene click chemistry is presented as a “one-pot” synthetic strategy to implant molecular features upon commercially available allyl germanane 2D-Ge–CH2CHCH2 by covalently grafting thiol-rich active molecular components (R′–SH).

Rational Design of Stimuli‐Responsive Inorganic 2D Materials via Molecular Engineering: Toward Molecule‐Programmable Nanoelectronics

“…[260] Indeed, the fact that the bandgap of germanene can be easily tuned by the tethered ligand has increased the interested in developing alternative functionalization methods to widen the library of 2D-GeR derivatives in order to advance toward the development of versatile and robust synthetic methods capable of customizing Xanes with the desired molecular component; for example, by the inclusion of Grignard reactions on previously synthesized 2D-GeI (Figure 6C), [264] or by clicking thiol-rich molecular components upon 2D-GeCH 2 CH═CH 2 via a thiol-ene click reaction (Figure 6D). [18,120] In this last regard, Muñoz et al also exploited this click approach to reach organic-inorganic 2D-germanene heterostructures by covalently anchoring thiol-rich carbon dots. [120] Further germanene functionalization approaches have been recently summarized by Ng and Pumera [265] and Hartman et al [266] Regarding to the family of silicanes, the so-called siloxene-[SiH 1-x (OH) x ], whose structure is terminated with ─H and ─OH ligands-is probably the most exploited one.…”

“…[5,[11][12][13][14][15] Their ultimate thinness in combination with their high surface area plenty of reactive sites represents an excellent atomic structure not only to move electrons, but also to harbor active molecules. [16][17][18] Indeed, this represents pivotal characteristics to reach novel nanoarchitectures for the development of new forms of computation with ability to process logical binary information at the molecular level. Considering the outstanding results in the field obtained by mainstream graphene (the best known 2D material) and taking into account its absence of energy gap-fact that can hinder the proper implementation of graphene toward logic applications-, [19][20][21][22][23] the Materials Chemistry community has moved to explore alternative 2D materials exhibiting complementary features, viz., inorganic 2D materials (i2DMs).…”

2D Methyl Germanane Enhanced 3D Printed Photoelectrodes

“…Unlike graphene, the covalent functionalization of germanene with hydrogen, alkyl, or hydroxyl functional groups yields germanane with different properties compared to germanene without disrupting its electronic mobility but increasing five times higher than the parental element germanium. [30][31][32][33][34][35] The methyl functionalization provided more thermal stability and ideal electronic bandwidth for visible light absorption to the germanene, boosting their potential for photoelectrocatalytic applications by absorbing photon energy [25,34,36,37] and transferring the electrons from the valance band to the conduction band thereby accelerating the rate of reduction reaction of hydride ions to hydrogen molecules. [33] In this project, the usage of 2D methyl functionalized germanane on the 3D printed electrode has been studied for demonstrated hydrogen evolution reaction.…”