Electrografting of calix[4]arenediazonium salts to form versatile robust platforms for spatially controlled surface functionalization

Abstract

An essential issue in the development of materials presenting an accurately functionalized surface is to achieve control of layer structuring. Whereas the very popular method based on the spontaneous adsorption of alkanethiols on metal faces stability problems, the reductive electrografting of aryldiazonium salts yielding stable interface, struggles with the control of the formation and organization of monolayers. Here we report a general strategy for patterning surfaces using aryldiazonium surface chemistry. Calix[4]tetra-diazonium cations generated in situ from the corresponding tetra-anilines were electrografted on gold and carbon substrates. The well-preorganized macrocyclic structure of the calix[4]arene molecules allows the formation of densely packed monolayers. Through adequate decoration of the small rim of the calixarenes, functional molecules can then be introduced on the immobilized calixarene subunits, paving the way for an accurate spatial control of the chemical composition of a surface at molecular level.

Chemically modulated graphene quantum dot for tuning the photoluminescence as novel sensory probe

“…The total amount of carbon, fluorine, oxygen and nitrogen were 45, 19, 30, and 6%, respectively, for HFHPB-GQD (Figs 3 and S2). The deconvoluted C1s spectra of HFHPB-GQD showed several components at 284.4, 285.6, 286.2, 287.6, and 289.2 eV, which were related to C-C, C-CF, C-O, C=O or C-F, and O-C=O, respectively212223. A strong chemically shifted peak was observed at 292.2 eV, and this is related to the binding energy of C-F because the high electronegativity of fluorine resulted in the functionalization of GQDs with a HFHPB moiety2224.…”

Controlled Zn‐Mediated Grafting of Thin Layers of Bipodal Diazonium Salt on Gold and Carbon Substrates

“…Besides, this phenol group is difficult to derivatize due to the steric hindrance of the surface. A similar problem has been observed in the electrografting of a calix [4]-tetraarenediazonium salt [41] but should not markedly affect the reactivity of the COOH group and hence the applicability of the modified surface for the attachment of other molecules.…”

One‐step Solvent‐free Synthesis and Grafting of Diazonium Ions at Glassy Carbon Electrodes

“…The resulting grafted film coverage ranges from submonolayer to multilayer . Strategies to yield thin layers include adding radical scavengers to the diazonium ion solution, performing electrografting in viscous ionic liquid media , adding protecting groups to the diazonium ion that are subsequently cleaved , and using diazonium ions with bulky substituents, including some that can be further functionalized after grafting .…”