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

• Published in: Nature communications Vol. 3; no. 1; p. 1130
• Main Authors: Mattiuzzi, Alice, Jabin, Ivan, Mangeney, Claire, Roux, Clément, Reinaud, Olivia, Santos, Luis, Bergamini, Jean-François, Hapiot, Philippe, Lagrost, Corinne
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 2012; Nature Publishing Group
• Subjects: 639/638/541/966; 639/638/542; Chemical Sciences; Humanities and Social Sciences; multidisciplinary; Organic chemistry; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/ncomms2121

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. The spontaneous adsorption of alkanethiols is widely utilized to fabricate functional surfaces but gives limited stability and regularity. Mattiuzzi et al . report a method that uses preorganized platforms (rigid tetrapodant calix[4]arenes), which allows further surface functionalization and spatial control.