Functionalization of oxide surfaces by terpyridine phosphonate ligands: surface reactions and anchoring geometry

A strategy for creating a general-purposes surface functionalization platform is reported, based on direct attachment of phosphate groups onto hydroxylated surfaces and subsequent formation of a terpyridine-based monolayer. Such a platform is suitable for the construction, onto technologically relevant oxide surfaces, of single- and multilayer structures of interest in technological applications. In particular, the paper describes the successful attachment of 4-(2,2':6',2''-terpyridine-4-yl)benzenephosphonic acid (1, PPTP) onto a SiO(2) surface previously functionalized by means of Zr-phosphate groups. Two alternative anchoring strategies of the PPTP were explored: (i) a direct one-step way, implying no protection of terpyridinic functionality, and (ii) a three-step way, implying protection and successive deprotection of this group. It was found that, in the first case, the PPTP ligand anchoring to the Zr-containing phosphate layer takes place by means of terpyridinic group. At variance of this, in the second case, due to the protection of the terpyridinic functionality, the anchoring process takes place through the phosphonic group, making the terpyridinic moiety available for further reactions, i.e., multilayer constructs. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to study the functionalized surfaces, providing information on coverage, chemical structure, and stoichiometry of the various functionalized layers and, among the others, clear evidence of the PPTP linkage and orientation.