A metal-ion coordinated hybrid multilayer

Metal-organic coordination is an attractive means for constructing supramol ecular systems, providing versatility, simple, synthesis, and a defined geo metry. The convenience of changing "building blocks" during multilayer asse mbly is exploited for the fabrication of novel ion-coordinated hybrid multi layers on gold. Two bifunctional linkers are used, a tetrahydroxamate and a n organic diphosphonate, while the connection between layers is accomplishe d through Zr(TV) coordination, to form a well-defined hybrid multilayer. Th e two ion binders are compatible with respect to multilayer assembly, allow ing the change of linkers during construction while maintaining the film st ructural integrity and organization. The different chemical reactivity of t he binders enables rational structural manipulation of the multilayer, by s elective dissolution of the acid-sensitive hydroxamate layers while keeping the acid-resistant phosphonates (and underlying hydroxamates) intact. The process demonstrates the multilayer structural quality, where two diphospho nate monolayers are capable of effectively blocking proton penetration to u nderlying hydroxamate layers. This allows nanometer-scale reshaping of the molecular film according to a scheme introduced during its construction.