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Surface-supported robust two-dimensional lanthanide-carboxylate coordination networks

AuthorsCirera, Borja; Urgel, Jose Ignacio; Wanf, Yang; Aurwärter, Willy; Otero, Roberto; Gallego, José M. ; Alcamí, Manuel; Klyatskaya, Svetlana; Ruben, Mario; Martín, Fernando; Miranda, Rodolfo ; Écija,David; Barth, Johannes
Issue Date2015
Citation31st European Conference on Surface Science (2015)
AbstractThe lanthanide metals are of vital relevance in different fields such as photonics, magnetism, sensing, catalysis, materials science and medicine. In particular, they recently also emerged as important playground for coordination chemists to engineer novel functional molecules and materials, by exploiting their special characteristics and typically high coordination numbers. On the other hand, the exploration of functional surfaces and interfaces is rapidly advancing, whereby the interest is concomitantly driven by the need to advance the control of matter at the molecular scale and the discovery of novel procedures to produce self-assembled nanostructures at well-defined templates. However, despite its scientific interest and technological potential, interfacial coordination chemistry of lanthanides is still in its infancy and further advances are mandatory to fully exploit the potential of rare-earth elements in this respect. Here we present a multi-technique study, combining low- and variable-temperature scanning tunneling microscopy, x-ray photoelectron spectroscopy experiments and density functional theory simulations, demonstrating the gadolinium-directed assembly of interfacial 2D coordination networks on Cu(111) by exploiting metal-ligand interactions between ditopic carboxylate linkers and Gd centers. Our gives detailed, atomistic insights into the geometry and electronic nature of the lanthanide-carboxylate bond in a 2D environment, notably indicating chelating arrangements based on an unprecedented lateral coordination number of 8 for Gd vertexes. Furthermore, our observations and theoretical analysis indicates a coupling motif with ionic characteristics between the anionic carboxylate moieties and the positively charged Gd centers. Thanks to the high coordination number and appreciable bonding strength, the assemblies are thermally stable.
DescriptionPaper presented at the 31st European Conference on Surface Science (eccos 31), held in Barcelona (Spain) on August 31st - September 4th, 2015.
Appears in Collections:(ICMM) Comunicaciones congresos
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