On‐Surface Synthesis of Organolanthanide Sandwich Complexes

• Published in: Advanced science Vol. 11; no. 24; pp. e2308125 - n/a
• Main Authors: Mathialagan, Shanmugasibi K., Parreiras, Sofia O., Tenorio, Maria, Černa, Lenka, Moreno, Daniel, Muñiz‐Cano, Beatriz, Navío, Cristina, Valvidares, Manuel, Valbuena, Miguel A., Urgel, José I., Gargiani, Pierluigi, Miranda, Rodolfo, Camarero, Julio, Martínez, José I., Gallego, José M., Écija, David
• Format: Journal Article
• Language: English
• Published: Germany John Wiley & Sons, Inc 01-06-2024; John Wiley and Sons Inc; Wiley
• Subjects: Adsorption; Annealing; Catalysis; Chemistry; density functional theory; lanthanides; Ligands; Nanomaterials; on‐surface synthesis; organometallic chemistry; STM/STS; XMCD; STM/STS; on‐surface synthesis; density functional theory; organometallic chemistry; XMCD; lanthanides
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202308125

The synthesis of lanthanide‐based organometallic sandwich compounds is very appealing regarding their potential for single‐molecule magnetism. Here, it is exploited by on‐surface synthesis to design unprecedented lanthanide‐directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six‐membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X‐ray absorption spectroscopy, X‐ray linear and circular magnetic dichroism, and X‐ray photoelectron spectroscopy, complemented by density functional theory‐based calculations. Both lanthanide complexes self‐assemble in close‐packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self‐assembly, the erbium‐based species is magnetically isotropic, whereas the dysprosium‐based compound features an in‐plane magnetization.
The growth of a new family of organometallic sandwich complexes prepared by on‐surface synthesis is demonstrated. These complexes are based on lanthanide atoms and partially deprotonated hexahydroxybenzene species. Their growth mechanism, structure, chemical configuration, electronic structure, and magnetic properties are disclosed.