On-surface preparation of coordinated lanthanide-transition-metal clusters

Abstract

The study of lanthanide (Ln)-transition-metal (TM) heterometallic clusters which play key roles in various high-tech applications is a rapid growing field of research. Despite the achievement of numerous Ln-TM cluster compounds comprising one Ln atom, the synthesis of Ln-TM clusters containing multiple Ln atoms remains challenging. Here, we present the preparation and self-assembly of a series of Au-bridged heterometallic clusters containing multiple cerium (Ce) atoms via on-surface coordination. By employing different pyridine and nitrile ligands, the ordered coordination assemblies of clusters containing 2, 3 and 4 Ce atoms bridged by Au adatoms are achieved on Au(111) and Au(100), as revealed by scanning tunneling microscopy. Density functional theory calculations uncover the indispensable role of the bridging Au adatoms in constructing the multi-Ce-containing clusters by connecting the Ce atoms via unsupported Ce-Au bonds. These findings demonstrate on-surface coordination as an efficient strategy for preparation and organization of the multi-Ln-containing heterometallic clusters.

Packing Biomolecules into Sierpiński Triangles with Global Organizational Chirality

“…Surface-supported molecular Sierpiński triangles (STs) were revealed by theoretical simulations first , and experimentally prepared later. − A representative ST formed by coordination between 120° V-shaped organic molecules and metal atoms is schematically displayed in Figure a. If chiral biomolecules could mimic metal atoms to form 3-fold nodes with 120° V-shaped ligands, biomolecular STs are anticipated (Figure a).…”

An intermetallic molecular nanomagnet with the lanthanide coordinated only by transition metals

“…However, the aforementioned examples of the rare-earth intermetallics: SmCo 5 1 and Nd 2 Fe 14 B 2 provide clues for the possible direction in the design of RT-MNMs. Focusing the efforts on molecules comprising a rare-earth metal center coordinated solely by transition metal ions 31 – 34 , mimicking the first coordination sphere of the Sm center in the SmCo 5 magnet (Fig. 1A–C ) could enable the appearance of the direct exchange coupling between the highly anisotropic lanthanide central ion and the coordinated transition metals.…”

Engineering Periodic Dinuclear Lanthanide‐Directed Networks Featuring Tunable Energy Level Alignment and Magnetic Anisotropy by Metal Exchange

“…The physics and chemistry of lanthanides are receiving nowadays widespread attention due to their relevance in modern Despite the functional properties of lanthanides, which arise from the localized character of f-electrons, big atomic size, and inherent high spin-orbit coupling, only in the past decade the synthesis of lanthanide-directed coordinative architectures have been developed on surfaces. [26][27][28][29][30][31][32][33][34] Notably, due to the inner character of f-electrons, metal-organic interactions therein are based on a dominant ionic character with a partial covalent character. [1] As a result, the lanthanide coordinative sphere maximizes the coordination number, only limited by the steric interactions imposed by the ligand design.…”