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.
Highlights
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
We show the preparation of a series of multi-Cecontaining heterometallic clusters in which the Ce atoms are bridged by Au atoms via the unsupported Ce–Au bonds with an on-surface coordination strategy
Given the critical role of the bridging Au adatoms in stabilizing the Ce2Au2(CN)[6] structure, we argue that the coordination centers of all the other multinuclear coordination structures achieved in this work are composed of the Ce–Au heterometallic clusters in which each pair of the nearest-neighboring Ce atoms are bridged by two Au adatoms, as proposed according to the atomic arrangement of the CeAu2 surface alloy prepared on Au(111)[32]
Summary
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. 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. Tremendous effort has been devoted to preparation of coordination compounds involving both Ln metals and TMs by wet chemistry, resulting in a number of Ln–TM heterometallic coordination complexes featuring unsupported d–f metal–metal bonds[4,5,6,7]. Density functional theory (DFT) studies reveal the indispensable role of the bridging Au adatoms in stabilizing the multiple Ce atoms within one cluster by forming the unsupported Ce–Au bonds between them. This work demonstrates on-surface coordination as an efficient strategy for preparing and organizing TM-bridged multi-Ln-containing heterometallic clusters stabilized by unsupported d–f metal–metal bonds
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