Diatomic C₂/NC Ligand Induced Conformation Variation of Trimetallic Clusters within a Carbon Cage

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Understanding the interplay between conformation and electronic properties of metal complexes at atomic level is key for rational design new functional molecules. Trimetallic clusterfullerenes (TMCFs) encapsulating quinary M3C2 carbide or M3NC carbonitride clusters offer an ideal model system elucidating conformation-electronic property correlation due to its unusual conformational versatility. Herein, we synthesize isolate two novel lanthanide-transition heteronuclear TMCFs, namely, CeTi2C2@Ih(7)-C80 CeTi2NC@Ih(7)-C80. Crystallographic studies reveal singly bonded C2/NC ligands coordinating vertically CeTi2 trimetallic plane within cluster, drastically different from bat-ray conformations reported all homonuclear TMCFs. Such bonding characters give rise variable structures [Ce4+(Ti2)8+(C2)6–]6+@C806– [Ce3+(Ti2)8+(NC)5–]6+@C806–, featuring a fixed tetravalent oxidation state Ti tunable states Ce (Ce4+/Ce3+), as confirmed by X-ray absorption spectroscopy magnetic measurements in combination with theoretical studies. Furthermore, scrutinizing TMCFs bearing M3C2/M3NC clusters, find that carbide/carbonitride are precisely dictated nature diatomic ligand so suffice strong coordination interactions encapsulated metals. Following such general rule governing variation, very field achieved on Ce3+ presence NC CeTi2NC@C80, giving first Ce-based single-molecule magnet shows open hysteresis 2 K.

Language: Английский

Fluoride Clusterfullerenes: Tuning Metal–Metal Bonding and Magnetic Properties via Single Fluorine Atom Doping

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 7, 2024

Endohedral fullerenes are known for their exceptional ability to host metal clusters that contain unique bonding motifs. In this study, we report a facile strategy synthesize new family of clusterfullerenes, fluoride clusterfullerenes (FCFs). This work demonstrates actinides and rare earth metals as well alkaline can be encapsulated within variety fullerene cages, these obtained in pristine form without additional functionalization methods. Notably, Th

Language: Английский