High-Nuclearity Ln 210 Al 140 Clusters: Neonates of Open Hollow Dodecahedral Cage Families

• Published in: Journal of the American Chemical Society 2024-08, Vol.146 (32), p.22134-22139
• Main Authors: Chen, Man-Ting, Xu, Qiao-Fei, Aibibula, Mukeremu, Kong, Xiang-Jian, Long, La-Sheng, Zheng, Lan-Sun
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.4c07231

Open hollow dodecahedral cage clusters have long been a coveted target in synthetic chemistry, yet their creation poses immense challenges. Here we report two open hollow dodecahedral lanthanide-aluminum (Ln-Al) heterometallic cage clusters, namely, [Ln Al (μ -OH) (μ -OH) (OAc) (H O) ](ClO ) ·(MeCN) ·(H O) , (Ln = Dy and = 27, = 300 for ; Ln = Y and = 28, = 420 for ). Remarkably, the 350 metal atoms in and display a Keplerate-type four-shell structure of truncated icosidodecahedron@dodecahedron@dodecahedron@icosidodecahedron. The diameter of the cationic cluster in is approximately 5.0 nm, with an inner cavity diameter of about 2.8 nm and a window diameter of roughly 0.66 nm. The cluster in boasts an accessible inner void volume of up to 15,000 Å . Notably, these cage clusters maintain stability in water, and the truncated icosidodecahedrons in and are the first of their kind synthesized to date. Given that the open hollow dodecahedral Ln-Al cage cluster has never been reported before, this work represents a member in the family of hollow open dodecahedral cages.