Tandem templating strategies facilitate the assembly of calix[8]arene-supported Ln18 clusters

Yushu Jiao, Sergio Sanz*, Jan van Leusen, David Gracia, Angelos B. Canaj, Marco Evangelisti*, Euan K. Brechin*, Scott J. Dalgarno*, Paul Kögerler*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

Calix[n]arenes offer ideal chemical functionality through the polyphenolic lower rim to construct nano-sized coordination clusters with lanthanide (Ln) metal ions (e.g., NdIII10, GdIII8). However, the number of metal centers they can accommodate is still limited compared to that achievable with smaller ligands (e.g., GdIII140, GdIII104). Here, we exploit a combination of the “anion template strategy” and “templating ligands” to synthesise three highly symmetric (D3h, trigonal planar) LnIII18 (Ln = La, Nd, and Gd) systems, representing the largest calix[n]arene-based coordination clusters yet. The LnIII18 fragment is templated by a chloride anion located at the center of the cluster, wherefrom twelve µ3-OH- ligands bind ‘internally’ to the eighteen LnIII ions. ‘Externally’ the metallic skeleton is connected by p-tert-butylcalix[8]arene, oxo, chloro and carbonate ligands. The crystal packing in the lattice reveals large cylindrical channels of ~26 Å in diameter, whose pore volume corresponds to ~50% of the unit cell volume (using a 1.2 Å spherical probe radius). Magnetic measurements reveal the predominance of weak antiferromagnetic exchange in the Gd analog. Heat capacity data of GdIII18 reveal a high magnetic entropy with -?Sm = 23.7 J K-1 kg-1, indicating potential for engineering magnetic refrigerant materials with calix[8]arenes.

Original languageEnglish
JournalDalton Transactions
Early online date7 Feb 2024
Publication statusE-pub ahead of print - 7 Feb 2024


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