A bis-calix[4]arene-supported [CuII16] cage

Lucinda r. b. Wilson, Marco Coletta, Mukesh k. Singh, Simon J. Teat, Adam Brookfield, Muralidharan Shanmugam, Eric j. l. Mcinnes, Stergios Piligkos, Scott j. Dalgarno, Euan k. Brechin

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

Reaction of 2,2′-bis-p-tBu-calix[4]arene (H8L) with Cu(NO3)2·3H2O and N-methyldiethanolamine (Me-deaH2) in a basic dmf/MeOH mixture affords [CuII16(L)2(Me-dea)4(μ4-NO3)2(μ-OH)4(dmf)3.5(MeOH)0.5(H2O)2](H6L)·16dmf·4H2O (4), following slow evaporation of the mother liquor. The central core of the metallic skeleton describes a tetracapped square prism, [Cu12], in which the four capping metal ions are the CuII ions housed in the calix[4]arene polyphenolic pockets. The [CuII8] square prism is held together “internally” by a combination of hydroxide and nitrate anions, with the N-methyldiethanolamine co-ligands forming dimeric [CuII2] units which edge-cap above and below the upper and lower square faces of the prism. Charge balance is maintained through the presence of one doubly deprotonated H6L2− ligand per [Cu16] cluster. Magnetic susceptibility measurements reveal the predominance of strong antiferromagnetic exchange interactions and an S = 1 ground state, while EPR is consistent with a large zero-field splitting.
Original languageEnglish
JournalDalton Transactions
Early online date9 Jun 2023
DOIs
Publication statusE-pub ahead of print - 9 Jun 2023

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