With complements of the ligands: an unusual S -shaped [Mn 7 ] 2 assembly from tethered calixarenes

The reaction between MnCl 2 ·4H 2 O, 2,2′-bis- p - t Bu-calix[4]arene (H 8 L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [MnIII10MnII4(L1) 3 (hmp) 4 (μ 3 -O) 4 (μ 3 -OH) 2 (MeOH) 4 (dmf) 6 ](dmf) 4 ( 6 ) upon vapour diffusion of petrole...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2020-07, Vol.49 (28), p.9882-9887
Main Authors: Coletta, Marco, Sanz, Sergio, Brechin, Euan K., Dalgarno, Scott J.
Format: Article
Language:English
Subjects:
Calixarenes
Crystallography
Ligands
Magnetic permeability
Molecular structure
Oxidation
Valence
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Summary:The reaction between MnCl 2 ·4H 2 O, 2,2′-bis- p - t Bu-calix[4]arene (H 8 L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [MnIII10MnII4(L1) 3 (hmp) 4 (μ 3 -O) 4 (μ 3 -OH) 2 (MeOH) 4 (dmf) 6 ](dmf) 4 ( 6 ) upon vapour diffusion of petroleum ether into the mother liquor. The crystals are in the monoclinic space group C 2/ c , with the asymmetric unit (ASU) comprising one half of the molecule. The structure describes a large S -shaped cluster (∼40 Å top to tail) where the unusual syn and anti conformations of the calixarene ligands results in two binding pockets each containing a [MnIII5MnII2] moiety comprised of two perpendicular, vertex-sharing [Mn 4 ] butterflies. One butterfly possesses a [MnIII4O 4 ] core and the second a [MnIII2MnII2O 3 ] unit with the Mn II ions in the central body positions. Magnetic susceptibility and magnetisation measurements reveal weak exchange interactions between the metal centres.
ISSN:1477-9226
1477-9234
DOI:10.1039/d0dt01766c