With complements of the ligands: an unusual S-shaped [Mn7]2 assembly from tethered calixarenes

Marco Coletta; Sergio Sanz; Euan K. Brechin; Scott J. Dalgarno

doi:10.1039/D0DT01766C

With complements of the ligands: an unusual S-shaped [Mn₇]₂ assembly from tethered calixarenes

Marco Coletta, Sergio Sanz, Euan K. Brechin, Scott J. Dalgarno

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Abstract

The reaction between MnCl₂·4H₂O, 2,2′-bis-p-^tBu-calix[4]arene (H₈L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [Mn^III₁₀Mn^II₄(L1)₃(hmp)₄(μ₃-O)₄(μ₃-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 C2/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 [Mn^III₅Mn^II₂] moiety comprised of two perpendicular, vertex-sharing [Mn₄] butterflies. One butterfly possesses a [Mn^III₄O₄] core and the second a [Mn^III₂Mn^II₂O₃] unit with the Mn^II ions in the central body positions. Magnetic susceptibility and magnetisation measurements reveal weak exchange interactions between the metal centres.

Original language	English
Pages (from-to)	9882-9887
Number of pages	6
Journal	Dalton Transactions
Volume	49
Issue number	28
Early online date	8 Jul 2020
DOIs	https://doi.org/10.1039/D0DT01766C
Publication status	Published - 28 Jul 2020

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@article{e91f9b8ee0604f488c629bcac60aa5a9,

title = "With complements of the ligands: an unusual S-shaped [Mn7]2 assembly from tethered calixarenes",

abstract = "The reaction between MnCl2·4H2O, 2,2′-bis-p-tBu-calix[4]arene (H8L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [MnIII10MnII4(L1)3(hmp)4(μ3-O)4(μ3-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 C2/c, with the asymmetric unit (ASU) comprising one half of the molecule. The structure describes a large S-shaped cluster (∼40 {\AA} 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 [Mn4] butterflies. One butterfly possesses a [MnIII4O4] core and the second a [MnIII2MnII2O3] unit with the MnII ions in the central body positions. Magnetic susceptibility and magnetisation measurements reveal weak exchange interactions between the metal centres.",

author = "Marco Coletta and Sergio Sanz and Brechin, {Euan K.} and Dalgarno, {Scott J.}",

year = "2020",

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doi = "10.1039/D0DT01766C",

language = "English",

volume = "49",

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publisher = "Royal Society of Chemistry",

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T1 - With complements of the ligands: an unusual S-shaped [Mn7]2 assembly from tethered calixarenes

AU - Coletta, Marco

AU - Sanz, Sergio

AU - Brechin, Euan K.

AU - Dalgarno, Scott J.

PY - 2020/7/28

Y1 - 2020/7/28

N2 - The reaction between MnCl2·4H2O, 2,2′-bis-p-tBu-calix[4]arene (H8L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [MnIII10MnII4(L1)3(hmp)4(μ3-O)4(μ3-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 C2/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 [Mn4] butterflies. One butterfly possesses a [MnIII4O4] core and the second a [MnIII2MnII2O3] unit with the MnII ions in the central body positions. Magnetic susceptibility and magnetisation measurements reveal weak exchange interactions between the metal centres.

AB - The reaction between MnCl2·4H2O, 2,2′-bis-p-tBu-calix[4]arene (H8L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [MnIII10MnII4(L1)3(hmp)4(μ3-O)4(μ3-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 C2/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 [Mn4] butterflies. One butterfly possesses a [MnIII4O4] core and the second a [MnIII2MnII2O3] unit with the MnII ions in the central body positions. Magnetic susceptibility and magnetisation measurements reveal weak exchange interactions between the metal centres.

U2 - 10.1039/D0DT01766C

DO - 10.1039/D0DT01766C

M3 - Article

SN - 1477-9226

VL - 49

SP - 9882

EP - 9887

JO - Dalton Transactions

JF - Dalton Transactions

IS - 28

ER -

With complements of the ligands: an unusual S-shaped [Mn7]2 assembly from tethered calixarenes

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With complements of the ligands: an unusual S-shaped [Mn₇]₂ assembly from tethered calixarenes