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

doi:10.1039/d3dt01448g

A bis-calix[4]arene-supported [Cu^II₁₆] 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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

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 [Cu^II₁₆(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 Cu^II ions housed in the calix[4]arene polyphenolic pockets. The [Cu^II₈] square prism is held together “internally” by a combination of hydroxide and nitrate anions, with the N-methyldiethanolamine co-ligands forming dimeric [Cu^II₂] 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 language	English
Pages (from-to)	8956-8963
Number of pages	8
Journal	Dalton Transactions
Volume	52
Issue number	26
DOIs	https://doi.org/10.1039/d3dt01448g
Publication status	Published - 9 Jun 2023

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10.1039/d3dt01448g

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@article{130a51dc03e24dd29a33784fdb8a1dfb,

title = "A bis-calix[4]arene-supported [CuII16] cage",

abstract = "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.",

author = "Wilson, {Lucinda R.B.} and Marco Coletta and Singh, {Mukesh K.} and Teat, {Simon J.} and Adam Brookfield and Muralidharan Shanmugam and McInnes, {Eric J.L.} and Stergios Piligkos and Dalgarno, {Scott J.} and Brechin, {Euan K.}",

note = "Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

year = "2023",

month = jun,

day = "9",

doi = "10.1039/d3dt01448g",

language = "English",

volume = "52",

pages = "8956--8963",

journal = "Dalton Transactions ",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "26",

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T1 - A bis-calix[4]arene-supported [CuII16] cage

AU - Wilson, Lucinda R.B.

AU - Coletta, Marco

AU - Singh, Mukesh K.

AU - Teat, Simon J.

AU - Brookfield, Adam

AU - Shanmugam, Muralidharan

AU - McInnes, Eric J.L.

AU - Piligkos, Stergios

AU - Dalgarno, Scott J.

AU - Brechin, Euan K.

PY - 2023/6/9

Y1 - 2023/6/9

N2 - 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.

AB - 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.

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U2 - 10.1039/d3dt01448g

DO - 10.1039/d3dt01448g

M3 - Article

C2 - 37325815

AN - SCOPUS:85163538375

SN - 1477-9226

VL - 52

SP - 8956

EP - 8963

JO - Dalton Transactions

JF - Dalton Transactions

IS - 26

ER -

A bis-calix[4]arene-supported [Cu^II₁₆] cage

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EPSRC National Research Facility for Electron Paramagnetic Resonance

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

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A bis-calix[4]arene-supported [Cu^II₁₆] cage