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Crowding out: Ligand modification and their structure directing effects on brucite-like {Mx(µ3-OH)y} (M = Co(II), Ni(II)) core growth within polymetallic cages

Crowding out: Ligand modification and their structure directing effects on brucite-like {Mx(µ3-OH)y} (M = Co(II), Ni(II)) core growth within polymetallic cages
Crowding out: Ligand modification and their structure directing effects on brucite-like {Mx(µ3-OH)y} (M = Co(II), Ni(II)) core growth within polymetallic cages
Previous employment of the ligands 2-methoxy-6-[(methylimino)methyl]phenol (L1H) and 2-methoxy-6-[(phenylimino)methyl]phenol (L2H) has resulted in the self-assembly of pseudo metallocalix[6]arene complexes of general formulae: [M7(μ3-OH)6(Lx)6](NO3)y (M = Ni(II), x = 1, y = 2 (1) and Co(II/III), x = 2, y = 3 (2)). Extrapolating upon this work, we report the coordination chemistry of ligands 2-methoxy-6-{[(2-methoxyphenyl)imino]methyl}phenol (L3H), 2-[(benzylimino)methyl]-6-methoxyphenol (L4H), 2-[(benzylamino)methyl]-6-methoxyphenol (L5H) and 2-[(benzylamino)methyl]-4-bromo-6-methoxyphenol (L6H), whose structures are modifications of ligands L1–2H. These ligands are employed in the synthesis and characterisation of the dimetallic complex [Ni(II)2(L3)3(H2O)](NO3)·2H2O·3MeOH (3); the monometallic complexes [Ni(II)(L4)2] (4) and [Co(III)(L4)3]·H2O·MeOH (5a); and the tetranuclear pseudo metallocalix[4]arene complexes: [(NO3)⊂Co(II)4(μ3-OH)2(L5)4(H2O)2](NO3)·H2O (6), [(NO3)⊂Ni(II)4(μ3-OH)2(L5)4(H2O)2](NO3)·H2O (7) and [Ni(II)4(μ3-OH)2(L6)4(NO3)2]·MeCN (8). The tetrametallic ‘butterfly’ core topologies in 6–8 are discussed with respect to their structural and topological relationship with their heptanuclear [M7] (M = Co(II), Ni(II)) pseudo metallocalix[6]arene ancestors (1 and 2).
0300-9246
1477-1488
Slater-Parry, Mari E.
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Durrant, James P.
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Howells, Joshua M.
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Pitak, Mateusz
eeb6a00f-2291-4376-830f-d30dfd607ed1
Horton, Peter
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Klooster, Wim
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Coles, Simon J.
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O'Connor, Helen M.
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Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc
Barra, Anne-Laure
b7bb4922-902f-4e54-9229-e406bbf213c3
Jones, Leigh F.
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Slater-Parry, Mari E.
9d17c714-ee83-4fec-a37e-0032790f896a
Durrant, James P.
602d38c2-bad4-4468-90d5-0e9e54ea4a1b
Howells, Joshua M.
973a0ed6-4c9f-4bdf-98bd-4a56ae89de4f
Pitak, Mateusz
eeb6a00f-2291-4376-830f-d30dfd607ed1
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
O'Connor, Helen M.
d826fdbd-f27d-4b62-b37f-7d4a551ee26b
Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc
Barra, Anne-Laure
b7bb4922-902f-4e54-9229-e406bbf213c3
Jones, Leigh F.
fdb8562f-36c2-4f8f-9221-947e1d05a45e

Slater-Parry, Mari E., Durrant, James P., Howells, Joshua M., Pitak, Mateusz, Horton, Peter, Klooster, Wim, Coles, Simon J., O'Connor, Helen M., Brechin, Euan K., Barra, Anne-Laure and Jones, Leigh F. (2018) Crowding out: Ligand modification and their structure directing effects on brucite-like {Mx(µ3-OH)y} (M = Co(II), Ni(II)) core growth within polymetallic cages. Dalton Transactions, 2019 (48), 1477-1488. (doi:10.1039/c8dt04229b).

Record type: Article

Abstract

Previous employment of the ligands 2-methoxy-6-[(methylimino)methyl]phenol (L1H) and 2-methoxy-6-[(phenylimino)methyl]phenol (L2H) has resulted in the self-assembly of pseudo metallocalix[6]arene complexes of general formulae: [M7(μ3-OH)6(Lx)6](NO3)y (M = Ni(II), x = 1, y = 2 (1) and Co(II/III), x = 2, y = 3 (2)). Extrapolating upon this work, we report the coordination chemistry of ligands 2-methoxy-6-{[(2-methoxyphenyl)imino]methyl}phenol (L3H), 2-[(benzylimino)methyl]-6-methoxyphenol (L4H), 2-[(benzylamino)methyl]-6-methoxyphenol (L5H) and 2-[(benzylamino)methyl]-4-bromo-6-methoxyphenol (L6H), whose structures are modifications of ligands L1–2H. These ligands are employed in the synthesis and characterisation of the dimetallic complex [Ni(II)2(L3)3(H2O)](NO3)·2H2O·3MeOH (3); the monometallic complexes [Ni(II)(L4)2] (4) and [Co(III)(L4)3]·H2O·MeOH (5a); and the tetranuclear pseudo metallocalix[4]arene complexes: [(NO3)⊂Co(II)4(μ3-OH)2(L5)4(H2O)2](NO3)·H2O (6), [(NO3)⊂Ni(II)4(μ3-OH)2(L5)4(H2O)2](NO3)·H2O (7) and [Ni(II)4(μ3-OH)2(L6)4(NO3)2]·MeCN (8). The tetrametallic ‘butterfly’ core topologies in 6–8 are discussed with respect to their structural and topological relationship with their heptanuclear [M7] (M = Co(II), Ni(II)) pseudo metallocalix[6]arene ancestors (1 and 2).

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Accepted/In Press date: 20 December 2018
e-pub ahead of print date: 20 December 2018

Identifiers

Local EPrints ID: 429231
URI: http://eprints.soton.ac.uk/id/eprint/429231
ISSN: 0300-9246
PURE UUID: 57721be2-1d7d-4e6f-9b1b-68e27b6cabe2
ORCID for Mateusz Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for Peter Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 22 Mar 2019 17:30
Last modified: 16 Mar 2024 03:13

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Contributors

Author: Mari E. Slater-Parry
Author: James P. Durrant
Author: Joshua M. Howells
Author: Mateusz Pitak ORCID iD
Author: Peter Horton ORCID iD
Author: Wim Klooster
Author: Simon J. Coles ORCID iD
Author: Helen M. O'Connor
Author: Euan K. Brechin
Author: Anne-Laure Barra
Author: Leigh F. Jones

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