Crowding out: ligand modifications and their structure directing effects on brucite-like {M x (μ 3 -OH) y } (M = Co(ii), Ni(ii)) core growth within polymetallic cages

Previous employment of the ligands 2-methoxy-6-[(methylimino)methyl]phenol (L H) and 2-methoxy-6-[(phenylimino)methyl]phenol (L H) has resulted in the self-assembly of pseudo metallocalix[6]arene complexes of general formulae: [M (μ -OH) (L ) ](NO ) (M = Ni(ii), x = 1, y = 2 (1) and Co(ii/iii), x =...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2019-01, Vol.48 (4), p.1477-1488
Main Authors: Slater-Parry, Mari E, Durrant, James P, Howells, Joshua M, Pitak, Mateusz B, Horton, Peter N, Klooster, Wim T, Coles, Simon J, O'Connor, Helen M, Brechin, Euan K, Barra, Anne-Laure, Jones, Leigh F
Format: Article
Language:English
Subjects:
Brucite
Cages
Chemical Sciences
Coordination chemistry
Crystallography
Ligands
Magnesium hydroxide
Nickel
Organic chemistry
Phenols
Self-assembly
Topology
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Summary:Previous employment of the ligands 2-methoxy-6-[(methylimino)methyl]phenol (L H) and 2-methoxy-6-[(phenylimino)methyl]phenol (L H) has resulted in the self-assembly of pseudo metallocalix[6]arene complexes of general formulae: [M (μ -OH) (L ) ](NO ) (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 (L H), 2-[(benzylimino)methyl]-6-methoxyphenol (L H), 2-[(benzylamino)methyl]-6-methoxyphenol (L H) and 2-[(benzylamino)methyl]-4-bromo-6-methoxyphenol (L H), whose structures are modifications of ligands L H. These ligands are employed in the synthesis and characterisation of the dimetallic complex [Ni(ii) (L ) (H O)](NO )·2H O·3MeOH (3); the monometallic complexes [Ni(ii)(L ) ] (4) and [Co(iii)(L ) ]·H O·MeOH (5a); and the tetranuclear pseudo metallocalix[4]arene complexes: [(NO )⊂Co(ii) (μ -OH) (L ) (H O) ](NO )·H O (6), [(NO )⊂Ni(ii) (μ -OH) (L ) (H O) ](NO )·H O (7) and [Ni(ii) (μ -OH) (L ) (NO ) ]·MeCN (8). The tetrametallic 'butterfly' core topologies in 6-8 are discussed with respect to their structural and topological relationship with their heptanuclear [M ] (M = Co(ii), Ni(ii)) pseudo metallocalix[6]arene ancestors (1 and 2).
ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt04229b