Crowding out: ligand modifications and their structure directing effects on brucite-like {Mx(μ3-OH)y} (M = Co(ii), Ni(ii)) core growth within polymetallic cages. Issue 4 (11th January 2019)

• Record Type: Journal Article
• 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.
• Is Part Of: Dalton transactions. Volume 48:Issue 4(2018)
• Page Start: 1477
• Page End: 1488
• Publication Date: 2019-01-11
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt04229b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A family of polymetallic cages are presented which includes a rare ferromagnetically coupled [Ni(ii )2 ] dimer. Abstract : Previous employment of the ligands 2-methoxy-6-[(methylimino)methyl]phenol (L1 H) and 2-methoxy-6-[(phenylimino)methyl]phenol (L2 H) has resulted in the self-assembly of pseudo metallocalix[6]arene complexes of general formulae: [M7 (μ3 -OH)6 (L x )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 (L3 H), 2-[(benzylimino)methyl]-6-methoxyphenol (L4 H), 2-[(benzylamino)methyl]-6-methoxyphenol (L5 H) and 2-[(benzylamino)methyl]-4-bromo-6-methoxyphenol (L6 H), whose structures are modifications of ligands L1–2 H. These ligands are employed in the synthesis and characterisation of the dimetallic complex [Ni(ii )2 (L3 )3 (H2 O)](NO3 )·2H2 O·3MeOH (3 ); the monometallic complexes [Ni(ii )(L4 )2 ] (4 ) and [Co(iii )(L4 )3 ]·H2 O·MeOH (5a ); and the tetranuclear pseudo metallocalix[4]arene complexes: [(NO3 )⊂Co(ii )4 (μ3 -OH)2 (L5 )4 (H2 O)2 ](NO3 )·H2 O (6 ), [(NO3 )⊂Ni(ii )4 (μ3 -OH)2 (L5 )4 (H2 O)2 ](NO3 )·H2 O (7 ) and [Ni(ii )4 (μ3 -OH)2 (L6 )4 (NO3 )2 ]·MeCN (8 ). The tetrametallic 'butterfly' core topologies in6–8 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 and2 ).