Molecular pac-man and tacos: layered cu(ii) cages from ligands with high binding site concentrations

McDonald, Cecelia
Williams, David W.
Comar, Priyanka
Coles, Simon J.
Keene, Tony D.
Pitak, Mateusz B.
Brechin, Euan K.
Jones, Leigh F.
McDonald, Cecelia; Williams, David W. Comar, Priyanka; Coles, Simon J.; Keene, Tony D.; Pitak, Mateusz B.; Brechin, Euan K.; Jones, Leigh F. (2015). Molecular pac-man and tacos: layered cu(ii) cages from ligands with high binding site concentrations. Dalton Trans. 44 (29), 13359-13368
The in situ formation and subsequent Cu(II) ligation of the polydentate pro-ligands o-[(E)-(2-hydroxy3- methoxyphenyl) methylideneamino] benzohydroxamic acid (L1H3), o-[(E)-(2-hydroxy-3-methoxy-5-bromophenyl) methylideneamino] benzohydroxamic acid (L2H3) and o-[(E)-(2-hydroxyphenyl) methylideneamino] benzohydroxamic acid (L3H3), leads to the self-assembly of the cages [Cu(II)(10)(L-1)(4)(2-aph)(2)(H2O)(2)](ClO4)(4)center dot 5MeOH (1), [Cu(II)(14)(L-1)(8)(MeOH)(2.5)(H2O)(7.5)](NO3)(4)center dot 3MeOH center dot 7H(2)O (2), [Cu(II)(14)(L-2)(8)(MeOH)(4)(H2O)(6)](NO3)(4)center dot 6H(2)O (3), [Cu(II)(14)(L-3)(8)(MeOH)(6)(H2O)(2)](NO3)(4)center dot 4MeOH center dot 8H(2)O (4) and [Cu(II)(30)O(OH)(4)(OMe)(2)(L-1)(16)(MeOH)4(H2O)(2)](ClO4)(4)center dot 2MeOH center dot 30H(2)O (5). Each member comprises a highly unusual topology derived from off-set, stacked, near planar layers of polynuclear subunits connected through long Cu(II)-O contacts. The exact topology observed is dependent on the specific reaction conditions and methodologies employed. Dc magnetic susceptibility studies on 1, 2, 4 and 5 reveals strong antiferromagnetic exchange between the Cu(II) centres in all siblings. We also present the 1D coordination polymer {[Cu(II)(L-4)]center dot H2O}(n) (6) comprising the pseudo macrocyclic ligand [[2-[(E)-(2-hydroxy-3-methoxyphenyl) methyleneamino] benzoyl] amino] ethanimidate (L4H2), which is formed upon the incorporation of an MeCN unit at the hydroxamate group of precursor ligand L1H3.
Royal Society of Chemistry (RSC)
Publisher DOI
Attribution-NonCommercial-NoDerivs 3.0 Ireland