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

McDonald, C
Williams, DW
Comar, P
Coles, SJ
Keene, TD
Pitak, MB
Brechin, EK
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2015-06-24
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© The Royal Society of Chemistry 2015. The in situ formation and subsequent Cu(ii) ligation of the polydentate pro-ligands o-[(E)-(2-hydroxy-3-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(L1)4(2-aph)2(H2O)2](ClO4)4·5MeOH (1), [Cu(ii)14(L1)8(MeOH)2.5(H2O)7.5](NO3)4·3MeOH·7H2O (2), [Cu(ii)14(L2)8(MeOH)4(H2O)6](NO3)4·6H2O (3), [Cu(ii)14(L3)8(MeOH)6(H2O)2](NO3)4·4MeOH·8H2O (4) and [Cu(ii)30O(OH)4(OMe)2(L1)16(MeOH)4(H2O)2](ClO4)4·2MeOH·30H2O (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)(L4)]·H2O}n (6) comprising the pseudo macrocyclic ligand [[2-[(E)-(2-hydroxy-3-methoxy-phenyl)methyleneamino]benzoyl]amino]ethanimidate (L4H2), which is formed upon the incorporation of an MeCN unit at the hydroxamate group of precursor ligand L1H3.
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McDonald, C., Williams, D. W., Comar, P., Coles, S. J., Keene, T. D., Pitak, M. B., Brechin, E. K., Jones, L. F. (2015) Molecular pac-man and tacos: layered cu(ii) cages from ligands with high binding site concentrations. Dalton Transactions 44 (29), pp. 13359-13368.
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26133039
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en
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1477-9226
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1477-9234
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