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Issue 15, 2015
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Alkyl linker effects on the coordination topology of ditopic di(2-pyridylmethyl)amine carboxylate ligands with ZnII and CuII: polymers vs. macrocycles

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Abstract

A series of ditopic ω-di(2-pyridylmethyl)amine carboxylic acid ligands incorporating a range of n-alkyl linkers (CnCOOH, n = 3–5, 7, 10 and 11) have been synthesised. Solution phase studies showed a 1 : 1 coordination stoichiometry between the ligands and M(ClO4)2·6H2O (M = ZnII or CuII) in all cases. The ZnII and CuII complexes were subsequently crystallised by liquid–liquid diffusion and the solid-state structures investigated by X-ray crystallography. The crystal structures obtained are entirely consistent with the 1 : 1 metal–ligand ratio of the solution-phase adducts. However, the coordination geometries and complex topologies are dependent on the alkyl chain length of the ligand CnCOOH. The ZnII and CuII complexes of the short alkyl chain ligands (n ≤ 5) exhibit 1D coordination polymeric structures with somewhat different conformations for {[Zn(C3COO)(H2O)](ClO4)·3.5H2O}n (1), {[Zn(C4COO)(H2O)]4(ClO4)4·1.5H2O}n (2), {[Zn(C5COO)(H2O)](ClO4)}n (3), {[Cu(C3COO)](ClO4)·MeOH}n (4), {[Cu(C4COO)(H2O)]2(ClO4)2·2H2O}n (5) and {[Cu(C5COO)(H2O)](ClO4)·2H2O}n (6). In contrast, the ligands with longer alkyl chains (n ≥ 7) participate in Zn2L2 metallomacrocyclic structures {[Zn(C7COO)(H2O)](ClO4)}2 (7), [Zn2(C10COO)2(H2O)2](ClO4)2·2H2O·MeOH (8) and {[Zn2(C11COO)2(H2O)2][Zn2(C11COO)2](ClO4)4·H2O}n (9). The formation of metallomacrocycles instead of the 1D coordination polymers is a persistent trend and, with identical crystal growth conditions and a non-coordinating anion employed, appears to be an effect of the longer alkyl chain.

Graphical abstract: Alkyl linker effects on the coordination topology of ditopic di(2-pyridylmethyl)amine carboxylate ligands with ZnII and CuII: polymers vs. macrocycles

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Publication details

The article was received on 22 Feb 2015, accepted on 08 Mar 2015 and first published on 10 Mar 2015


Article type: Paper
DOI: 10.1039/C5CE00375J
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CrystEngComm, 2015,17, 2974-2988
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    Alkyl linker effects on the coordination topology of ditopic di(2-pyridylmethyl)amine carboxylate ligands with ZnII and CuII: polymers vs. macrocycles

    K. Rodpun, A. G. Blackman, M. G. Gardiner, E. W. Tan, C. J. Meledandri and N. T. Lucas, CrystEngComm, 2015, 17, 2974
    DOI: 10.1039/C5CE00375J

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