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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

Citation

Rodpun, K and Blackman, AG and Gardiner, MG and Tan, EW and Meledandri, CJ and Lucas, NT, Alkyl linker effects on the coordination topology of ditopic di(2-pyridylmethyl)amine carboxylate ligands with ZnII and CuII: polymers vs. macrocycles, CrystEngComm, 17, (15) pp. 2974-2988. ISSN 1466-8033 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 The Royal Society of Chemistry

DOI: doi:10.1039/c5ce00375j

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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:102507
Year Published:2015
Web of Science® Times Cited:5
Deposited By:Chemistry
Deposited On:2015-08-25
Last Modified:2017-11-02
Downloads:0

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