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Metal ion-controlled self-assembly using pyrimidine hydrazone molecular strands with terminal hydroxymethyl groups: a comparison of Pb(II) and Zn(II) complexes
Department of Chemistry, University of Otago.ORCID iD: 0000-0003-0028-1204
Department of Chemistry, University of Otago.ORCID iD: 0000-0003-4004-9565
Department of Chemistry, University of Otago.
2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 16, p. 7637-49Article in journal (Refereed) Published
Abstract [en]

Metal complexation studies were performed with the ditopic pyrimidine-hydrazone (pym-hyz) strand 6-hydroxymethylpyridine-2-carboxaldehyde (2-methyl-pyrimidine-4,6-diyl)bis(1-methylhydrazone) (1) and Pb(ClO(4))(2).3H(2)O, Pb(SO(3)CF(3))(2).H(2)O, Zn(SO(3)CF(3))(2), and Zn(BF(4))(2) to examine the ability of 1 to form various supramolecular architectures. X-ray crystallographic and NMR studies showed that coordination of the Pb(II) salts with 1 on a 2:1 metal/ligand ratio in CH(3)CN and CH(3)NO(2) resulted in the linear complexes [Pb(2)1(ClO(4))(4)] (2), [Pb(2)1(ClO(4))(3)(H(2)O)]ClO(4) (3), and [Pb(2)1(SO(3)CF(3))(3)(H(2)O)]SO(3)CF(3) (4). Two unusually distorted [2 x 2] grid complexes, [Pb1(ClO(4))](4)(ClO(4))(4) (5) and [Pb1(ClO(4))](4)(ClO(4))(4).4CH(3)NO(2) (6), were formed by reacting Pb(ClO(4))(2).6H(2)O and 1 on a 1:1 metal/ligand ratio in CH(3)CN and CH(3)NO(2). These grids formed despite coordination of the hydroxymethyl arms due to the large, flexible coordination sphere of the Pb(II) ions. A [2 x 2] grid complex was formed in solution by reacting Pb(SO(3)CF(3))(2).H(2)O and 1 on a 1:1 metal/ligand ratio in CH(3)CN as shown by (1)H NMR, microanalysis, and ESMS. Reacting the Zn(II) salts with 1 on a 2:1 metal/ligand ratio gave the linear complexes [Zn(2)1(H(2)O)(4)](SO(3)CF(3))(4).C(2)H(5)O (7) and [Zn(2)1(BF(4))(H(2)O)(2)(CH(3)CN)](BF(4))(3).H(2)O (8). (1)H NMR studies showed the Zn(II) and Pb(II) ions in these linear complexes were labile undergoing metal ion exchange. All of the complexes exhibited pym-hyz linkages in their cisoid conformation and binding between the hydroxymethyl arms and the metal ions. No complexes were isolated from reacting either of the Zn(II) salts with 1 on a 1:1 metal/ligand ratio, due to the smaller size of the Zn(II) coordination sphere as compared to the much larger Pb(II) ions.

Place, publisher, year, edition, pages
2011. Vol. 50, no 16, p. 7637-49
National Category
Inorganic Chemistry
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URN: urn:nbn:se:kth:diva-240974DOI: 10.1021/ic200670wISBN: 1520-510X (Electronic) 0020-1669 (Linking) OAI: oai:DiVA.org:kth-240974DiVA, id: diva2:1275576
Note

QC 20190108

Available from: 2019-01-07 Created: 2019-01-07 Last updated: 2019-01-08Bibliographically approved

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Publisher's full texthttps://www.ncbi.nlm.nih.gov/pubmed/21749160

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