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Control of self-assembly through the influence of terminal hydroxymethyl groups on the metal coordination of pyrimidine-hydrazone Cu(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.
2010 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 49, no 13, p. 5923-34Article in journal (Refereed) Published
Abstract [en]

The synthesis and characterization of 6-hydroxymethylpyridine-2-carboxaldehyde (2-methyl-pyrimidine-4,6-diyl)bis(1-methylhydrazone) (1) is reported. Ligand 1 was designed as a ditopic pyrimidine-hydrazone molecular strand with hydroxymethyl groups attached to the terminal pyridine rings. Coordination of 1 with Cu(ClO(4))(2) x 6 H(2)O or Cu(SO(3)CF(3))(2) x 4 H(2)O in a 1:2 molar ratio resulted in the dinuclear Cu(II) complexes [Cu(2)1(CH(3)CN)(4)](ClO(4))(4) x CH(3)CN (4) and [Cu(2)1(SO(3)CF(3))(2)(CH(3)CN)(2)](SO(3)CF(3))(2) x CH(3)CN (5). X-ray crystallography and (1)H NMR NOESY experiments showed that 1 adopted a horseshoe shape with both pyrimidine-hydrazone (pym-hyz) bonds in a transoid conformation, while 4 and 5 were linear in shape, with both pym-hyz bonds in a cisoid conformation. Coordination of 1 with Cu(ClO(4))(2) x 6 H(2)O or Cu(SO(3)CF(3))(2) x 4 H(2)O in a 1:1 molar ratio resulted in three different bent complexes, [Cu(1H)(ClO(4))(2)](ClO(4)) (6), [Cu(1H)(CH(3)CN)](ClO(4))(3) x 0.5 H(2)O (7), and [Cu1(SO(3)CF(3))](2)(SO(3)CF(3))(2) x CH(3)CN (8), where the pym-hyz bond of the occupied coordination site adopted a cisoid conformation, while the pym-hyz bond of the unoccupied site retained a transoid conformation. Both 6 and 7 showed protonation of the pyridine nitrogen donor in the empty coordination site; complex 8, however, was not protonated. A variety of Cu(II) coordination geometries were seen in structures 4 to 8, including distorted octahedral, trigonal bipyramidal, and square pyramidal geometries. Coordination of the hydroxymethyl arm in the mononuclear Cu(II) complexes 6, 7, and 8 appeared to inhibit the formation of a [2 x 2] grid by blocking further access to the Cu(II) coordination sphere. In addition, the terminal hydroxymethyl groups contributed to the supramolecular structures of the complexes through coordination to the Cu(II) ions and hydrogen bonding.

Place, publisher, year, edition, pages
2010. Vol. 49, no 13, p. 5923-34
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-240973DOI: 10.1021/ic100384eISBN: 1520-510X (Electronic) 0020-1669 (Linking) OAI: oai:DiVA.org:kth-240973DiVA, id: diva2:1275574
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/20509604

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