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Design of Neutral Metallomesogens from 5,5-Dimethyldipyrromethane: Metal Ion Mediated Control of Folding and Hairpin Structures

Ames, Kelly A. ; Collinson, Simon R.; Blake, Alexander J.; Wilson, Claire; Love, Jason B. ; Bruce, Duncan W. ; Donnio, Bertrand; Guillon, Daniel and Schröder, Martin (2008). Design of Neutral Metallomesogens from 5,5-Dimethyldipyrromethane: Metal Ion Mediated Control of Folding and Hairpin Structures. European Journal of Inorganic Chemistry, 2008(32) pp. 5056–5066.

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New ligands derived from 5,5-dimethyldipyrromethane and their corresponding neutral complexes with Zn(II) and Pd(II) are described. The ligands incorporate either hexacatenar [H2(1n), n = 1, 10, 12, 14 and 16], tetracatenar [H2(2n), n = 1 and 16] or an extended dicatenar structure [H2(3n), n = 1 and 16]. Single crystal X-ray structure determinations on [Zn2(11)2] and [Zn2(31)2] confirm a distorted tetrahedral geometry at Zn(II) to afford double-stranded helical structures, while the Pd(II) species [Pd(31)] shows a distorted square planar geometry with the ligand adopting an alternative hairpin conformation. The metal-free hexacatenar ligands H2(1n) (n = 10, 12, 14, 16) and the corresponding complexes [Zn2(116)2] and [Pd(1n)] (n = 12, 14, 16) are not mesomorphic. However, the tetracatenar complex [Zn2(216)2] generates a smectic mesophase, as confirmed by X-ray diffraction, while [Pd(216)] and the metal-free ligand H2(216) show no mesomorphic behaviour. Two of the extended dicatenar compounds, H2(316) and [Zn2(316)2] are non-mesomorphic, while [Pd(316)] displays a smectic A phase.

Item Type: Journal Article
Copyright Holders: 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN: 1099-0682
Project Funding Details:
Funded Project NameProject IDFunding Body
Not SetNot SetEPSRC (Engineering and Physical Sciences Research Council)
Keywords: metallomesogens; liquid crystals; helical structures; co-ordination chemistry; supramolecular chemistry; zinc; palladium; pyrromethane; dipyrrolide
Academic Unit/Department: Science > Life, Health and Chemical Sciences
Other Departments > Student Services
Other Departments
Interdisciplinary Research Centre: Biomedical Research Network (BRN)
Item ID: 31294
Depositing User: Simon Collinson
Date Deposited: 13 Jan 2012 11:32
Last Modified: 29 Feb 2016 04:51
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