Metal-directed columnar phase formation in tetrahedral zinc(II) and manganese(II) metallomesogens

Morale, Francesca; Finn, Rachel L.; Collinson, Simon; Blake, Alexander J.; Wilson, Claire; Bruce, Duncan W.; Guillon, Daniel; Donnio, Bertrand and Schroder, Martin (2008). Metal-directed columnar phase formation in tetrahedral zinc(II) and manganese(II) metallomesogens. New Journal of Chemistry, 32 pp. 297–305.

DOI: https://doi.org/10.1039/b710745e

Abstract

New, non-discoid M(II) complexes [MCl2(L)] {M = Mn, Zn; L = 2,6-diformyl-4- methylphenolbis[3’,4’,5’-tris(hexadecyloxy)phenylimine]} have been prepared and shown to exhibit columnar mesophases, the nature of which was found to be metal-dependent. As analysed by DSC and small-angle X-ray diffraction experiments, the complex [ZnCl2(L)] exhibits a single mesophase with rectangular symmetry (Colr) between 46 and 145 °C, whereas the Mn(II) analogue [MnCl2(L)] displays a purely hexagonal mesophase (Colh) phase between 55 and 285 °C. By combining these results with those obtained from dilatometry, a model for the molecular organisation within the columnar mesophases is proposed. The single-crystal X-ray structure of the related complex [Zn(NO3)(L’)2]NO3.3MeOH {L’ = 2,6-diformyl-4-methylphenolbis[3’,4’,5’-tris(methoxy)phenylimine]} has been determined and supports the proposed mode of binding of the ligand to the metal via only one imine and a phenol.

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