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Morale, Francesca
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article
Metal-directed columnar phase formation in tetrahedral zinc(II) and manganese(II) metallomesogens
Abstract
New, non-discoid M(II) complexes [MCl<sub>2</sub>(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 [ZnCl<sub>2</sub>(L)] exhibits a single mesophase with rectangular symmetry (Col<sub>r</sub>) between 46 and 145 °C, whereas the Mn(II) analogue [MnCl<sub>2</sub>(L)] displays a purely hexagonal mesophase (Col<sub>h</sub>) 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(NO<sub>3</sub>)(L’)<sub>2</sub>]NO<sub>3</sub>.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.