Effects of Ligand Substituents (F for H; OR for R) on Mesogenic Properties of M(Salen) Derivatives (M = Cu, Ni, VO). New Fluoro-substituted Complexes and Crystal Structure of the Mesogen Ni(5-hexylSalen)
The preparation of new metallomesogens containing fluoro-substituted bis(salicylaldehyde) ethylenediimine (Salen) ligands is reported for the complexes of copper(II), nickel(II), and oxovanadium(IV), in which substitution for individual atoms is shown to have a dramatic effect on packing and mesogenic properties. In other mesogens, fluoro substitution reduces melting points or extends the mesogenic range, or both. By contrast, in the title compounds the melting points are lowered by up to 50°C, while the mesogenicity is eliminated or drastically reduced in range by fluorination, presumed to exert its influence through the dipolar effect. When the alkoxy O atom in Ni(5-(hexyloxy)Salen) is replaced with CH 2, the structure changes dramatically from roughly planar to an irregular S-shape, but mesogenic properties are retained. The crystal structure of (5-n-hexylSalen)Ni shows it to be an S-shaped molecule with especially dramatic bending at the n-hexyl chains from their phenyl rings (58, 85°). Crystal data: C 28H 38N 2O 2Ni, space group P1, a = 12.640(2) Å, b = 16.872(2) Å, c = 6.650(2) Å, α = 98.54(3)°, β = 92.89(3)°, γ = 71.43(1)°, Z = 2, R = 5.44%, R w = 5.96% for 1612 observed unique reflections. © 1995 American Chemical Society.
A. B. Blake et al., "Effects of Ligand Substituents (F for H; OR for R) on Mesogenic Properties of M(Salen) Derivatives (M = Cu, Ni, VO). New Fluoro-substituted Complexes and Crystal Structure of the Mesogen Ni(5-hexylSalen)," Inorganic Chemistry, American Chemical Society (ACS), Jan 1995.
The definitive version is available at http://dx.doi.org/10.1021/ic00109a020
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© 1995 American Chemical Society (ACS), All rights reserved.