The effect of polyether terminal chains in the liquid crystalline behavior of ortho-palladated complexes

A series of benzylideneanilines bearing terminal polyether chains, HL (HL = R-C6H4–CHdouble bond; length as m-dashN–C6H4-R′: R = OC8H17, R′ = O(CH2CH2O)2C2H5; R = O(CH2CH2O)2C2H5, R′ = OC8H17; R = R′ = O(CH2CH2O)2C2H5; R = OC12H25, R′ = O(CH2CH2O)3C2H5; R = O(CH2CH2O)3C2H5, R′ = OC12H25; R = R′ = O(CH2CH2O)3C2H5) have been prepared. Their dinuclear, [Pd(μ-X)L]2 (X = OAc, Cl, Br, SC8), [Pd2(μ-SCn)(μ-X)L2] (X = OAc, Cl; n = 8, 2) and mononuclear orthopalladated derivatives, Pd(acac)L, Pd(Ala)L, are reported and their mesogenic properties are compared with those of the analogous compounds with alkoxy chains. In general a great lowering in the melting points is produced for all the products. The free ligands and the alanine complexes are not liquid crystals. The chloro-bridged complexes bearing alkoxy and short polyether chains (O(CH2CH2O)2C2H5) show the larger improvement of mesogenic properties. Longer polyether chains (O(CH2CH2O)3C2H5) result usually in a destabilization of the mesophases. If only polyether chains are present, the destabilization is important regardless of the chain length. The ability of these molecules as ionic extractants and transporters was qualitatively evaluated for the more propitious cis-dinuclear complexes, which in fact showed some extracting ability, modest but improved compared to the free ligands.