title: Tris(β-diketonato) Ru(III) complexes as chiral dopants for nematic liquid crystals: the effect of the molecular structure on the helical twisting power.
abstract: Doping nematic liquid crystals with optically active compounds transforms them into chiral nematic phases with helical structures. In this phenomenon, the chirality of the dopant molecules is transferred or amplified to the bulk of the liquid crystals. Δ-[Ru(acac)3] (acac = acetylacetonato) is known to work as one of the dopants with a strong helical twisting power (HTP). In this study, we have systematically modified [Ru(acac)3] to clarify the correlation between the molecular structure and HTP; we have designed and synthesized five new Ru(III) complexes, [Ru(acac)2(acacC8)] (RuC8-1, acac = acetylacetonate, acacC8 = 3-(4'-octyloxy-phenylalkynyl)-pentane-2,4-dionato), [Ru(acac)(acacC8)2] (RuC8-2), [Ru(acacC8)3] (RuC8-3), [Ru(acacC0)3] (RuC0-3, acacC0 = 3-(phenylalkynyl)-pentane-2,4-dionato), and [Ru(acacC24)3] (RuC24-3, acacC24 = 3-(3',4',5'-tri(octyloxy)-phenylalkynyl)-pentane-2,4-dionato). All the complexes, except for RuC0-3, could be separated into Δ, Λ isomers by HPLC on a chiral column and were examined as chiral dopants for a nematic liquid crystal, N-(4-methoxybenzilidene)-4-butylaniline (MBBA). The Δ isomers of RuC8-1, RuC8-2, RuC8-3, and RuC24-3 induced a right-handed (P) helix and the magnitudes of the HTPs (/μm(-1)) were determined as follows: RuC8-1 (+60) < RuC8-2 (+109) > RuC8-3 (+78) > RuC24-3 (+41). The HTPs of the ruthenium dopants were not simply proportional to their size. The highest HTP observed in biaxial RuC8-2 was attributed to the balance of the molecular helicity and high ordering in MBBA based on the surface chirality model.
authors.affiliation: Department of Chemistry and ‡Department of Physics, School of Science, Kitasato University , 1-15-1 Kitasato, Minami-ku, Sagamihara, Kanagawa 252-0373, Japan.
authors.forename: Jun
authors.initials: J
authors.lastname: Yoshida
authors.forename: Go
authors.initials: G
authors.lastname: Watanabe
authors.forename: Kaori
authors.initials: K
authors.lastname: Kakizawa
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Kawabata
authors.forename: Hidetaka
authors.initials: H
authors.lastname: Yuge