The influence of molecular shape and electronic properties on the formation of the ferroelectric nematic phase

Abstract

The synthesis and characterisation of two series of ferroelectric nematogens based on RM734 having an additional methoxy group on the central phenyl ring are reported, the 3-methoxy-4-((4-nitrophenoxy)carbonyl)phenyl 2-alkoxy-4-alkoxybenzoates (7-m-n) and the 3-methoxy-4-((3-fluoro-4-nitrophenoxy)carbonyl)phenyl 2-alkoxy-4-alkoxybenzoates (8-m-n). In order to compare the behaviour of these series to those of the corresponding materials that do not contain the methoxy group on the central phenyl ring, we also report the synthesis and characterisation of 4-[(4-nitrophenoxy)carbonyl]phenyl 4-methoxybenzoate (11-0-1), 4-[(3-fluoro-4-nitrophenoxy)carbonyl]phenyl 4-methoxybenzoate (12-0-1) and 4-[(3-fluoro-4-nitrophenoxy)carbonyl]phenyl 2,4-diethoxybenzoate (12-2-2). Two compounds in which a lateral ethoxy chain is attached to the central ring, 3-ethoxy-4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (18-2-1) and 3-ethoxy-4-[(3-fluoro-4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (19-2-1), are also described. The behaviour of these materials shows that the relative stabilities of the ferroelectric nematic, NF, and conventional nematic, N, phases are governed by a subtle interplay of steric and electronic factors. Furthermore, the electronic factors are better understood in terms of isolated regions of electron density rather than by a single large longitudinal dipole moment. In terms of molecular shape, to observe the NF phase it appears that the molecular structure must include one or more lateral substituents that enhance molecular biaxiality and destabilise the N phase.