TY - JOUR
T1 - Molecular Shape, Electronic Factors and the Ferroelectric Nematic Phase
AU - Tufaha, Naila
AU - Cruickshank, Ewan
AU - Pociecha, Damian
AU - Gorecka, Ewa
AU - Storey, John Mervyn David
AU - Imrie, Corrie Thomas
PY - 2023/2/20
Y1 - 2023/2/20
N2 - The synthesis and characterisation of two series of low molar mass mesogens, the (4-nitrophenyl) 2-alkoxy-4-(4-methoxybenzoyl)oxybenzoates (NT3.m) and the (3-fluoro-4-nitrophenyl) 2-alkoxy-4-(4-methoxybenzoyl)oxybenzoates (NT3F.m), are reported in order to investigate the effect of changing the position of a lateral alkoxy chain from the methoxy-substituted terminal ring to central phenyl ring in these two series of materials based on RM734. All members of the NT3.m series exhibited a conventional nematic phase, N, which preceded the ferroelectric nematic phase, NF, whereas all the members of the NT3F.m series exhibited direct NF-I transitions except for NT3F.1 which also exhibited a N phase. These materials cannot be described as wedge-shaped, yet their values of TNFN exceed those of the corresponding materials with the lateral alkoxy chain located on the methoxy-substituted terminal ring. In part, this may be attributed to the effect that changing the position of the lateral alkoxy chain has on the electronic properties of these materials, specifically in the electron density associated with the methoxy-substituted terminal aromatic ring. The value of TNI decreased with the addition of a fluorine atom ortho to the nitro group in NT3F.1, however, the opposite behaviour is found comparing the transition temperatures of the NF phase which are higher for the NT3F.m series, and this may reflect a change in the polarity and polarizability of those materials. This suggests that, rather than simply promoting a tapered shape, the role of the lateral chain in inhibiting anti-parallel associations and its effect on the electronic properties of the molecules are the key factors in driving the formation of the NF phase.
AB - The synthesis and characterisation of two series of low molar mass mesogens, the (4-nitrophenyl) 2-alkoxy-4-(4-methoxybenzoyl)oxybenzoates (NT3.m) and the (3-fluoro-4-nitrophenyl) 2-alkoxy-4-(4-methoxybenzoyl)oxybenzoates (NT3F.m), are reported in order to investigate the effect of changing the position of a lateral alkoxy chain from the methoxy-substituted terminal ring to central phenyl ring in these two series of materials based on RM734. All members of the NT3.m series exhibited a conventional nematic phase, N, which preceded the ferroelectric nematic phase, NF, whereas all the members of the NT3F.m series exhibited direct NF-I transitions except for NT3F.1 which also exhibited a N phase. These materials cannot be described as wedge-shaped, yet their values of TNFN exceed those of the corresponding materials with the lateral alkoxy chain located on the methoxy-substituted terminal ring. In part, this may be attributed to the effect that changing the position of the lateral alkoxy chain has on the electronic properties of these materials, specifically in the electron density associated with the methoxy-substituted terminal aromatic ring. The value of TNI decreased with the addition of a fluorine atom ortho to the nitro group in NT3F.1, however, the opposite behaviour is found comparing the transition temperatures of the NF phase which are higher for the NT3F.m series, and this may reflect a change in the polarity and polarizability of those materials. This suggests that, rather than simply promoting a tapered shape, the role of the lateral chain in inhibiting anti-parallel associations and its effect on the electronic properties of the molecules are the key factors in driving the formation of the NF phase.
U2 - 10.1002/chem.202300073
DO - 10.1002/chem.202300073
M3 - Article
C2 - 36807424
JO - Chemistry : a European Journal
JF - Chemistry : a European Journal
SN - 0947-6539
M1 - e202300073
ER -