Novel liquid crystals based on fluorinated carbon chains and terminated with SF5 groups are presented for the first time. Attachment of an SF5 group separated from a benzylidine group by a fluorinated spacer leads to monotropic nematic and smectic phases, while an enantiotropic nematic phase is observed in mixtures. The phase sequence of these new compounds is comparable to hydrocarbon analogues of nO.m (n-alkoxy-m-alkylbenzylidine) series. Despite a long alkoxy chain, the nematic --> smectic A transition is closer to second order, with M-TCP(predicted) approximate to 0.995 values that are even higher than for the nCB (n-alkylcyanobiphenyls) series. Single crystal and quantum computational studies suggest that electrostatic interactions play a major role in governing the value of M-TCP. Molecular packing in the crystal structure exhibits monoclinic P2(1)/a symmetry. A flexible synthetic strategy that allows the synthesis of another homologous series with a bend in the molecular structure is also presented. The bent core structure of 100.2 SF5 investigated shows a monotropic, tilted smectic phase for the higher C-10 alkoxy chain. The compounds in this series reveal a high degree of undercooling (well above 50 degreesC), which is rationalized using finite size effects on nucleation.