Phase transitions of compounds 2–6 on heating^a.

Compd.	A	B	D	E	T/°C [ΔH kJ mol−1]
2	H	H	H	H	Cr 149 [27.0] SmCb 243 [12.0] Iso
3/10	R	R	H	H	Cr 97 [63.2] (CrIso[*] 90 [17.6]) Cubbi/I23[*] 131 [2.2] Iso1 138 [5.7] Iso
4	R	H	R	H	Cr 151 [69.5] (Cubbi/Ia3̄d 141 Colhex 143 [12.4]c) Iso
5	R	R	R	H	Cr 92 [14.2] Colhexd 105 [7.1] Iso
6	R	R	R	R	Cr 84 [33.2] Iso

^aDSC peak temperatures at 10 K min⁻¹; values in round parantheses indicate monotropic phases, only observed on cooling; abbreviations: Cr = crystalline solid, SmC = tilted lamellar phase, Cub_bi/Ia3̄d = achiral Cub_bi phase with the Ia3̄d space group, Cub_bi/I23^[*^] = mirror symmetry broken Cub_bi phase with the I23 space group; Iso = achiral isotropic liquid; Iso₁^[*^] = mirror symmetry broken Iso phase; for DSC traces, see Fig. S1, and for textures, see Fig. S2–S5.

^b d = 3.66 nm.

^cEnthalpies of both transitions.

^d a _hex = 4.39 nm.