## 3 Results and Discussion
### Thermal and Mesomorphic Properties  
The thermal stability was determined by thermogravimetric analysis (TGA) (Supplementary materials, Figure S2), while the transition temperatures and the enthalpychanges associated were investigated by differential scanning calorimetry (DSC) (Supplementary materials, Figure S3). The data are presented in Table 1.  
For **Zn_tpy**, weight-loss from degradation becomes significant above ca. 170 \({}^{\circ}\)C, with a 5% weight-loss at 230 \({}^{\circ}\)C (at a rate of 5 \({}^{\circ}\)C min\({}^{-1}\)). Polarized optical microscopy investigations (POM) showed that, on cooling from the isotropic liquid, the complex self-assembles into a liquid crystalline mesophase (Figure 2a) below 114 \({}^{\circ}\)C, as indicated by the growth of a fan-shaped, fluid but non-characteristic, optical texture. The final identification of the type and symmetry of the mesophase was achieved by small- and wide-angle X-ray scattering studies (S/WAXS-Figure 2b, Supplementary materials, Figure S4). The SWAXS patterns are typical of a liquid crystalline smectic phase, with the overlapping broad scattering signal arising from liquid-like lateral distances between undifferentiated molecular segments, i.e., molten chains, h\({}_{\text{ch}}\), and aromatic parts, har, in the wide-angle region (h\({}_{\text{ch}}\) + h\({}_{\text{har}}\)), and with two sharp small-angle reflections corresponding to the first two lamellar orders (h00) (100, very strong, and 200, weak), emerging from the nanosegregated structure formed by the antagonistic aromatic and aliphatic segments (Figure 2b); an additional broad signal, corresponding to short-range periodicity from the \begin{table}
\begin{tabular}{l l} \hline \hline \multirow{2}{*}{**T\({}_{\text{dec5\%}}\)**, [a] [\({}^{\circ}\)C]**} & **Mesophases [b]**, **Transition Temperatures (\({}^{\circ}\)C) and Enthalpies** \\  & **[AH (k)-mol-1] [c]** \\ \hline
245 & Cr 89 [12.0] SmA 109 [2.5] Isso/Isso 114 [2.6] SmA 73 [10.2] Sm + Cr \\ \hline \hline \end{tabular} \({}^{\text{[a]}}\) Decomposition temperature at 5% weight-loss (from TGA); \({}^{\text{[b]}}\) SmA: smectic A mesophase; \({}^{\text{[c]}}\) DSC data on second heating and cooling cycles.  
\end{table} 
Table 1: Thermal and mesomorphic data for **Zn_tpy**. Figure 2: (**a**) POM texture of **Zn_tpy** on cooling at 110 \({}^{\circ}\)C, magnification 20\(\times\); SWAXS patterns of **Zn_tpy**; (**b**) at 85 \({}^{\circ}\)C in the mesophase and (**c**) at room temperature in the pasty pseudo-crystalline state, showing coexistence of the signals of the crystal phase and smectic A phase. arrangement of the metallic-typ moiety within aromatic layers, \(\text{D}_{\text{ar}}\), was also observed at ca. 7.5-8.0 A. Due to the specific amphiphilic molecular structure of the zinc complex, with the six alkyl chains radiating in the same direction, whereas the tpy moiety is deprived of chains, the complexes are probably self-organized pairwise in a more or less head-to-head fashion (Figure 3), with the aromatic and metallic moieties confined into a median sublayer (\(D_{\text{ar}}\)), whose periodic alternation with molten chain sublayers generates a SmA-like structure with a periodicity \(d_{\text{lam}}\) of ca. 29.3 A at 85 \({}^{\circ}\)C (ca. 28.9 A at 100 \({}^{\circ}\)C, Table 2). The geometry of the Zn complexes can be deduced from the single-crystal structures of molecules, including the same complex moiety. In this way, structures of several Zinc bis(enzoate)-phenylterpyridine derivatives are available (CSD-BETWOO, CSD-BETWUU, CSD-BETXAB, CSD-LEXWES) [52] and show irregular trigonal bipyramidal geometries, in which both benzoate ligands are nearly orthogonal to the terpyridine ring plane. In **Zn_tpy**, benzoate ligands consist of gallate units substituted by three long dodecyl chains, whose rejection into adjacent molten aliphatic layers generates a smectic A-like