**4. Experimental**

### *4.1. Materials and Physical Measurements*

Solvents and reagents were obtained commercially and were used as supplied. BMTTM [30] and BMTTE [16,17] ligands were synthesized by ourselves. Elemental organic analysis (C, H, N) was carried out on a Carlo Erba 1108/Chromatographic combustion elemental analyzer. FT-IR spectra in the 4000–400 cm<sup>−</sup><sup>1</sup> region were recorded on a Jasco FT/IR-6100 spectrophotometer. Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry analysis (DSC) profiles were obtained with a TGA-ATD/DSC, SETSYS Evolution 1750 (Setaram) thermal analyzer.

### *4.2. Synthesis and Crystallization of the Complexes*

### 4.2.1. ∞1Cu3Cl6(H2O)2(BMTTM)2 (**1**) and ∞1Cu3Cl6(H2O)2(BMTTM)2·4CH3CN (**1**·**solv**)

The pseudopolymorphs **1** and **1**·**solv** were obtained as crystalline materials using different synthetic methodologies:
