The starting material 3,3',3'',3'''-([2,2'-bi(1,3-dithiolylidene)]-4,4',5,5'tetrayltetrakis(sulfanediyl))tetrapropanenitrile (1) was prepared using classical phosphite mediated coupling. The synthesis was done in two steps to obtain the desired target ligand L (Scheme 1) further used to prepare the TTF-CuMOP described herein (vide infra). In a first step, the propionitrile protecting groups are removed in basic media to generate a tetrathiolate, followed by the addition of the methyl 4-(bromomethyl)benzoate, affording the intermediate 2 with an 83 % yield. This compound is then saponified in a basic aqueous media to yield after re-acidification the tetraacid L with 84 % yield. Noteworthy, a TTF-tetrakis(4-picolylthio) was reported for the construction of metallamacrocycles and 1-D coordination polymers. The flexibility is defined by Furukawa, Fujita et coll. as "the number of rotatable bonds in the main scaffold" for a given ligand, and reaches 12 for L (3 rotatable bonds between the TTF core and each benzoic acid moiety). This makes L the most flexible carboxylate based ligand ever reported to form a cage to the best of our knowledge. Electrochemical properties of 2 and L were investigated by cyclic voltammetry. In both cases two reversible oxidations waves are observed (Figure , 2 : 𝐸 1 1/2 = + 0.55 V, 𝐸 2 1/2 = + 0.72 V and L : 𝐸 1 1/2 = + 0.55 V, 𝐸 2 1/2 = + 0.72 V vs. SCE). The reference compound tetramethylthio-TTF (TMT-TTF) is described in the literature with values of : 𝐸 1 1/2 = + 0.51 V, 𝐸 2 1/2 = + 0.78 V vs SCE. Neither the presence of benzoic ester nor the acids have therefore a stringent impact on the redox activity of the ligand. Suitable crystals of L for X-ray structural determination were obtained by slow evaporation of a DMSO solution (Figure ). The ligand crystallizes as orange plates in the monoclinic space group P21/c. The asymmetric unit contains half of a neutral ligand molecule and one disordered DMSO molecule. The central C=C bond is 1.338(5) Å long, which is in accordance with a non-oxidized TTF. Each DMSO molecule connects two carboxylic acids from two different molecules of L through H-bonding with 2.652(7) and 2.98(1) Å intermolecular OL-ODMSO distances. Two benzoic acids located on the same fulvalene moieties are associated through these DMSO mediated H-bonds to two benzoic acid moieties of an adjacent molecule of L. This creates an infinite one-dimensional H-bonded polymer (Figure )