Metal-organic polyhedron from flexible tetrakis(thiobenzyl-carboxylate)-Tetrathiafulvalene

The synthesis of crystalline self-assembled materials starting from building blocks with a large degree of freedom is challenging. Furthermore, incorporating redox active moieties in self-assembled metal-organic polyhedra is of the outmost interest to modulate the properties of the cavity through redox stimuli. Herein is presented the synthesis of a novel electroactive ligand bearing 4 coordinating moieties around an S-alkylated tetrathiafulvalene scaffold. The redox behavior of the ligand is similar to a tetra-S-alkylated tetrathiafulvalene. In the solid state it presents a densely packed H-bonded 1D polymeric structure. Upon reaction with Cu(OAc)2 in the presence of dimethylformamide or dimethylacetamide, two novel M4L4-type metal-organic cages (MOCs) bearing paddlewheel metal clusters as their connecting nodes are obtained. The structural features of the ligand and MOC are devised. Both MOCs adopt the same structure with a tetrahedral arrangement of the four TTF moieties.