Synthesis and Characterization of [Mo3S4(NDABu)(HNDABu)2]3– and [Mo3S4(HNDAPr)3]2– Anions as Building Blocks for Organic–Inorganic Hybrid Solids



The polymetallic cation [Mo3S4(H2O)9]4+ was used as an inorganic precursor to generate new hybrid organic–inorganic chalcogenide clusters. Three organic compounds with flexible and hanging arms were synthesized and investigated as ligands for coordination complexes with the rigid and electroactive inorganic {Mo3S4} unit. Interestingly, the {Mo3S4} core formed hybrid structures with the flexible H3NDABu [N-(3-carboxypropyl)iminodiacetic acid] and H3NDAPr [N-(2-carboxyethyl)iminodiacetic acid] ligands, which were characterized by X-ray crystallography. Surprisingly, no crystals were isolated, when the more rigid H3NDABn [N-(4-methoxycarbonylbenzyl)iminodiacetic acid] ligand was used. The two coordination complexes [Mo3S4(NDABu)(HNDABu)2]3– and [Mo3S4(HNDAPr)3]2– were characterized by X-ray diffraction (XRD), IR spectroscopy, thermal gravimetric analysis (TGA), 1H NMR spectroscopy, elemental analysis, and electrochemistry. The organic ligands H3NDABu, H3NDAPr, and H3NDABn were characterized by XRD, IR, HR mass, and 13C and 1H NMR spectroscopy. [Mo3S4(NDABu)(HNDABu)2]3– and [Mo3S4(HNDAPr)3]2– constitute promising preformed building blocks to generate new organic–inorganic hybrid molecular or extended materials.