Abstract The polymetallic cation [Mo 3 S 4 (H 2 O) 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 {Mo 3 S 4} unit. Interestingly, the {Mo 3 S 4} core formed hybrid structures with the flexible H 3 NDABu [N-( ...