The reactions of the organometallic ligand complex [Cp2Mo2(CO)4(μ,η2‐Sb2)] (C) with Ag[TEF] ([TEF]−=[Al{OC(CF3)3}4]−) in the presence of a number of di‐ or polytopic N‐donor molecules (1,6,7,12‐tetraazaperylene (L1), 2,2’‐bipyrimidine (L2), 4,4’‐bipyridine (L3), trans‐1,2‐di(4‐pyridyl)ethylene (L4) and 1,3‐di(4‐pyridyl)propane (L5)), were studied. Depending on the reaction stoichiometry and choice of linker, these reactions lead to the selective formation of dimeric or tetrameric supramolecular coordination complexes as well as 1D and 2D coordination polymers (CPs). The presented compounds are unique examples of supramolecular complexes incorporating both organometallic Sb‐donor and organic N‐donor molecules as ligands to stabilize metal ions. Moreover, one of the formed compounds, the CP [Ag4(η2 : 1‐C)4(L4)4]n[TEF]4n, represents an exceptional 1D polymer incorporating both N‐ and Sb‐donor ligands as connectors for metal ions.
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