Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp(2)Mo(2)(CO)(4)(μ,η(2)‐As(2))], Ag(I) Salts and N‐Donor Organic Molecules

The reaction of the organometallic diarsene complex [Cp(2)Mo(2)(CO)(4)(η(2)‐As(2))] (1) with Ag[Al{OC(CF(3))(3)}(4)] (Ag[TEF]) yielded the Ag(I) monomer [Ag(η(2)‐1)(3)][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic–organic hybrid assemblies upon its reaction with N‐donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2′‐bipyrimidine (L1) yielded the dicationic molecular compound [{(η(2)‐1)(2)Ag}(2)(μ‐L1)][TEF](2) (3) or the 1D polymer [{(η(2)‐1)Ag}(μ‐L1)](n)[TEF](n) (4) depending on the ratio of the reactants. However, its reactions with the pyridine‐based linkers 4,4′‐bipyridine (L2), 1,2‐bis(4‐pyridyl)ethylene (L3) and 1,2‐bis(4‐pyridyl)ethyne (L4) allowed the formation of the 2D polymers [{(η(2)‐1)Ag}(2)(μ‐Lx)(3)](n)[TEF](2n) [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step‐by‐step one‐pot reactions of 1, [Ag(CH(3)CN)(3)][Al{OC(CF(3))(2)(CCl(3))}(4)] ([Ag(CH(3)CN)(3)][TEF(Cl)]) and linkers L2–L4 to produce the 2D polymers [{(η(2)‐1)Ag}(2)(μ,Lx)(3)](n)[TEF(Cl)](2n) [Lx=L2 (8), L3 (9), L4 (10), respectively].