Mixed Organometallic-Organic Hybrid Assemblies Based on the Diarsene Complex [Cp Mo (CO) (μ,η -As )], Ag Salts and N-Donor Organic Molecules.

The reaction of the organometallic diarsene complex [Cp Mo (CO) (η -As )] (1) with Ag[Al{OC(CF ) } ] (Ag[TEF]) yielded the Ag monomer [Ag(η -1) ][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 -1) Ag} (μ-L1)][TEF] (3) or the 1D polymer [{(η -1)Ag}(μ-L1)] [TEF] (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 -1)Ag} (μ-Lx) ] [TEF] [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1, [Ag(CH CN) ][Al{OC(CF ) (CCl )} ] ([Ag(CH CN) ][TEF ]) and linkers L2-L4 to produce the 2D polymers [{(η -1)Ag} (μ,Lx) ] [TEF ] [Lx=L2 (8), L3 (9), L4 (10), respectively].