Mixed Organometallic-Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2 Mo2 (CO)4 (μ,η2 -As2 )], AgI Salts and N-Donor Organic Molecules.

The reaction of the organometallic diarsene complex [Cp2 Mo2 (CO)4 (η2 -As2 )] (1) with Ag[Al{OC(CF3 )3 }4 ] (Ag[TEF]) yielded the AgI monomer [Ag(η2 -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 [{(η2 -1)2 Ag}2 (μ-L1)][TEF]2 (3) or the 1D polymer [{(η2 -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 [{(η2 -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(CH3 CN)3 ][Al{OC(CF3 )2 (CCl3 )}4 ] ([Ag(CH3 CN)3 ][TEFCl ]) and linkers L2-L4 to produce the 2D polymers [{(η2 -1)Ag}2 (μ,Lx)3 ]n [TEFCl ]2n [Lx=L2 (8), L3 (9), L4 (10), respectively].