The reaction of the organometallic diarsene complex [Cp2Mo2(CO)(4)(mu,eta(2)-As-2)] (B) (Cp = C5H5) with Ag[FAl{OC6F10(C6F5)}(3)] (Ag[FAl]) and Ag[Al{OC(CF3)(3)}(4)] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(eta(2)-B)(4)Ag-2][FAl](2)(4), [(mu,eta(1):eta(2)-B)(3)(eta(2)-B)(2)Ag-3][TEF](3)(5) and [(mu,eta(1):eta(2)-B)(4)Ag-3][TEF](3)(6). These products are only composed of the complexes Band Ag-I. Moreover, compounds 5and6are the only supramolecular assemblies featuringBas a linking unit, and the first examples of [Ag-I](3)units stabilized by organometallic bichelating ligands. According to DFT calculations, complex Bcoordinates to metal centers through both the As lone pair and the As-As sigma-bond thus showing this unique feature of this diarsene ligand.