Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers.
Molecular growth processes utilizing a beta-octamolybdate synthon and {Ag2} dimers are described and the directing influence of "encapsulating" cations and coordinating solvent is also demonstrated. The growth of two 1D chains, (nBu4N)2n[Ag2Mo8O26]n (1) and (nBu4N)2n[Ag2Mo8O26(CH3CN)2]n (2), is achieved when nBu4N+ ions are used, and the diameter of the chains can be expanded by the coordination of CH3CN solvent (2). The formation of a type of gridlike structure in which 1D chains are crossed-over each other in alternatively packed layers is achieved in DMSO as the solvent; DMSO acts as a linking group to give (nBu4N)2n[Ag2Mo8O26(dmso)2]n (3), which, similar to 1 and 2, still incorporates the Bu4N+ ions that exert an "encapsulating" influence. However, in (HDMF)n[Ag3(Mo8O26)(dmf)4]n (4) the relatively bulky Bu4N+ ions are exchanged for protonated DMF cations, thereby allowing the chains to condense to a 2D array. The building block concept is further enforced by the isolation of a "monomeric" unit (Ph4P)2[Ag2Mo8O26(dmso)4] (5), which is isolated when the Ph4P+ ions are so "encapsulating" as to prevent aggregation of the {Ag-Mo8-Ag} building blocks. The nature of the AgAg dimers in each of the compounds 1-4 is examined by DFT calculations and the interplay between these Ag-Ag interactions and the structure types is described.
Abbas
Hamera
H
Department of Chemistry, The University of Glasgow, Glasgow, G12 8QQ, UK.
Pickering
Alexandra L
AL
Long
De-Liang
DL
Kögerler
Paul
P
Cronin
Leroy
L
D000097:Acetonitriles / Q000737:chemistry; D018360:Crystallography, X-Ray; D019281:Dimerization; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry
D000097:Acetonitriles; D009942:Organometallic Compounds; D012997:Solvents; D012834:Silver; D008982:Molybdenum