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Controllable Growth of Chains and Grids from Polyoxomolybdate Building Blocks Linked by Silver( I ) Dimers
Author(s) -
Abbas Hamera,
Pickering Alexandra L.,
Long DeLiang,
Kögerler Paul,
Cronin Leroy
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401088
Subject(s) - synthon , protonation , chemistry , solvent , monomer , ion , crystallography , stereochemistry , organic chemistry , polymer
Molecular growth processes utilizing a β‐octamolybdate synthon and {Ag 2 } dimers are described and the directing influence of “encapsulating” cations and coordinating solvent is also demonstrated. The growth of two 1D chains, ( n Bu 4 N) 2 n [Ag 2 Mo 8 O 26 ] n ( 1 ) and ( n Bu 4 N) 2 n [Ag 2 Mo 8 O 26 (CH 3 CN) 2 ] n ( 2 ), is achieved when n Bu 4 N + ions are used, and the diameter of the chains can be expanded by the coordination of CH 3 CN 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 ( n Bu 4 N) 2 n [Ag 2 Mo 8 O 26 (dmso) 2 ] n ( 3 ), which, similar to 1 and 2 , still incorporates the Bu 4 N + ions that exert an “encapsulating” influence. However, in (HDMF) n [Ag 3 (Mo 8 O 26 )(dmf) 4 ] n ( 4 ) the relatively bulky Bu 4 N + 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 (Ph 4 P) 2 [Ag 2 Mo 8 O 26 (dmso) 4 ] ( 5 ), which is isolated when the Ph 4 P + ions are so “encapsulating” as to prevent aggregation of the {Ag‐Mo 8 ‐Ag} building blocks. The nature of the Ag⋅⋅⋅Ag 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.