Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers

Abbas, H., Pickering, A.L., Long, D.-L. , Kögerler, P. and Cronin, L. (2005) Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers. Chemistry: A European Journal, 11(4), pp. 1071-1078. (doi: 10.1002/chem.200401088)

Abstract

Molecular growth processes utilizing a β-octamolybdate synthon and {Ag<SUB>2</SUB>} dimers are described and the directing influence of "encapsulating" cations and coordinating solvent is also demonstrated. The growth of two 1D chains, (<I>n</I>Bu<SUB>4</SUB >N)<SUB>2<I>n</I></SUB>[Ag<SUB>2</SUB>Mo<SUB>8</SUB>O<SUB>26</SUB>]<SUB><I>n</I></SUB> (<B>1</B>) and (<I>n</I>Bu<SUB>4</SUB>N)<SUB>2<I>n</I></SUB>[Ag<SUB>2</SUB>Mo<SUB>8</SUB>O<SUB>26</SUB>(CH<SUB>3</SUB>CN)<SUB>2</SUB>]<SUB><I>n</I></SUB> (<B>2</B>), is achieved when <I>n</I>Bu<SUB>4</SUB>N<SUP>+</SUP> ions are used, and the diameter of the chains can be expanded by the coordination of CH<SUB>3</SUB>CN solvent (<B>2</B>). 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 (<I>n</I>Bu<SUB>4</SUB>N)<SUB>2<I>n</I></SUB>[Ag<SUB>2</SUB>Mo<SUB>8</SUB>O<SUB>26</SUB>(dmso)<SUB>2</SUB>]<SUB><I>n</I></SUB> (<B>3</B>), which, similar to <B>1</B> and <B>2</B>, still incorporates the Bu<SUB>4</SUB>N<SUP>+</SUP> ions that exert an "encapsulating" influence. However, in (HDMF)<SUB><I>n</I></SUB>[Ag<SUB>3</SUB>(Mo<SUB>8</SUB>O<SUB>26</SUB>)(dmf)<SUB>4</SUB>]<SUB><I>n</I></SUB> (<B>4</B>) the relatively bulky Bu<SUB>4</SUB>N<SUP>+</SUP> 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<SUB>4</SUB>P)<SUB>2</SUB>[Ag<SUB>2</SUB>Mo<SUB>8</SUB>O<SUB>26</SUB>(dmso)<SUB>4</SUB>] (<B>5</B>), which is isolated when the Ph<SUB>4</SUB>P<SUP>+</SUP> ions are so "encapsulating" as to prevent aggregation of the {Ag-Mo<SUB>8</SUB>-Ag} building blocks. The nature of the Ag … Ag dimers in each of the compounds <B>1</B>-<B>4</B> is examined by DFT calculations and the interplay between these Ag-Ag interactions and the structure types is described.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Abbas, Miss Hamera and Long, Dr Deliang and Cronin, Professor Lee
• Authors: Abbas, H., Pickering, A.L., Long, D.-L., Kögerler, P., and Cronin, L.
• Subjects: Q Science > QD Chemistry
• College/School: College of Science and Engineering > School of Chemistry; University Centres > Glasgow Materials Research Initiative
• Journal Name: Chemistry: A European Journal
• Journal Abbr.: Chem. Eur J.
• ISSN: 0947-6539
• ISSN (Online): 1521-3765