Ancillary Ligands and Spectator Cations as Controlling Factors in the Construction of Coordination and Hydrogen-Bonded Networks with the tert-Bu-CC⊃Agn (n=4, 5) Supramolecular Synthon

✍ Scribed by Liang Zhao; Chong-Qing Wan; Jie Han; Xu-Dong Chen; Thomas C. W. Mak

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 817 KB
• Volume: 14
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200800968

✦ Synopsis

Abstract

Supramolecular networks constructed with the __t__BuCC⊃Ag~n~ (n=4 or 5) metal–ligand synthon and trifluoroacetate have been transformed through the introduction of ancillary terminal nitrile ligands, from acetonitrile through propionitrile to tert‐butyronitrile, giving rise to a 2D coordination network in AgCC__t__Bu⋅3 AgCF~3~CO~2~⋅H~2~O (1), a 2D hydrogen‐bonded network in AgCC__t__Bu⋅5 AgCF~3~CO~2~⋅4 CH~3~CN⋅H~2~O (2), a 2D hybrid coordination/hydrogen‐bonded network in AgCC__t__Bu⋅3 AgCF~3~CO~2~⋅CH~3~CH~2~CN⋅2 H~2~O (3), and another 2D coordination network in AgCC__t__Bu⋅4 AgCF~3~CO~2~⋅ (CH~3~)~3~CCN⋅2 H~2~O (4). Concomitantly, the linkage modes between adjacent ethynide‐bound Ag~n~ aggregates in these compounds are also changed. A layer‐type hydrogen‐bonded host lattice in isostructural AgCC__t__Bu⋅4 AgCF~3~CO~2~⋅(R~4~N)(CF~3~CO~2~)⋅ 2 H~2~O (R~4~=BnMe~3~, 5; R~4~=Et~4~, 6; R~4~=__n__Pr~4~, 7) is obtained by introducing quaternary ammonium cations as guest templates, which occupy the interstices and thereby mediate the interlayer separation. Use of the bulky __n__Bu~4~N^+^ cation leads to disruption of the host network in AgCC__t__Bu⋅4 AgCF~3~CO~2~⋅3[(__n__Bu~4~N)(CF~3~CO~2~)]⋅H~2~O (8) with generation of a discrete dense nido‐Ag~5~ cluster.