Abstract

The multinuclear R-C≡C⊃Ag_n(n =3, 4, 5; R = alkyl, aryl, heteroaryl metal-ligand supramolecular synthon is a versatile building unit for the anion-templated synthesis of high-nuclearity silver(I)-ethynide clusters. Recently, we isolated a series of neutral and anionic high-nuclearity silver(I) ethynide clusters based on oxovanadium(V) phosphonate building blocks, which are synthesized in the reaction between AgC≡C^tBu, AgNO₃, ^tBuPO₃H₂ and (Et₄N)VO₃. In the presence of ^tBuPO₃H₂, the precursor (Et₄N)VO₃ undergoes transformation to yield various oxovanadium(V) phosphonate building blocks, namely [(^tBuPO₃)VO₂(OH)]²⁻, [(^tBuPO₃)₂(VO₂)]³⁻, [(^tBuPO₃)₃V₃O₆(OH)]⁴⁻ and [(^tBuPO₃)₄(V₄O₈]4⁻, which induce the formation of silver(I)-ethynide cluster shells via Ag–O bonding interactions. The molecular structures and chemical properties of nanoscale silver ethynide complexes are discussed.

© 2013 Optical Society of America