Nitrile functionalised pendant-arm derivatives of aza- and mixed donor macrocyclic ligands as new building blocks for inorganic crystal engineering

Abstract

A range of nitrile-functionalised pendant arm derivatives of [9]aneN₃, [9]aneN₂S, [9]aneNS₂, [12]aneNS₂O and [15]aneO₂N₃ have been prepared: L¹ = 1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane, L² = 1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane, L³ = 1,2-bis[4,7-bis(2-cyanoethyl)-1,4,7-triazacyclonon-1yl]ethane, L⁴ = 4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane, L⁵ = 7-(2-cyanoethyl)-7-aza-1,4-dithiacyclononane, L⁶ = 1-(2-cyanoethyl)-1-aza-4,10-dithia-7-oxacyclododecane, L⁷ = 1,4,7-tris(cyanomethyl)-1,4,7-triaza-10,13-dioxacyclopentadecane, L⁸ = 1,4,7-tris(cyanoethyl)-1,4,7-triaza-10,13-dioxacyclopentadecane. Reaction of these ligands with Ag^I salts affords a range of complex products, the structures of which vary according to the type, number and length of the pendant arms. The synthesis and structures of {[Ag(L¹)]PF₆}_∞, {[Ag₂(L²)₂][BF₄]₂}_∞, {[Ag₂(L³)][PF₆]₂}_∞, [Ag₂(L⁴)₂][BF₄]₂, {[Ag(L⁵)]BF₄}_∞, [Ag₂(L⁶)₂][BF₄]₂, {[Ag(L⁷)]BF₄}_∞ and [Ag(L⁸)]PF₂O₂ are reported.