Polyrotaxaned versus interdigitated super-arrays of loop-and-chain strands: Role of the anion in formation of silver(0) particles

Self-assembly of AgX (X^- = BF₄^-, ClO₄^-, and NO₃^-) with C₃-symmetric 1,3,5-tris(isonicotinoyloxyethyl)cyanurate (L) yields 1D loop-and-chain strands. However, the formation of a super-array of strands depends on the nature of the polyatomic anions: BF₄^- and ClO₄^- anions induce 1D polyrotaxaned loop-and-chain strands, whereas NO₃^- anion leads to the formation of 2D-like interdigitated loop-and-chain strands in the crystalline state. Calcination of [Ag₃(L)₂]3X (X^- = BF₄^- and NO₃^-) crystals at 500 °C produces silver(0) particles, whereas the same treatment of [Ag₃(L)₂]3ClO₄ crystals affords a mixture of silver(0) and silver(I) chloride. The rates of formation of Ag⁰ nanoparticles by reduction of crystalline products using ascorbic acid are in the order X^- = ClO₄^- > BF₄^- > NO₃^-, and their crystalline morphologies are dependent on the nature of the polyatomic anions.