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Issue 21, 2014

Effect of anion on Ag(i) meso-helical chains formed with 4,4′-dipyridyl ketone: solvent versus anion bridging and anion effects on the strength of ligand binding

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Abstract

The synthesis and characterisation by IR spectroscopy and elemental analysis of ten new Ag(I)–L complexes are described. Of these complexes, nine are characterised by single crystal X-ray diffraction: {[Ag(L)](CF3SO3)·1/2H2O} (1), {[Ag(L)](ClO4)·1/2H2O} (2), {[Ag2(L)2(CH3CN)](ClO4)2·2CH3CN·H2O} (3), {[Ag2(L)2(CH3CN)2](ClO4)2·CH3CN} (4), {[Ag2(L)2(CH3CN)2](PF6)2·2CH3CN} (5), {[Ag(L)2](CF3SO3)·1/2H2O} (6), {[Ag(L)2](BF4)} (7), {[Ag(L)2](PF6)} (8) and {[Ag(L)2](PF6)·2CH3CN} (9). The primary structures of 1–6 were meso-helical one-dimensional (1D) polymers, while 7 was a helical 1D polymer and 8 and 9 were (4,4) networks. Complexes 1–5 possessed 1 : 1 metal-to-ligand (M : L) ratios, while complexes 6–9 possessed 1 : 2 M : L ratios. The meso-helical chains of complexes 1 and 2 were di-μ-bridged at the Ag(I) nodes by the counteranions CF3SO3 and ClO4, respectively, while the meso-helical chains of complexes 3–5 were di-μ-bridged at the Ag(I) nodes by the CH3CN molecules. The effect of counteranions and solvent molecules on delicate anion–Ag, π–π-stacking and argentophilic interactions was studied through complexes 1–5. The 1D chains of complexes 6 and 7 possessed monodentate L ligand side arms. The uncoordinated N-donors of these side arms were inclined towards the Ag(I) centre of the adjacent chains and demonstrated narrower Ag–Npy–Cg(pyridyl) angles. In the case of complexes 8 and 9, wider Ag–Npy–Cg(pyridyl) angles and stronger N⋯Ag interactions resulted in (4,4) nets. The effects of the size and the nature of the counteranions on the topology were studied through complexes 6–9.

Graphical abstract: Effect of anion on Ag(i) meso-helical chains formed with 4,4′-dipyridyl ketone: solvent versus anion bridging and anion effects on the strength of ligand binding

Supplementary files

Article information


Submitted
21 Jan 2014
Accepted
10 Mar 2014
First published
12 Mar 2014

This article is Open Access

CrystEngComm, 2014,16, 4587-4601
Article type
Paper
Author version available

Effect of anion on Ag(I) meso-helical chains formed with 4,4′-dipyridyl ketone: solvent versus anion bridging and anion effects on the strength of ligand binding

K. M. Patil, S. A. Cameron, S. C. Moratti and L. R. Hanton, CrystEngComm, 2014, 16, 4587 DOI: 10.1039/C4CE00155A

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