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Issue 21, 2000
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Multi-modal bridging ligands; effects of ligand functionality, anion and crystallisationsolvent in silver(I) co-ordination polymers

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The influence of solvent and anion on the formation of co-ordination polymers of silver(I) and the multi-modal ligands 2,2′-bipyrazine (bpyz) and pyrazino[2,3- f ]quinoxaline (pyq) has been studied. Reaction of AgX (X = BF4 or PF6) with bpyz or pyq in MeNO2 affords three-dimensional co-ordination networks, {[Ag(bpyz)]X} or {[Ag(pyq)]X}. Whereas {[Ag(bpyz)]X} form diamond-like networks, which adopt a chiral structure due to the different bridging modes of the bpyz ligand, {[Ag(pyq)]X} form unusual achiral three-dimensional frameworks which are constructed from bridged [Ag(pyq)] tubes. In the case of {[Ag(bpyz)]X} an increase in anion volume from BF4 to PF6 leads to a corresponding increase in helix volume and concomitant contraction of the helical pitch of the diamondoid framework. The use of co-ordinating solvents of crystallisation in the reactions of AgBF4 with bpyz results in the formation of an undulating two-dimensional sheet, {[Ag(bpyz)(MeCN)]BF4}, when MeCN replaces MeNO2, or a one-dimensional polymer {[Ag2(bpyz)2(PhCN)][BF4]2}, when PhCN is used. Reaction of AgBF4 with pyq in either MeCN or PhCN affords the discrete molecular complex [Ag(pyq)2]BF4 in which only the chelating donors of the pyq ligand are co-ordinated to the silver(I) ion. [Ag(pyq)2]BF4 exhibits dimorphism with the two structures observed differing in the nature of their π–π interactions.

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Supplementary files

Article information

20 Apr 2000
06 Jun 2000
First published
10 Oct 2000

J. Chem. Soc., Dalton Trans., 2000, 3811-3819
Article type

Multi-modal bridging ligands; effects of ligand functionality, anion and crystallisation solvent in silver(I) co-ordination polymers

A. J. Blake, N. R. Champness, P. A. Cooke, J. E. B. Nicolson and C. Wilson, J. Chem. Soc., Dalton Trans., 2000, 3811
DOI: 10.1039/B003202F

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