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Issue 3, 2015
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Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

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Abstract

Tri- and hexa-cyanoethyl functionalized 17- (L1) and 42-membered (L2) macrocyclic compounds were obtained by [1 + 1] (for L1) or [2 + 2] (for L2) cyclocondensation of the corresponding dialdehyde and diethylenetriamine, followed by hydrogenation by KBH4 and subsequent cyano-functionalization with acrylonitrile. They react with silver nitrate, leading to the formation of [AgL1](NO3) (1) and of the metal–organic coordination polymers [Ag2(NO3)2L1]n (2) and {[Ag2L2](NO3)2}n (3). The complexes were characterized by elemental analysis, 1H NMR, 13C NMR, IR spectroscopies, and ESI-MS; moreover, L2, 1, 2 and 3 were also characterized by single crystal X-ray diffraction. The metal cation in 1 is pentacoordinated with a N3O2 coordination environment; in 2, the metal cations display N4O2 octahedral and N2O3 square-pyramid coordination and in 3 they are in square-planar N4 sites. In 1, the ligand acts as a pentadentate chelator, and in the other two cases, the ligands behave as octadentate chelators in a 1κ3N2O,2κN,3κN,4κN (in 2) or 1κ3N,2κ3N,3κN,4κN fashion (in 3). The cyanoethyl strands of the ligands are directly involved in the formation of the 2D frameworks of 2 and 3, which in the former polymer can be viewed as a net composed of hexametallic 36-membered macrocyclic rings and in the latter generates extra hexametallic 58-membered cyclic sets that form zig-zag layers. The thermal analytical and electrochemical properties of these silver complexes were also studied.

Graphical abstract: Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

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Publication details

The article was received on 27 Aug 2014, accepted on 07 Nov 2014 and first published on 07 Nov 2014


Article type: Paper
DOI: 10.1039/C4DT02604G
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 1388-1396
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    Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

    Z. Ma, H. Shi, X. Deng, M. F. C. Guedes da Silva, L. M. D. R. S. Martins and A. J. L. Pombeiro, Dalton Trans., 2015, 44, 1388
    DOI: 10.1039/C4DT02604G

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