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Polymers 2016, 8(4), 137; doi:10.3390/polym8040137

Hg(II) Coordination Polymers Based on N,N’-bis(pyridine-4-yl)formamidine

Department of Chemistry, Chung Yuan Christian University, Chung-Li 320, Taiwan, R. O. C.
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Academic Editors: Félix Zamora, Thomas Junkers and Frank Wiesbrock
Received: 25 January 2016 / Revised: 29 March 2016 / Accepted: 1 April 2016 / Published: 11 April 2016
(This article belongs to the Special Issue Coordination Polymers: New Materials for Multiple Applications)
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Abstract

Reactions of N,N’-bis(pyridine-4-yl)formamidine (4-Hpyf) with HgX2 (X = Cl, Br, and I) afforded the formamidinate complex {[Hg(4-pyf)2]·(THF)}n, 1, and the formamidine complexes {[HgX2(4-Hpyf)]·(MeCN)}n (X = Br, 2; I, 3), which have been structurally characterized by X-ray crystallography. Complex 1 is a 2D layer with the {44·62}-sql topology and complexes 2 and 3 are helical chains. While the helical chains of 2 are linked through N–H···Br hydrogen bonds, those of 3 are linked through self-complementary double N–H···N hydrogen bonds, resulting in 2D supramolecular structures. The 4-pyf- ligands of 1 coordinate to the Hg(II) ions through one pyridyl and one adjacent amine nitrogen atoms and the 4-Hpyf ligands of 2 and 3 coordinate to the Hg(II) ions through two pyridyl nitrogen atoms, resulting in new bidentate binding modes. Complexes 1–3 provide a unique opportunity to envisage the effect of the halide anions of the starting Hg(II) salts on folding and unfolding the Hg(II) coordination polymers. Density function theory (DFT) calculation indicates that the emission of 1 is due to intraligand π→π * charge transfer between two different 4-pyf- ligands, whereas those of 2 and 3 can be ascribed to the charge transfer from non-bonding p-type orbitals of the halide anions to π * orbitals of the 4-pyf- ligands (n→π *). The gas sorption properties of the desolvated product of 1 are compared with the Cu analogues to show that the nature of the counteranion and the solvent-accessible volume are important in determining their adsorption capability. View Full-Text
Keywords: coordination polymer; mercury; formamidine coordination polymer; mercury; formamidine
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Hsu, W.; Yang, X.-K.; Chhetri, P.M.; Chen, J.-D. Hg(II) Coordination Polymers Based on N,N’-bis(pyridine-4-yl)formamidine. Polymers 2016, 8, 137.

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