Elsevier

Inorganica Chimica Acta

Volume 403, 1 July 2013, Pages 2-8
Inorganica Chimica Acta

Review
Silver coordination polymers with isonicotinic acid derived short polyethylene glycol – Synthesis, structures, anion effect and solution behavior

https://doi.org/10.1016/j.ica.2012.12.021Get rights and content

Abstract

Silver coordination compounds and one-dimensional polymers have been studied, using a linear, flexible N-donor ligand. The solid state structures are well known and show panoply of different structures including a large number of polymorphism, pseudo-polymorphism and isomers. We have studied these structures under the influence of anions, solvents and crystallization conditions, studying also some solution effects. We here present an overview with highlights of some case studies of the synthesis, structures, anion and solvent effects as well as solution behavior during formation of silver coordination polymers. Finally, we will give an outlook on the potential applications of these materials.

Graphical abstract

Silver ions form with neutral “linear” ligands oligomeric complexes in solution, from which a number of 1D-chain solid state structures are obtained which afford polymorphism and pseudo-polymorphism, as well as isomerism.

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Highlights

► We give an overview on silver coordination compounds obtained with short ligands. ► The solid state structures are discussed with respect to solvent and counter ions. ► Results from solution studies prove the formation of oligomeric species. ► Crystal engineering aspects are discussed.

Introduction

Silver coordination polymers are studied by many groups due to their structural diversity [1], [2] as well as potential use e.g. in catalysis [3], in gas sorption [4], luminescence [5] or as antimicrobial coating [6], [7]. In most cases, the solid state structures are the most prominently discussed results obtained in this kind of research areas, while solution studies of the formation of silver coordination polymers remain rare [8]. Nevertheless, this is an important issue in the understanding of the formation of these structures. Thus, we here would like to present (a) an overview on the different structures as a function of solvent, anion and crystallization conditions, and (b) some case studies taken from our previous research.

We started to investigate silver coordination polymers using the neutral ligand ethanediyl bis(isonicotinate) Li1 (Scheme 1) [9], [10] and its derivatives, which can be modified by simple elongation of the middle spacer, using diethylene glycol [11], triethylene glycol [12], [13] and tetraethylene glycol [13], [14] as starting materials for the synthesis of the ligands. In this manuscript however, we will focus on the shortest variant of the ligand, Li1.

Section snippets

Results and discussion

We have shown that the free ligand Li1 crystallizes in the anti conformation, while both conformations, anti and gauche, have a very similar energy and a low energy of activation [13]. Upon coordination of the ligand Li1 to silver ions, we thus expected solid state structures with both ligand conformations. So far, we have obtained the structural motifs described in Scheme 2 [16], [17], [18].

In total, seven different coordination polymers were obtained in our group so far with Li1, of which

Acknowledgements

We thank the Swiss National Science Foundation and the University of Fribourg for continuous support and the Fribourg Center for Nanomaterials FriMat for co-funding of machines.

Katharina M. Fromm received her PhD in organometallic chemistry from the University of Karlsruhe, Germany. After postdoctoral studies with Prof. J. Strähle in Tübingen, Germany, and Prof. J.-M. Lehn in Strasbourg, France, she started own investigations at the University of Geneva, Switzerland and received an Emmy Noether Program II to go back to Karlsruhe. She then accepted a stipend as assistant professor Lehn in Strasbourg, France, she started own investigations at the University of Geneva,

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    Katharina M. Fromm received her PhD in organometallic chemistry from the University of Karlsruhe, Germany. After postdoctoral studies with Prof. J. Strähle in Tübingen, Germany, and Prof. J.-M. Lehn in Strasbourg, France, she started own investigations at the University of Geneva, Switzerland and received an Emmy Noether Program II to go back to Karlsruhe. She then accepted a stipend as assistant professor Lehn in Strasbourg, France, she started own investigations at the University of Geneva, Switzerland and received an Emmy Noether Program II to go back to Karlsruhe. She then accepted a stipend as assistant professor at the University of Basel, Switzerland before becoming a full professor at the University of Fribourg, Switzerland in 2006.

    Adeline Y. Robin did her PhD with KMF at the Universities of Geneva and Basel, where she graduated 2005. Her PhD was followed by postdoctoral studies at the CEA CNRS INRA of the Université Joseph Fourier. Adeline is now in Australia, where she is associated with the Walter and Eliza Hall Institute of Medical Research in Parkville, Victoria, and the Department of Medical Biology of the University of Melbourne.

    Jorge L. Sague received his PhD in 2006 from the University of Basel. He moved with the group to Fribourg, then to the University of Geneva, where he stayed for a second postdoc. Since 2009, he is a polymer specialist and group leader since 2011 at the RMS Foundation in Bettlach, Switzerland. He lectures in the Master of Science and Biomedical Engineering at the University of Bern.

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