- A rigid angular bidentate ligand for the design of a new class of coordination polymers based on silver(I) salts - Influence of the anion on coordination assemblies
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The synthesis of a new family of coordination polymers [AgL 2X]n (1a, X = CF3SO3; 1b, X = BF4; 1c, X = NO3; 1d, X = PF6) using 5-methoxy-1,3-bis(pyridin-3-ylethynyl)benzene (L2) as the self-assembling ligand is described. All compounds have been fully characterized by spectroscopic techniques and elemental analysis. In particular the X-ray molecular structures of 1a and 1b are reported and confirm the formation of 1D silver(I) chains. Their arrangements are described as a function and the nature of the anion. The supramolecular product 1a exhibits argentophilic Ag···Ag interactions to afford infinite double chains. Additionally, I·1-AgI-π interactions lead to the formation of a network of stacked layers of double chains. In contrast, 1b lacks metal-counterion bonding and is constituted of infinite coordination polymers, which are held together by π-π interactions. The pivotal role of the counteranions on the overall packing arrangement of the polymers is presented and discussed.
- Desmarets, Christophe,Azcarate, Iban,Gontard, Geoffrey,Amouri, Hani
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- Folding of coordination polymers into double-stranded helical organization
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Self-assembling coordination polymers based on PdII and Cu II metal ions were prepared from complexation of a bent-shaped bispyridine ligand and a corresponding transition metal. These coordination polymers were observed to self-assemble into supramolecular structures that differ significantly depending on the coordination geometry of the metal center. The polymer based on PdII self-assembles into a layer structure formed by bridging bispyri dine ligands connected in a trans-position of the square-planar coordination geometry of metal center. In contrast, the polymer based on CuII adopts a double-helical conformation with regular grooves, driven by interstranded, copper-chloride dimeric interaction. The double-stranded helical organization is further confirmed by structure optimization from density functional theory with aromatic framework, showing that the optimized double-helical structure is energetically favorable and consistent with the experimental results. These results demonstrate that weak metal-ligand bridging interactions can provide a useful strategy to construct stable double-stranded helical nanotubes.
- Kim, Ho-Joong,Lee, Eunji,Kim, Min Gyu,Kim, Min-Cheol,Lee, Myongsoo,Sim, Eunji
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supporting information; experimental part
p. 3883 - 3888
(2009/04/17)
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