Abstract
Reactions of 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) with AgPF6 and AgBF4 afforded cationic silver complexes [Ag(HacacPyen)2]+ with essentially linear coordination of the Ag I cation by two pyridine N atoms. Rather unexpectedly, the HacacPyen ligands in the PF6- salt 1 adopt the diketo form, in contrast to the uncoordinated HacacPyen molecule, whereas the corresponding BF4- salt 2 and the majority of 3-substituted acetylacetones crystallizes as the enol tautomer. In both compounds 1 and 2, complex cations aggregate via short Ag...Ag interactions to pairs. These contacts amount to 3 . 21 Å in 1 and 3 . 26 Å or 3 . 31 Å in 2. As they are unsupported by any additional bridging ligands and correspond to the closest interionic interactions between neighbouring complex cations, they may be addressed as argentophilic interactions. The PF6- anions in 1 and the BF4- counter ions in 2 are involved in long and presumably electrostatic Ag...F contacts of ca. 2 . 9 Å. Additional coordination between Ag I and keto O atoms of symmetry-equivalent ligands occurs in 1 and leads to an extended two-periodic supramolecular structure.
Highlights
The increasing interest in metal-organic frameworks (MOFs) is due to the structural diversity and inherent beauty of this class of compounds and to their physical properties.The organic linkers may connect nodes with attractive magnetic [1,2] or optical [3] features, and often a large inner surface area enables a variety of applications such as gas storage [4] or catalysis [5,6,7,8].The incorporation of more than a single cation type as nodes can obviously increase the range of accessible coordination polymers and in principle enable more potential applications
In both compounds 1 and 2, complex cations aggregate via short Ag···Ag interactions to pairs. These contacts amount to 3.21 Å in 1 and 3.26 Å or 3.31 Å in 2. As they are unsupported by any additional bridging ligands and correspond to the closest interionic interactions between neighbouring complex cations, they may be addressed as argentophilic interactions
We recently investigated the crystal structure of HacacPyen by temperature-dependent neutron diffraction and confirmed that the uncoordinated organic molecule exists as the enol tautomer [35]
Summary
The increasing interest in metal-organic frameworks (MOFs) is due to the structural diversity and inherent beauty of this class of compounds and to their physical properties.The organic linkers may connect nodes with attractive magnetic [1,2] or optical [3] features, and often a large inner surface area enables a variety of applications such as gas storage [4] or catalysis [5,6,7,8].The incorporation of more than a single cation type as nodes can obviously increase the range of accessible coordination polymers and in principle enable more potential applications. The increasing interest in metal-organic frameworks (MOFs) is due to the structural diversity and inherent beauty of this class of compounds and to their physical properties. The organic linkers may connect nodes with attractive magnetic [1,2] or optical [3] features, and often a large inner surface area enables a variety of applications such as gas storage [4] or catalysis [5,6,7,8]. The incorporation of more than a single cation type as nodes can obviously increase the range of accessible coordination polymers and in principle enable more potential applications. Pearson hardness [9,10] and have been successfully employed to assemble well-ordered bimetallic extended structures. Scheme 1 compiles two widely used examples and our candidate from this class of compounds
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