American Chemical Society
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Influence of Counteranions on the Structural Modulation of Silver–Di(3-pyridylmethyl)amine Coordination Polymers

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journal contribution
posted on 2013-07-03, 00:00 authored by Jing-Yun Wu, Tzu-Ching Chao, Ming-Shiou Zhong
The coordination chemistry of a flexible N-donor ligand di­(3-pyridylmethyl)­amine (dpma) with silver salts has been investigated. Six new silver coordination polymers, namely, [Ag­(dpma)­(H2O)]­(NO3) (1), [Ag­(dpma)­(CF3CO2)]­·1/2H2O (2), [Ag­(dpma)]­(CF3SO3)­·1/2H2O (3), [Ag­(dpma)]­(BF4)­·3/2H2O (4), [Ag3(dpma)2(H2O)]­(ClO4)3 (5), and [Ag­(dpma)]­(PF6) (6), have been prepared by slow diffusion reactions. All the polymeric structures of compounds 16 are described as topologic binodal networks in terms of Ag and dpma building blocks. Compounds 14 show a one-dimensional ladder-like chain structure, with both Ag and dpma as three-connected T-nodes; compound 5 is an uncommon one-dimensional metallamacrocycle-based chain structure, with Ag as two-connected I-node and dpma as three-connected T-node; compound 6 is a two-dimensional honeycomb-like layer structure, with both Ag and dpma as three-connected Y-nodes. Within the structures, the dpma ligand adopts a variety of structure conformations including gauche–trans–anti (1 and 2), trans–trans–anti (3 and 4), trans–trans–syn (3), gauche–gauche–syn (5), and trans–gauche–syn (6) conformations. For these Ag–dpma coordination polymers, the structural diversity and complexity are most likely attributed to the different coordinating nature, hydrogen-bonding propensity, and templating effect of the counteranions and solvent molecules. Solution studies suggest that compounds 16 would disaggregate to break down the polymeric structures and then to give multiple rapidly exchanging solution species in DMSO or acetonitrile. The thermal stabilities of compounds 16 are examined. In addition, the photoluminescent properties of compounds 16 are investigated in the solid state at room temperature.