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Silver(I) pyrophosphonates: structural, photoluminescent and thermal expansion studies.

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Title: Silver(I) pyrophosphonates: structural, photoluminescent and thermal expansion studies.
Authors: Guo, Li-Rong1, Tong, Jian-Wei2, Liang, Xü1, Köhler, Jürgen2, Nuss, Jürgen2, Li, Yi-Zhi1, Zheng, Li-Min1
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. Jun2011, Vol. 40 Issue 24, p6392-6400. 9p.
Subjects: Silver compounds, Phosphonates, Photoluminescence, Thermal expansion, Chemical reactions, Chemical structure, Phosphonic acids
Abstract: The solvothermal reactions of silver(i) salts with mono-organophosphonic acids, i.e.3-thienylphosphonic acid (3-TPA), phenylphosphonic acid (PPA), α-naphthylphosphonic acid (α-NPA) and cyclohexylphosphonic acid (CPA), yield four new silver(i) pyrophosphonates, namely: [Ag2(ptp)] (1), [Ag2(ppp)] (2), [Ag3(CH3CN)(pnp)(pnpH)] (3), and [Ag3(pcp)(pcpH)] (4) [ptp2−= pyro-3-thienylphosphonate, ppp2−= pyrophenylphosphonate, pnp2−= pyro-α-naphthylphosphonate, pcp2−= pyrocyclohexylphosphoante]. In all cases, the pyrophosphonate ligands are generated in situfrom their relative mono-organophosphonic acids, mediated by silver(i) ions. Single crystal structural determinations reveal that compounds 1and 2display two-dimensional layer architectures, while 3and 4show one-dimensional chain structures. Structure 1can be best described as a layer made up of Ag4O(P)6clusters linked by O–P–O units and AgAg contacts, with the organic groups grafted on the two sides of the inorganic layer. A similar layer structure is found in 2except that the AgAg interactions are absent. Compound 3shows a chain structure where the silver ions are bridged by the phosphonate oxygen atoms forming an infinite Ag–O(P) chain which is decorated by the pyrophosphonate ligand and CH3CN. Compound 4has another type of chain structure made up of Ag–O(P) with extensive AgAg argentophilic interactions. Solid state photoluminescent properties and thermal expansion behaviors are also investigated. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
Description
Abstract:The solvothermal reactions of silver(i) salts with mono-organophosphonic acids, i.e.3-thienylphosphonic acid (3-TPA), phenylphosphonic acid (PPA), α-naphthylphosphonic acid (α-NPA) and cyclohexylphosphonic acid (CPA), yield four new silver(i) pyrophosphonates, namely: [Ag2(ptp)] (1), [Ag2(ppp)] (2), [Ag3(CH3CN)(pnp)(pnpH)] (3), and [Ag3(pcp)(pcpH)] (4) [ptp2−= pyro-3-thienylphosphonate, ppp2−= pyrophenylphosphonate, pnp2−= pyro-α-naphthylphosphonate, pcp2−= pyrocyclohexylphosphoante]. In all cases, the pyrophosphonate ligands are generated in situfrom their relative mono-organophosphonic acids, mediated by silver(i) ions. Single crystal structural determinations reveal that compounds 1and 2display two-dimensional layer architectures, while 3and 4show one-dimensional chain structures. Structure 1can be best described as a layer made up of Ag4O(P)6clusters linked by O–P–O units and AgAg contacts, with the organic groups grafted on the two sides of the inorganic layer. A similar layer structure is found in 2except that the AgAg interactions are absent. Compound 3shows a chain structure where the silver ions are bridged by the phosphonate oxygen atoms forming an infinite Ag–O(P) chain which is decorated by the pyrophosphonate ligand and CH3CN. Compound 4has another type of chain structure made up of Ag–O(P) with extensive AgAg argentophilic interactions. Solid state photoluminescent properties and thermal expansion behaviors are also investigated. [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/c1dt10236b