Silver(I) Coordination Polymer Ligated by Bipyrazole Me4bpzH2, [Ag(X)(Me4bpzH2)] (X = CF3CO2− and CF3SO3−, Me4bpzH2 = 3,3′,5,5′-Tetramethyl-4,4′-bipyrazole): Anion Dependent Structures and Photoluminescence Properties
Coordination polymers of transition metal ions are fascinating and important to coordination chemistry. One of the ligands known to form particularly interesting coordination polymers is 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (Me4bpzH2). Group 11 metal(I) ion coordination polymers, other than those o...
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| Published in | Molecules (Basel, Switzerland) Vol. 28; no. 7; p. 2936 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
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| Abstract | Coordination polymers of transition metal ions are fascinating and important to coordination chemistry. One of the ligands known to form particularly interesting coordination polymers is 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (Me4bpzH2). Group 11 metal(I) ion coordination polymers, other than those of copper(I), are relatively easy to handle because of their low reactivity towards dioxygen and moisture. However, the known silver(I) coordination polymers often have poor solubility in common solvents and so cannot be easily analyzed in solution. By using a tetramethyl substituted bipyrazole ligand, we have synthesized more soluble silver(I) complexes that contain the trifluoromethyl group in the coordinated ions CF3CO2− and CF3SO3− in [Ag(CF3CO2)(Me4bpzH2)] and [Ag(CF3SO3)(Me4bpzH2)]. We determined both structures by single-crystal X-ray analysis at low temperatures and compared them in detail. Moreover, we investigated the solution behavior of these coordination polymers by 1H-NMR, IR, Raman, UV–Vis spectroscopies, and their low-temperature, solid-state photoluminescence. The high-energy band at ~330 nm corresponded to ligand-centered (bipyrazole) fluorescence, and the low-energy band at ~400 nm to ligand-centered phosphorescence resulting from the heavy atom effect. |
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| AbstractList | Coordination polymers of transition metal ions are fascinating and important to coordination chemistry. One of the ligands known to form particularly interesting coordination polymers is 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (Me4bpzH2). Group 11 metal(I) ion coordination polymers, other than those of copper(I), are relatively easy to handle because of their low reactivity towards dioxygen and moisture. However, the known silver(I) coordination polymers often have poor solubility in common solvents and so cannot be easily analyzed in solution. By using a tetramethyl substituted bipyrazole ligand, we have synthesized more soluble silver(I) complexes that contain the trifluoromethyl group in the coordinated ions CF3CO2− and CF3SO3− in [Ag(CF3CO2)(Me4bpzH2)] and [Ag(CF3SO3)(Me4bpzH2)]. We determined both structures by single-crystal X-ray analysis at low temperatures and compared them in detail. Moreover, we investigated the solution behavior of these coordination polymers by 1H-NMR, IR, Raman, UV–Vis spectroscopies, and their low-temperature, solid-state photoluminescence. The high-energy band at ~330 nm corresponded to ligand-centered (bipyrazole) fluorescence, and the low-energy band at ~400 nm to ligand-centered phosphorescence resulting from the heavy atom effect. Coordination polymers of transition metal ions are fascinating and important to coordination chemistry. One of the ligands known to form particularly interesting coordination polymers is 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (Me 4 bpzH 2 ). Group 11 metal(I) ion coordination polymers, other than those of copper(I), are relatively easy to handle because of their low reactivity towards dioxygen and moisture. However, the known silver(I) coordination polymers often have poor solubility in common solvents and so cannot be easily analyzed in solution. By using a tetramethyl substituted bipyrazole ligand, we have synthesized more soluble silver(I) complexes that contain the trifluoromethyl group in the coordinated ions CF 3 CO 2 − and CF 3 SO 3 − in [Ag(CF 3 CO 2 )(Me 4 bpzH 2 )] and [Ag(CF 3 SO 3 )(Me 4 bpzH 2 )] . We determined both structures by single-crystal X-ray analysis at low temperatures and compared them in detail. Moreover, we investigated the solution behavior of these coordination polymers by 1 H-NMR, IR, Raman, UV–Vis spectroscopies, and their low-temperature, solid-state photoluminescence. The high-energy band at ~330 nm corresponded to ligand-centered (bipyrazole) fluorescence, and the low-energy band at ~400 nm to ligand-centered phosphorescence resulting from the heavy atom effect. |
| Author | Kondo, Shiori Okano, Mitsuki Iwabuchi, Ryota Fujisawa, Kiyoshi Young, David James Kobayashi, Yui |
| AuthorAffiliation | 2 Faculty of Science and Technology, Charles Darwin University, Darwin, NT 0909, Australia; david.young@cdu.edu.au 1 Department of Chemistry, Ibaraki University, Mito 310-8512, Ibaraki, Japan |
| AuthorAffiliation_xml | – name: 1 Department of Chemistry, Ibaraki University, Mito 310-8512, Ibaraki, Japan – name: 2 Faculty of Science and Technology, Charles Darwin University, Darwin, NT 0909, Australia; david.young@cdu.edu.au |
| Author_xml | – sequence: 1 givenname: Kiyoshi orcidid: 0000-0002-4023-0025 surname: Fujisawa fullname: Fujisawa, Kiyoshi – sequence: 2 givenname: Yui surname: Kobayashi fullname: Kobayashi, Yui – sequence: 3 givenname: Mitsuki surname: Okano fullname: Okano, Mitsuki – sequence: 4 givenname: Ryota surname: Iwabuchi fullname: Iwabuchi, Ryota – sequence: 5 givenname: Shiori surname: Kondo fullname: Kondo, Shiori – sequence: 6 givenname: David James surname: Young fullname: Young, David James |
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| Snippet | Coordination polymers of transition metal ions are fascinating and important to coordination chemistry. One of the ligands known to form particularly... |
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| StartPage | 2936 |
| SubjectTerms | bipyrazole ligand coordination polymer Coordination polymers crystal structure Energy bands Fluorescence Geometry Hydrogen bonds Ligands Low temperature Luminescence Metal ions NMR Nuclear magnetic resonance Phosphorescence Photoluminescence Photons Polymers Silver Single crystals Transition metals X ray analysis |
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| Title | Silver(I) Coordination Polymer Ligated by Bipyrazole Me4bpzH2, [Ag(X)(Me4bpzH2)] (X = CF3CO2− and CF3SO3−, Me4bpzH2 = 3,3′,5,5′-Tetramethyl-4,4′-bipyrazole): Anion Dependent Structures and Photoluminescence Properties |
| URI | https://www.proquest.com/docview/2799734017/abstract/ https://search.proquest.com/docview/2800625728 https://pubmed.ncbi.nlm.nih.gov/PMC10096423 https://doaj.org/article/2add632675d34a40bca9a0d31b88071d |
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