Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers
We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>1</b>), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>2</b>), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>3</b>), 4′-(4′-brom...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-02-01
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| Series: | Chemistry |
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| Online Access: | https://www.mdpi.com/2624-8549/3/1/15 |
| _version_ | 1797416714021896192 |
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| author | Dalila Rocco Samantha Novak Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft |
| author_facet | Dalila Rocco Samantha Novak Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft |
| author_sort | Dalila Rocco |
| collection | DOAJ |
| description | We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>1</b>), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>2</b>), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>3</b>), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>4</b>), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>5</b>), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>L]<i><sub>n</sub></i> 1D-coordination polymers with L = <b>1</b>–<b>5</b> have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>1</b>)]<i><sub>n</sub></i> and [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>2</b>)]<i><sub>n</sub></i> are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in <b>1</b> by an F substituent in <b>2</b> has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for <b>1</b> or H...F for <b>2</b>) are only secondary packing interactions. Upon going from [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>1</b>)]<i><sub>n</sub></i> and [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>2</b>)]<i><sub>n</sub></i> to [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>3</b>)]<i><sub>n</sub></i>, [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>4</b>)]<i><sub>n</sub></i>, and [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>5</b>)]<i><sub>n</sub></i>·<i>n</i>MeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility. |
| first_indexed | 2024-03-09T06:07:05Z |
| format | Article |
| id | doaj.art-35727fad24ba46efb22e58e553c8a14c |
| institution | Directory Open Access Journal |
| issn | 2624-8549 |
| language | English |
| last_indexed | 2024-03-09T06:07:05Z |
| publishDate | 2021-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Chemistry |
| spelling | doaj.art-35727fad24ba46efb22e58e553c8a14c2023-12-03T12:01:56ZengMDPI AGChemistry2624-85492021-02-013118219810.3390/chemistry3010015Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-PolymersDalila Rocco0Samantha Novak1Alessandro Prescimone2Edwin C. Constable3Catherine E. Housecroft4Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandWe report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>1</b>), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>2</b>), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>3</b>), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>4</b>), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (<b>5</b>), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>L]<i><sub>n</sub></i> 1D-coordination polymers with L = <b>1</b>–<b>5</b> have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>1</b>)]<i><sub>n</sub></i> and [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>2</b>)]<i><sub>n</sub></i> are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in <b>1</b> by an F substituent in <b>2</b> has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for <b>1</b> or H...F for <b>2</b>) are only secondary packing interactions. Upon going from [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>1</b>)]<i><sub>n</sub></i> and [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>2</b>)]<i><sub>n</sub></i> to [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>3</b>)]<i><sub>n</sub></i>, [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>4</b>)]<i><sub>n</sub></i>, and [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(<b>5</b>)]<i><sub>n</sub></i>·<i>n</i>MeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility.https://www.mdpi.com/2624-8549/3/1/153,2′:6′,3″-terpyridinecoordination polymercopper(II) acetatepaddle-wheel building blockX-ray diffraction |
| spellingShingle | Dalila Rocco Samantha Novak Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers Chemistry 3,2′:6′,3″-terpyridine coordination polymer copper(II) acetate paddle-wheel building block X-ray diffraction |
| title | Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers |
| title_full | Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers |
| title_fullStr | Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers |
| title_full_unstemmed | Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers |
| title_short | Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu<sub>2</sub>(μ-OAc)<sub>4</sub>(3,2′:6′,3″-tpy)]<i><sub>n</sub></i> 1D-Polymers |
| title_sort | manipulating the conformation of 3 2 6 3 terpyridine in cu sub 2 sub μ oac sub 4 sub 3 2 6 3 tpy i sub n sub i 1d polymers |
| topic | 3,2′:6′,3″-terpyridine coordination polymer copper(II) acetate paddle-wheel building block X-ray diffraction |
| url | https://www.mdpi.com/2624-8549/3/1/15 |
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