Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes
Heteroleptic [Cu(BIPHEP)(N^N)][PF<sub>6</sub>] complexes (BIPHEP = 1,1′-biphenyl-2,2′-diylbis(diphenylphosphane)), in which N^N is 2,2′-bipyridine (bpy), 6-methyl-2,2′-bipyridine (6-Mebpy), 6-ethyl-2,2′-bipyridine (6-Etbpy), or 5,5...
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/21/3934 |
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| author | Sarah Keller Matthias Bantle Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft |
| author_facet | Sarah Keller Matthias Bantle Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft |
| author_sort | Sarah Keller |
| collection | DOAJ |
| description | Heteroleptic [Cu(BIPHEP)(N^N)][PF<sub>6</sub>] complexes (BIPHEP = 1,1′-biphenyl-2,2′-diylbis(diphenylphosphane)), in which N^N is 2,2′-bipyridine (bpy), 6-methyl-2,2′-bipyridine (6-Mebpy), 6-ethyl-2,2′-bipyridine (6-Etbpy), or 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me<sub>2</sub>bpy), have been synthesized and characterized using multinuclear NMR spectroscopies and electrospray ionization mass spectrometry. The single crystal structures of [Cu(BIPHEP)(bpy)][PF<sub>6</sub>]∙CH<sub>2</sub>Cl<sub>2</sub>, [Cu(BIPHEP)(5,5′-Me<sub>2</sub>bpy)][PF<sub>6</sub>]∙CH<sub>2</sub>Cl<sub>2</sub>, [Cu(BIPHEP)(6-Mebpy)][PF<sub>6</sub>]∙Et<sub>2</sub>O∙0.5H<sub>2</sub>O and [Cu(BIPHEP)(6-Etbpy)][PF<sub>6</sub>] confirm distorted tetrahedral {Cu(P^P)(N^N)} coordination environments. Each compound shows a quasi-reversible Cu<sup>+</sup>/Cu<sup>2+</sup> process. In deaerated solution, the compounds are weak emitters. Powdered samples are yellow emitters (<i>λ</i><sub>em</sub><sup>max</sup> in the range 558−583 nm) and [Cu(BIPHEP)(5,5′-Me<sub>2</sub>bpy)][PF<sub>6</sub>] exhibits the highest photoluminescence quantum yield (PLQY = 14%). On cooling to 77 K (frozen 2-methyloxolane), the emission maxima are red-shifted and the excited state lifetimes increase from <i>τ</i><sub>1/2</sub> < 8 μs, to <i>τ</i><sub>1/2</sub> values of up to 53 μs, consistent with the compounds with N^N = 6-Mebpy, 6-Etbpy and 5,5′-Me<sub>2</sub>bpy exhibiting thermally activated delayed fluorescence (TADF). |
| first_indexed | 2024-12-20T14:40:15Z |
| format | Article |
| id | doaj.art-f716dc3e5d514f3a98454cdd3f9c9830 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T14:40:15Z |
| publishDate | 2019-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f716dc3e5d514f3a98454cdd3f9c98302022-12-21T19:37:19ZengMDPI AGMolecules1420-30492019-10-012421393410.3390/molecules24213934molecules24213934Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] ComplexesSarah Keller0Matthias Bantle1Alessandro 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, SwitzerlandHeteroleptic [Cu(BIPHEP)(N^N)][PF<sub>6</sub>] complexes (BIPHEP = 1,1′-biphenyl-2,2′-diylbis(diphenylphosphane)), in which N^N is 2,2′-bipyridine (bpy), 6-methyl-2,2′-bipyridine (6-Mebpy), 6-ethyl-2,2′-bipyridine (6-Etbpy), or 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me<sub>2</sub>bpy), have been synthesized and characterized using multinuclear NMR spectroscopies and electrospray ionization mass spectrometry. The single crystal structures of [Cu(BIPHEP)(bpy)][PF<sub>6</sub>]∙CH<sub>2</sub>Cl<sub>2</sub>, [Cu(BIPHEP)(5,5′-Me<sub>2</sub>bpy)][PF<sub>6</sub>]∙CH<sub>2</sub>Cl<sub>2</sub>, [Cu(BIPHEP)(6-Mebpy)][PF<sub>6</sub>]∙Et<sub>2</sub>O∙0.5H<sub>2</sub>O and [Cu(BIPHEP)(6-Etbpy)][PF<sub>6</sub>] confirm distorted tetrahedral {Cu(P^P)(N^N)} coordination environments. Each compound shows a quasi-reversible Cu<sup>+</sup>/Cu<sup>2+</sup> process. In deaerated solution, the compounds are weak emitters. Powdered samples are yellow emitters (<i>λ</i><sub>em</sub><sup>max</sup> in the range 558−583 nm) and [Cu(BIPHEP)(5,5′-Me<sub>2</sub>bpy)][PF<sub>6</sub>] exhibits the highest photoluminescence quantum yield (PLQY = 14%). On cooling to 77 K (frozen 2-methyloxolane), the emission maxima are red-shifted and the excited state lifetimes increase from <i>τ</i><sub>1/2</sub> < 8 μs, to <i>τ</i><sub>1/2</sub> values of up to 53 μs, consistent with the compounds with N^N = 6-Mebpy, 6-Etbpy and 5,5′-Me<sub>2</sub>bpy exhibiting thermally activated delayed fluorescence (TADF).https://www.mdpi.com/1420-3049/24/21/3934copper(i)bis(phosphane)2,2′-bipyridinex-ray structurephotophysicstadf |
| spellingShingle | Sarah Keller Matthias Bantle Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes Molecules copper(i) bis(phosphane) 2,2′-bipyridine x-ray structure photophysics tadf |
| title | Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes |
| title_full | Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes |
| title_fullStr | Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes |
| title_full_unstemmed | Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes |
| title_short | Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF<sub>6</sub>] Complexes |
| title_sort | hinged and wide a new p p ligand for emissive cu p p n n pf sub 6 sub complexes |
| topic | copper(i) bis(phosphane) 2,2′-bipyridine x-ray structure photophysics tadf |
| url | https://www.mdpi.com/1420-3049/24/21/3934 |
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