Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6]
We report the synthesis and characterization of [Cu(P^P)(N^S)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl) ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) and N^S = 2-(iso-propylthio)pyridine (iPrSpy) or 2-(tert-butylthio)pyridine (tBuSpy). The single crysta...
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MDPI AG
2019-01-01
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| Series: | Inorganics |
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| Online Access: | http://www.mdpi.com/2304-6740/7/1/11 |
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| author | Isaak Nohara Alessandro Prescimone Catherine E. Housecroft Edwin C. Constable |
| author_facet | Isaak Nohara Alessandro Prescimone Catherine E. Housecroft Edwin C. Constable |
| author_sort | Isaak Nohara |
| collection | DOAJ |
| description | We report the synthesis and characterization of [Cu(P^P)(N^S)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl) ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) and N^S = 2-(iso-propylthio)pyridine (iPrSpy) or 2-(tert-butylthio)pyridine (tBuSpy). The single crystal structures of [Cu(POP)(iPrSPy)][PF6] and [Cu(POP)(tBuSPy)][PF6] have been determined and confirm a distorted tetrahedral copper(I) centre and chelating P^P and N^S ligands in each complex. Variable temperature (VT) 1H and 31P{1H} NMR spectroscopy reveals dynamic behavior with motion of the POP backbone in [Cu(POP)(iPrSPy)][PF6] and [Cu(POP)(tBuSPy)][PF6] frozen out at 238 K. VT NMR spectroscopic data including EXSY peaks in the ROESY spectrum of [Cu(xantphos)(tBuSPy)][PF6] at 198 K reveal that two conformers exist in an approximate ratio of 5:1. Replacing bpy by the N^S ligands shifts the Cu+/Cu2+ oxidation to a higher potential. The copper(I) compounds are weak emitters in the solid state with PLQY values of <2%. These values are similar to those for [Cu(POP)(bpy)][PF6] and [Cu(xantphos)(bpy)][PF6] in the solid state. |
| first_indexed | 2024-12-14T12:29:58Z |
| format | Article |
| id | doaj.art-a34e77f8df394ac0bbc2cd3e22b12429 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-12-14T12:29:58Z |
| publishDate | 2019-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-a34e77f8df394ac0bbc2cd3e22b124292022-12-21T23:01:12ZengMDPI AGInorganics2304-67402019-01-01711110.3390/inorganics7010011inorganics7010011Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6]Isaak Nohara0Alessandro Prescimone1Catherine E. Housecroft2Edwin C. Constable3Department 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 synthesis and characterization of [Cu(P^P)(N^S)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl) ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) and N^S = 2-(iso-propylthio)pyridine (iPrSpy) or 2-(tert-butylthio)pyridine (tBuSpy). The single crystal structures of [Cu(POP)(iPrSPy)][PF6] and [Cu(POP)(tBuSPy)][PF6] have been determined and confirm a distorted tetrahedral copper(I) centre and chelating P^P and N^S ligands in each complex. Variable temperature (VT) 1H and 31P{1H} NMR spectroscopy reveals dynamic behavior with motion of the POP backbone in [Cu(POP)(iPrSPy)][PF6] and [Cu(POP)(tBuSPy)][PF6] frozen out at 238 K. VT NMR spectroscopic data including EXSY peaks in the ROESY spectrum of [Cu(xantphos)(tBuSPy)][PF6] at 198 K reveal that two conformers exist in an approximate ratio of 5:1. Replacing bpy by the N^S ligands shifts the Cu+/Cu2+ oxidation to a higher potential. The copper(I) compounds are weak emitters in the solid state with PLQY values of <2%. These values are similar to those for [Cu(POP)(bpy)][PF6] and [Cu(xantphos)(bpy)][PF6] in the solid state.http://www.mdpi.com/2304-6740/7/1/11Coppercoordination complex2-(alkylthio)pyridinebis(phosphane)X-ray structuredynamic behavior |
| spellingShingle | Isaak Nohara Alessandro Prescimone Catherine E. Housecroft Edwin C. Constable Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6] Inorganics Copper coordination complex 2-(alkylthio)pyridine bis(phosphane) X-ray structure dynamic behavior |
| title | Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6] |
| title_full | Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6] |
| title_fullStr | Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6] |
| title_full_unstemmed | Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6] |
| title_short | Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6] |
| title_sort | softening the donor set from cu p p n n pf6 to cu p p n s pf6 |
| topic | Copper coordination complex 2-(alkylthio)pyridine bis(phosphane) X-ray structure dynamic behavior |
| url | http://www.mdpi.com/2304-6740/7/1/11 |
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