Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands
A series of [Cu(P^P)(N^N)][PF<sub>6</sub>] compounds are reported in which N^N is 2,9-dibromo-1,10-phenanthroline (2,9-Br<sub>2</sub>phen), 3,8-dibromo-1,10-phenanthroline (3,8-Br<sub>2</sub>phen) or 4,7-dibromo-1,10-phenanthroline (4,7-Br<sub>2</sub>p...
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MDPI AG
2020-01-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/8/1/4 |
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| author | Isaak Nohara Aramis Keller Nikolai Tarassenko Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft |
| author_facet | Isaak Nohara Aramis Keller Nikolai Tarassenko Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft |
| author_sort | Isaak Nohara |
| collection | DOAJ |
| description | A series of [Cu(P^P)(N^N)][PF<sub>6</sub>] compounds are reported in which N^N is 2,9-dibromo-1,10-phenanthroline (2,9-Br<sub>2</sub>phen), 3,8-dibromo-1,10-phenanthroline (3,8-Br<sub>2</sub>phen) or 4,7-dibromo-1,10-phenanthroline (4,7-Br<sub>2</sub>phen) and P^P is bis(2-(diphenylphosphano)phenyl)ether (POP) or 4,5-bis(diphenylphosphano)-9,9-dimethylxanthene (xantphos). The compounds were characterized by solution multinuclear NMR spectroscopy, mass spectrometry and a single-crystal X-ray analysis. Each compound underwent a partially reversible or irreversible copper-centred oxidation, the highest potential being for 2,9-Br<sub>2</sub>phen-containing compounds. In solution, the compounds are weak yellow or orange emitters, whereas powdered samples exhibit yellow emissions with photoluminescence quantum yields of up to 45% for [Cu(xantphos)(2,9-Br<sub>2</sub>phen)][PF<sub>6</sub>] with an excited state lifetime <i>τ</i><sub>1/2</sub> = 9.9 μs. Values of <i>λ</i><sub>em</sub><sup>max</sup> for [Cu(POP)(2,9-Br<sub>2</sub>phen)][PF<sub>6</sub>] and [Cu(xantphos)(2,9-Br<sub>2</sub>phen)][PF<sub>6</sub>] are blue-shifted with respect to compounds with the 3,8-and 4,7-isomers, both in solution and in the solid state. |
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| last_indexed | 2024-12-23T05:55:40Z |
| publishDate | 2020-01-01 |
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| spelling | doaj.art-dd9e51e947324b4f89f24621215050b12022-12-21T17:57:50ZengMDPI AGInorganics2304-67402020-01-0181410.3390/inorganics8010004inorganics8010004Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline LigandsIsaak Nohara0Aramis Keller1Nikolai Tarassenko2Alessandro Prescimone3Edwin C. Constable4Catherine E. Housecroft5Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, 4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, 4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, 4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, 4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, 4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, 4058 Basel, SwitzerlandA series of [Cu(P^P)(N^N)][PF<sub>6</sub>] compounds are reported in which N^N is 2,9-dibromo-1,10-phenanthroline (2,9-Br<sub>2</sub>phen), 3,8-dibromo-1,10-phenanthroline (3,8-Br<sub>2</sub>phen) or 4,7-dibromo-1,10-phenanthroline (4,7-Br<sub>2</sub>phen) and P^P is bis(2-(diphenylphosphano)phenyl)ether (POP) or 4,5-bis(diphenylphosphano)-9,9-dimethylxanthene (xantphos). The compounds were characterized by solution multinuclear NMR spectroscopy, mass spectrometry and a single-crystal X-ray analysis. Each compound underwent a partially reversible or irreversible copper-centred oxidation, the highest potential being for 2,9-Br<sub>2</sub>phen-containing compounds. In solution, the compounds are weak yellow or orange emitters, whereas powdered samples exhibit yellow emissions with photoluminescence quantum yields of up to 45% for [Cu(xantphos)(2,9-Br<sub>2</sub>phen)][PF<sub>6</sub>] with an excited state lifetime <i>τ</i><sub>1/2</sub> = 9.9 μs. Values of <i>λ</i><sub>em</sub><sup>max</sup> for [Cu(POP)(2,9-Br<sub>2</sub>phen)][PF<sub>6</sub>] and [Cu(xantphos)(2,9-Br<sub>2</sub>phen)][PF<sub>6</sub>] are blue-shifted with respect to compounds with the 3,8-and 4,7-isomers, both in solution and in the solid state.https://www.mdpi.com/2304-6740/8/1/4copper(i)1,10-phenanthrolinebromo-substitutionphotophysical properties |
| spellingShingle | Isaak Nohara Aramis Keller Nikolai Tarassenko Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands Inorganics copper(i) 1,10-phenanthroline bromo-substitution photophysical properties |
| title | Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands |
| title_full | Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands |
| title_fullStr | Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands |
| title_full_unstemmed | Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands |
| title_short | Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands |
| title_sort | heteroleptic cu p p n n pf sub 6 sub compounds with isomeric dibromo 1 10 phenanthroline ligands |
| topic | copper(i) 1,10-phenanthroline bromo-substitution photophysical properties |
| url | https://www.mdpi.com/2304-6740/8/1/4 |
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