Heteroleptic [Cu(P^P)(N^N)][PF<sub>6</sub>] Compounds with Isomeric Dibromo-1,10-Phenanthroline Ligands

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...

Full description

Bibliographic Details
Main Authors: Isaak Nohara, Aramis Keller, Nikolai Tarassenko, Alessandro Prescimone, Edwin C. Constable, Catherine E. Housecroft
Format: Article
Language:English
Published: MDPI AG 2020-01-01
Series:Inorganics
Subjects:
copper(i)
1,10-phenanthroline
bromo-substitution
photophysical properties
Online Access:https://www.mdpi.com/2304-6740/8/1/4
id doaj-dd9e51e947324b4f89f24621215050b1
record_format Article
spelling doaj-dd9e51e947324b4f89f24621215050b12020-11-25T01:27:50ZengMDPI 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>&#964;</i><sub>1/2</sub> = 9.9 &#956;s. Values of <i>&#955;</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
collection DOAJ
language English
format Article
sources DOAJ
author Isaak Nohara
Aramis Keller
Nikolai Tarassenko
Alessandro Prescimone
Edwin C. Constable
Catherine E. Housecroft
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
author_facet Isaak Nohara
Aramis Keller
Nikolai Tarassenko
Alessandro Prescimone
Edwin C. Constable
Catherine E. Housecroft
author_sort Isaak Nohara
title 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_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_sort heteroleptic [cu(p^p)(n^n)][pf<sub>6</sub>] compounds with isomeric dibromo-1,10-phenanthroline ligands
publisher MDPI AG
series Inorganics
issn 2304-6740
publishDate 2020-01-01
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>&#964;</i><sub>1/2</sub> = 9.9 &#956;s. Values of <i>&#955;</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.
topic copper(i)
1,10-phenanthroline
bromo-substitution
photophysical properties
url https://www.mdpi.com/2304-6740/8/1/4
work_keys_str_mv AT isaaknohara heterolepticcuppnnpfsub6subcompoundswithisomericdibromo110phenanthrolineligands
AT aramiskeller heterolepticcuppnnpfsub6subcompoundswithisomericdibromo110phenanthrolineligands
AT nikolaitarassenko heterolepticcuppnnpfsub6subcompoundswithisomericdibromo110phenanthrolineligands
AT alessandroprescimone heterolepticcuppnnpfsub6subcompoundswithisomericdibromo110phenanthrolineligands
AT edwincconstable heterolepticcuppnnpfsub6subcompoundswithisomericdibromo110phenanthrolineligands
AT catherineehousecroft heterolepticcuppnnpfsub6subcompoundswithisomericdibromo110phenanthrolineligands
_version_ 1725102978978807808

Similar Items