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The effects of introducing sterically demanding aryl substituents in [Cu(N^N)(P^P)]+ complexes

Brunner, Fabian and Graber, Stefan and Baumgartner, Yann and Häussinger, Daniel and Prescimone, Alessandro and Constable, Edwin C. and Housecroft, Catherine E.. (2017) The effects of introducing sterically demanding aryl substituents in [Cu(N^N)(P^P)]+ complexes. Dalton Transactions, 46. pp. 6379-6391.

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Abstract

The syntheses and characterizations of six [Cu(N^N)(POP)][PF 6 ] and [Cu(N^N)(xantphos)][PF 6 ] compounds (POP = bis(2-(diphenylphosphino)phenyl)ether, xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), in which N^N is a bpy ligand (1-Naphbpy, 2-Naphbpy, 1-Pyrbpy) bearing a sterically hindered 1-naphthyl, 2-naphthyl or 1-pyrenyl substituent in the 6-position, are reported. Single-crystal structure determinations of five complexes confirm a distorted tetrahedral environment for copper( I ) and a preference for the N^N ligand to be oriented with the sterically-demanding aryl group being remote from the (C 6 H 4 ) 2 O unit of POP or the xanthene ‘bowl’ of xantphos. The angle between the ring planes of the bpy range from 5.8 to 26.0° and this is associated with interactions between the aryl unit and the phenyl substituents of the P^P ligand. In solution at room temperature, the complexes undergo dynamic behaviour which has been investigated using variable temperature 2D NMR spectroscopy. The [Cu(N^N)(xantphos)] + complexes exist as a mixture of conformers which interconvert through inversion of the xanthene bowl-shaped unit; the preference for one conformer over the other is significantly changed on going from N^N = Phbpy to 1-Pyrbpy (Phbpy = 6-phenyl-2,2’-bipyridine). The electrochemical and photophysical properties of the [Cu(N^N)(POP)][PF 6 ] and [Cu(N^N)(xantphos)][PF 6 ] compounds are presented; the compounds are orange emitters but the introduction of the 1-naphthyl, 2-naphthyl or 1-pyrenyl substituents result in poor photoluminescence quantum yields.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Graber, Stefan and Baumgartner, Yann and Prescimone, Alessandro and Häussinger, Daniel
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
ISSN:1477-9226
e-ISSN:1477-9234
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:09 Feb 2018 13:37
Deposited On:17 May 2017 12:29

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