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[Cu(N^N)(P^P)]+ complexes with 2,2':6',2''-terpyridine ligands as the N^N domain

Murray, N. S. and Keller, S. and Constable, E. C. and Housecroft, C. E. and Neuburger, M. and Prescimone, A.. (2015) [Cu(N^N)(P^P)]+ complexes with 2,2':6',2''-terpyridine ligands as the N^N domain. Dalton transactions, 44 (16). pp. 7626-7633.

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Abstract

The first examples of [Cu(N^N)(POP)]+ complexes (POP = bis(2-(diphenylphosphino)phenyl)ether) in which the N^N domain is a 2,2′:6′,2′′-terpyridine (tpy) ligand have been prepared and characterized; N^N = tpy, 5,5′′-dimethyl-2,2′:6′,2′′-terpyridine (1), 4′-(4-tolyl)-2,2′:6′,2′′-terpyridine (2), 4′-(4-npropoxyphenyl)-2,2′:6′,2′′-terpyridine (3) and 4′-(4-nbutoxyphenyl)-2,2′:6′,2′′-terpyridine (4). In solution, the tpy domain in each [Cu(N^N)(POP)][PF6] complex is C2-symmetric, consistent with either tridentate coordination or a low energy dynamic process involving bidentate ligands; for [Cu(2)(POP)][PF6] and [Cu(4)(POP)][PF6], the 1H NMR spectra showed negligible change between 295 and 210 K. The single crystal structures of [Cu(tpy)(POP)][PF6] and [Cu(4)(POP)][PF6] are presented. The asymmetric unit of [Cu(tpy)(POP)][PF6] contains two independent cations; in one the tpy ligand is tridentate and in the other, it is bidentate with the non-coordinated pyridine ring facing the Cu atom (Cu⋯N = 3.146(1) Å). In contrast, the solid-state structure of [Cu(4)(POP)][PF6] features a [Cu(4)(POP)]+ cation containing a bidentate tpy-domain with the non-coordinated pyridine ring oriented with the N-atom facing away from the Cu atom; this conformation may be associated with inter-cation N⋯HC non-classical hydrogen bonds. The photophysical properties of [Cu(N^N)(POP)][PF6] with N^N = tpy or 1–4 are described. In the solid state at room temperature, the compounds are poorly emissive. In solution, the emission behaviour is consistent with ligand dissociation. This is supported by 1H and 31P NMR spectroscopic data which show POP and [Cu(POP)2]+ in solutions of aged samples; mass spectrometric data are consistent with the formation of [Cu(N^N)2]2+ in these samples.
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 Keller, Sarah and Murray, Niamh Sarah and Prescimone, Alessandro and Neuburger, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Bibsysno:Link to catalogue
Publisher:Royal Society of Chemistry
ISSN:1477-9226
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:31 Dec 2015 10:57
Deposited On:05 Jun 2015 08:53

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