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Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]+ Complexes?

Brunner, Fabian and Prescimone, Alessandro and Constable, Edwin C. and Housecroft, Catherine E.. (2020) Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]+ Complexes? Molecules, 25 (12). p. 2760.

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Abstract

The synthesis and structural characterization of 5,60-dimethyl-2,20-bipyridine (5,60-Me2bpy) are reported, along with the preparations and characterizations of [Cu(POP)(5,60-Me2bpy)][PF6] and [Cu(xantphos)(5,60-Me2bpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether, xantphos = 4,5- bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene). Single-crystal X-ray structure determinations of [Cu(POP)(5,60-Me2bpy)][PF6] and [Cu(xantphos)(5,60-Me2bpy)][PF6] confirmed distorted tetrahedral copper(I) coordination environments with the 5-methylpyridine ring of 5,60-Me2bpy directed towards the (C6H4)2O unit of POP or the xanthene unit of xantphos. In the xantphos case, this preference may be attributed to C-H : : : interactions involving both the 6-CH unit and the 5-methyl substituent in the 5-methylpyridine ring and the arene rings of the xanthene unit. 1H NMR spectroscopic data indicate that this ligand orientation is also preferred in solution. In solution and the solid state, [Cu(POP)(5,60-Me2bpy)][PF6] and [Cu(xantphos)(5,60-Me2bpy)][PF6] are yellow emitters, and, for powdered samples, photoluminescence quantum yields (PLQYs) are 12 and 11%, respectively, and excited-state lifetimes are 5 and 6 s, respectively. These values are lower than PLQY and values for [Cu(POP)(6,60-Me2bpy)][PF6] and [Cu(xantphos)(6,60-Me2bpy)][PF6], and the investigation points to the 6,60-dimethyl substitution pattern in the bpy ligand being critical for enhancement of the PLQY.
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 Brunner, Fabian and Prescimone, Alessandro
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:MDPI
ISSN:1420-3049
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
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Last Modified:30 Jun 2020 08:54
Deposited On:30 Jun 2020 08:54

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