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Hinged and Wide: A New PˆP Ligand for Emissive [Cu(PˆP)(NˆN)][PF6] Complexes

Keller, Sarah and Bantle, Matthias and Prescimone, Alessandro and Constable, Edwin C. and Housecroft, Catherine E.. (2019) Hinged and Wide: A New PˆP Ligand for Emissive [Cu(PˆP)(NˆN)][PF6] Complexes. Molecules, 24 (21). p. 3934.

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Official URL: https://edoc.unibas.ch/72451/

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Abstract

Heteroleptic [Cu(BIPHEP)(NˆN)][PF6 ] complexes (BIPHEP = 1,10 -biphenyl-2,20 - diylbis(diphenylphosphane)), in which NˆN is 2,20 -bipyridine (bpy), 6-methyl-2,20 -bipyridine (6-Mebpy), 6-ethyl-2,20 -bipyridine (6-Etbpy), or 5,50 -dimethyl-2,20 -bipyridine (5,50 -Me2 bpy), have been synthesized and characterized using multinuclear NMR spectroscopies and electrospray ionization mass spectrometry. The single crystal structures of [Cu(BIPHEP)(bpy)][PF6 ] CH2 Cl2 , [Cu(BIPHEP)(5,50 -Me2 bpy)][PF6 ] CH2 Cl2 , [Cu(BIPHEP)(6-Mebpy)][PF6 ] Et2 O 0.5H2 O and [Cu(BIPHEP) (6-Etbpy)][PF6 ] confirm distorted tetrahedral {Cu(PˆP)(NˆN)} coordination environments. Each compound shows a quasi-reversible Cu+/ Cu2+ process. In deaerated solution, the compounds are weak emitters. Powdered samples are yellow emitters (em max in the range 558-583 nm) and [Cu(BIPHEP)(5,50 -Me2 bpy)][PF6 ] exhibits the highest photoluminescence quantum yield (PLQY = 14%). On cooling to 77 K (frozen 2-methyloxolane), the emission maxima are red-shifted and the excited state lifetimes increase from 1/2 < 8 s, to 1/2 values of up to 53 s, consistent with the compounds with NˆN = 6-Mebpy, 6-Etbpy and 5,50 -Me2 bpy exhibiting thermally activated delayed fluorescence (TADF).
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Keller, Sarah and Bantle, Matthias 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:03 Dec 2019 15:23
Deposited On:06 Nov 2019 10:39

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