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Open AccessArticle

Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties, and Solution Dynamic Behavior

Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland
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Academic Editors: Burgert Blom, Erika Ferrari, Vassilis Tangoulis, Cédric R. Mayer, Axel Klein and Constantinos C. Stoumpos
Molecules 2021, 26(1), 125; https://doi.org/10.3390/molecules26010125
Received: 14 December 2020 / Revised: 24 December 2020 / Accepted: 24 December 2020 / Published: 29 December 2020
The preparation, characterization and electrochemical and photophysical properties of a series of desymmetrized heteroleptic [Cu(P^P)(N^N)][PF6] compounds are reported. The complexes incorporate the chelating P^P ligands bis(2-(diphenylphosphanyl)phenyl)ether (POP) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos), and 6-substituted 2,2′-bipyridine (bpy) derivatives with functional groups attached by –(CH2)n– spacers: 6-(2,2′-bipyridin-6-yl)hexanoic acid (1), 6-(5-phenylpentyl)-2,2′-bipyridine (2) and 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-2,2′-bipyridine (3). [Cu(POP)(1)][PF6], [Cu(xantphos)(1)][PF6], [Cu(POP)(2)][PF6], [Cu(xantphos)(2)][PF6], and [Cu(xantphos)(3)][PF6] have been characterized in solution using multinuclear NMR spectroscopy, and the single crystal structure of [Cu(xantphos)(3)][PF6].0.5Et2O was determined. The conformation of the 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-substituent in the [Cu(xantphos)(3)]+ cation is such that the α- and β-CH2 units reside in the xanthene ‘bowl’ of the xantphos ligand. The 6-substituent desymmetrizes the structure of the [Cu(P^P)(N^N)]+ cation and this has consequences for the interpretation of the solution NMR spectra of the five complexes. The NOESY spectra and EXSY cross-peaks provide insight into the dynamic processes operating in the different compounds. For powdered samples, emission maxima are in the range 542–555 nm and photoluminescence quantum yields (PLQYs) lie in the range 13–28%, and a comparison of PLQYs and decay lifetimes with those of [Cu(xantphos)(6-Mebpy)][PF6] indicate that the introduction of the 6-substituent is not detrimental in terms of the photophysical properties. View Full-Text
Keywords: copper(I); bisphosphane; 2,2′-bipyridine; photophysics; X-ray diffraction copper(I); bisphosphane; 2,2′-bipyridine; photophysics; X-ray diffraction
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MDPI and ACS Style

Meyer, M.; Brunner, F.; Prescimone, A.; Constable, E.C.; Housecroft, C.E. Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties, and Solution Dynamic Behavior. Molecules 2021, 26, 125. https://doi.org/10.3390/molecules26010125

AMA Style

Meyer M, Brunner F, Prescimone A, Constable EC, Housecroft CE. Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties, and Solution Dynamic Behavior. Molecules. 2021; 26(1):125. https://doi.org/10.3390/molecules26010125

Chicago/Turabian Style

Meyer, Marco; Brunner, Fabian; Prescimone, Alessandro; Constable, Edwin C.; Housecroft, Catherine E. 2021. "Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties, and Solution Dynamic Behavior" Molecules 26, no. 1: 125. https://doi.org/10.3390/molecules26010125

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