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Solid-State 63Cu, 65Cu, and 31P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

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    Solid-State 63Cu, 65Cu, and 31P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes
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    † Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
    ‡ School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, P. R. China
    ∥ Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
    § College of Physics Science and Technology, Yangzhou University, Yangzhou 225002, P. R. China
    *Phone: +1-780-492-4336. Fax: +1-780-492-8231. E-mail: [email protected]. (R.E.W.)
    *Phone: +86-797-8312204. Fax: +86-797-8312204. E-mail: [email protected]. (J.C.)
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2015, 119, 30, 8279–8293
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    https://doi.org/10.1021/acs.jpca.5b04270
    Published June 23, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    The results of a solid-state 63/65Cu and 31P NMR investigation of several copper(I) complexes with functionalized 3-(2′-pyridyl)-1,2,4-triazole and phosphine ligands that have shown potential in the preparation of photoluminescent devices are reported. For each complex studied, distinct NMR parameters, with moderate 63Cu nuclear quadrupolar coupling constant (CQ) values ranging from −17.2 to −23.7 MHz, are attributed to subtle variations in the distorted four-coordinate environments about the copper nuclei. The spans of the copper chemical shift (CS) tensors, δ11–δ33, for the mono- and bisphosphine complexes are also similar, ranging from 1000 to 1150 ppm, but that for a complex with a strained bidentate phosphine ligand is only 650 ppm. The effects of residual dipolar and indirect spin–spin coupling arising from the 63/65Cu– 31P spin pairs, observed in the solid-state 31P NMR spectra of these complexes, yield information about the orientations of the copper electric field gradient (EFG) tensors relative to the Cu–P bond. Variable-temperature 31P NMR measurements for [Cu(bptzH)(dppe)]ClO4 (bptzH = 5-tert-butyl-3-(2′-pyridyl)-1,2,4-triazole; dppe = 1,2-bis(diphenylphosphino)ethane), undertaken to investigate the cause of the broad unresolved spectra observed at room temperature, demonstrate that the broadening arises from partial self-decoupling of the 63/65Cu nuclei, a consequence of rapid quadrupolar relaxation. Ab initio calculations of copper EFG and CS tensors were performed to probe relationships between NMR parameters and molecular structure. The analysis demonstrated that CQ(63/65Cu) is negative for all complexes studied here and that the largest components of the EFG tensors are generally coincident with δ11.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    Theory and background; NMR acquisition details; calculations on some linear molecules; structural parameters for 1–7; DFT NMR calculations on 1–7; computational investigation of the effect of the trifluoromethyl and tert-butyl groups on the NMR parameters of 4–6; 63/65Cu NMR spectra acquired at B0 = 11.75 T; additional 31P and 13C CP/MAS NMR spectra. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.5b04270.

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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2015, 119, 30, 8279–8293
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.5b04270
    Published June 23, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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