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Issue 48, 2019
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Triplet state structure–property relationships in a series of platinum acetylides: effect of chromophore length and end cap electronic properties

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Abstract

To develop quantitative structure–spectroscopic property relationships in platinum acetylides, we investigated the triplet state behavior of nominally centrosymmetric chromophores trans-Pt(PBu3)2(C[triple bond, length as m-dash]C-Phenyl-X)2, where X = diphenylamino, NH2, OCH3, t-Bu, CH3, H, F, benzothiazole, CF3, CN, and NO2. We measured ground state absorption, phosphorescence, excitation and triplet state absorption spectra and triplet lifetimes. By DFT we calculated the phosphorescence emission energy (ET), the spin density on the end cap (SD(X)), triplet state geometry and the distance between the triplet centroid and the central platinum atom (〈RS–Pt(X)〉). Compounds with electron-donating X have smaller triplet state lifetime, blue-shifted phosphorescence and larger triplet potential energy surface displacement associated with the C[triple bond, length as m-dash]C bond. Compounds with electron-withdrawing X have larger triplet lifetime, red-shifted phosphorescence and smaller triplet potential energy surface displacement associated with the C[triple bond, length as m-dash]C bond. The range of spin–orbit-coupling between the platinum atom and the triplet centroid was determined to be 6 Å. The quantity 〈RS–Pt〉 is shown to be a linear function of one-dimensional well length calculated from experimental ET. The multiple examples demonstrate 〈RS–Pt〉 is a useful descriptor for analyzing triplet state behavior.

Graphical abstract: Triplet state structure–property relationships in a series of platinum acetylides: effect of chromophore length and end cap electronic properties

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Publication details

The article was received on 21 May 2019, accepted on 21 Nov 2019 and first published on 22 Nov 2019


Article type: Paper
DOI: 10.1039/C9CP02892G
Phys. Chem. Chem. Phys., 2019,21, 26420-26429

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    Triplet state structure–property relationships in a series of platinum acetylides: effect of chromophore length and end cap electronic properties

    T. M. Cooper, J. E. Haley, D. M. Krein, A. R. Burke, D. J. Stewart, J. L. Fore and J. E. Slagle, Phys. Chem. Chem. Phys., 2019, 21, 26420
    DOI: 10.1039/C9CP02892G

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