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Classical vs. non-classical cyclometalated Pt(II) complexes
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Maidich, Luca, Pilo, Maria I., Rourke, Jonathan P., Clarkson, Guy J., Canu, Patrizia, Stoccoro, Sergio and Zucca, Antonio (2022) Classical vs. non-classical cyclometalated Pt(II) complexes. Molecules, 27 (21). 7249. doi:10.3390/molecules27217249 ISSN 1420-3049.
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Official URL: https://doi.org/10.3390/molecules27217249
Abstract
Rollover cyclometalated complexes constitute a family of derivatives which differ from classical cyclometalated species in certain aspects. Various potential application fields have been developed for both classes of compounds, which have both similarities and differences. In order to uncover the relationships and distinctions between these two families of compounds, four Pt(II) cyclometalated complexes derived from 2-phenylpyridine (ppy) and 2,2′-bipyridine (bpy), assumed as prototypical ligands, were compared. For this study, an electron rich isostructural and isoelectronic pair of compounds, [Pt(N^C)Me(PPh3)], and an electron-poorer compound, [Pt(N^C)Cl(PPh3)] were chosen (N^C = ppy or bpy). DFT calculations, cyclic voltammetry, and UV-Vis spectra also helped to shed light into these species. Due to the presence of the more electronegative nitrogen in place of a C-H group, the rollover bpy-H ligand becomes a slightly weaker donor than the classical ppy-H ligand, and hence, generates (slightly) more stable cyclometalated complexes, lower energy frontier molecular orbitals, and electron-poorer platinum centers. On the whole, it was revealed that classical and rollover complexes have overall structural similarity, which contrasts to their somewhat different chemical behavior.
Item Type: | Journal Article | ||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
SWORD Depositor: | Library Publications Router | ||||||
Journal or Publication Title: | Molecules | ||||||
Publisher: | MDPI | ||||||
ISSN: | 1420-3049 | ||||||
Official Date: | 25 October 2022 | ||||||
Dates: |
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Volume: | 27 | ||||||
Number: | 21 | ||||||
Article Number: | 7249 | ||||||
DOI: | 10.3390/molecules27217249 | ||||||
Status: | Peer Reviewed | ||||||
Publication Status: | Published | ||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||
Date of first compliant deposit: | 30 November 2022 | ||||||
Date of first compliant Open Access: | 30 November 2022 | ||||||
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