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Classical vs. Non-classical cyclometalated pt(ii) complexes

Maidich, Luca, Pilo, Maria I., Rourke, Jonathan P. ORCID:, Clarkson, Guy J., Canu, Patrizia, Stoccoro, Sergio and Zucca, Antonio 2022. Classical vs. Non-classical cyclometalated pt(ii) complexes. Molecules 27 (21) , 7249. 10.3390/molecules27217249

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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: Article
Date Type: Published Online
Status: Published
Schools: Chemistry
Additional Information: License information from Publisher: LICENSE 1: URL:, Type: open-access
Publisher: MDPI
Date of First Compliant Deposit: 17 November 2022
Date of Acceptance: 19 October 2022
Last Modified: 23 Dec 2022 02:10

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