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dc.contributor.author | Hulushe, Siya T.![]() |
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dc.contributor.author | Malan, F.P. (Frederick)![]() |
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dc.contributor.author | Hosten, Eric C.![]() |
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dc.contributor.author | Akerman, Matthew P.![]() |
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dc.contributor.author | Lemmerer, Andreas![]() |
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dc.contributor.author | Khanye, Setshaba D.![]() |
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dc.contributor.author | Watkins, Gareth M.![]() |
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dc.date.accessioned | 2024-05-16T12:31:14Z | |
dc.date.available | 2024-05-16T12:31:14Z | |
dc.date.issued | 2023-06 | |
dc.description.abstract | A new family of single-pocket metal complexes bearing O,N,O-tridentate and O,N-bidentate chelating members {Cu, 1b (P21/n); Ni, 1c (C2/c); Mn, 1d (I2/a); Cu, 2b; and Ni, 2c (both P21/c)}, starting from synthesized and fully characterized Zn(II) (1a; I2/a) and Cu(II) (2a; C2) precursors, were conveniently prepared via cation-induced solvent-assisted and ligand-induced solvent-assisted transformations. Herein, we show multistep solvent-assisted transformations from cis-1a → trans-1b → cis-1c → cis-1d, as well as all-trans 2a → 2b → 2c. All processes are one-way irreversible, as substantiated by thermodynamic aspects (enthalpies based on Gibbs free energies) derived from density functional theory calculations. On the other hand, complex 2a′ (C2/c; a polymorphic form of 2a) was obtained through a routine synthetic procedure. The compounds have been established by various spectroscopic techniques (infrared, UV−vis, ESI-MS, 1H, and 13C NMR), elemental analysis, and X-ray crystallography. Single-crystal X-ray studies reveal that complexes 1a−d exhibit a pseudo-octahedral geometry around each metal center, with 2a displaying a four-coordinate seesaw geometry Cu(II) sphere (Addison parameter; τ = 0.42), while 2a′ (τ = 0.00), 2b (τ = 0.00), and 2c (τ = 0.00) possess a perfect square-planar configuration around each metal center. Furthermore, distortion is stabilized by the presence of peripheral Odonor atoms from the bulky −OMe group, and by virtue of its size, increased bond lengths and angles are accommodated. Ligand substitution induced coordination geometry transformation from quasi-square-planar 2a to perfect square-planar 2b. Assessment of the metric parameter shows that the distances between the two Cu−Omethoxy are all largely positive due to Jahn−Teller distortion, indicating an unprecedented tetragonal bipyramidal geometry in 1b. | en_US |
dc.description.department | Chemistry | en_US |
dc.description.sdg | None | en_US |
dc.description.sponsorship | The National Research Foundation (NRF, South Africa), Atlantic Philanthropies Scholarship and Rhodes University Research Council. | en_US |
dc.description.uri | http://pubs.acs.org/journal/cgdefu | en_US |
dc.identifier.citation | Hulushe, S.T., Malan, F.P., Hosten, E.C., et al., 2023, 'Cation-/ligand-induced solvent-assisted transformations of Zn(II) and Cu(II) complexes featuring single-pocket multidentate chelating members', Crystal Growth & Design, vol. 23, no. 7, pp. 4836-4854, DOI: 10.1021/acs.cgd.3c00055. | en_US |
dc.identifier.issn | 1528-7483 (print) | |
dc.identifier.issn | 1528-7505 (online) | |
dc.identifier.other | 10.1021/acs.cgd.3c00055 | |
dc.identifier.uri | http://hdl.handle.net/2263/96019 | |
dc.language.iso | en | en_US |
dc.publisher | American Chemical Society | en_US |
dc.rights | © 2023 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0. | en_US |
dc.subject | Spectroscopic techniques | en_US |
dc.subject | Geometry | en_US |
dc.subject | Thermodynamic | en_US |
dc.subject | Cation-induced | en_US |
dc.subject | Ligand-induced | en_US |
dc.subject | Density functional theory | en_US |
dc.subject | Solvent-assisted | en_US |
dc.title | Cation-/ligand-induced solvent-assisted transformations of Zn(II) and Cu(II) complexes featuring single-pocket multidentate chelating members | en_US |
dc.type | Article | en_US |