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Title: | Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid |
Author: | Sánchez-Férez, Francisco Rius-Barta, J. M. Ayllón, J. A. Calvet Pallàs, Maria Teresa Font Bardia, Ma. Mercedes Pons, Josefina |
Keywords: | Química organometàl·lica Cristal·lografia Organometallic chemistry Crystallography |
Issue Date: | 17-Feb-2022 |
Publisher: | MDPI |
Abstract: | Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the π electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO)-Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)2·2H2O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(μ-Pip)2(4-Acpy)]2 (1); a mixture of one dimer and two monomers [Zn(µ-Pip)(Pip)(Isn)2]2·2[Zn(Pip)2(HPip)(Isn)]·2MeOH (2); and two dimers [Cd(μ-Pip)(Pip)(4-Acpy)2]2 (3) and [Cd(μ-Pip)(Pip)(Isn)2]2·MeOH (4). They exhibit bridged (1, µ2-η1:η1), bridged, chelated and monodentated (2, µ2-η1:η1, µ1-η1:η1 and µ1-η1), or simultaneously bridged and chelated (3 and 4, µ2-η2:η1) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations. |
Note: | Reproducció del document publicat a: https://doi.org/10.3390/molecules27041365 |
It is part of: | Molecules, 2022, vol. 27, num. 4, p. 1365 |
URI: | http://hdl.handle.net/2445/183276 |
Related resource: | https://doi.org/10.3390/molecules27041365 |
ISSN: | 1420-3049 |
Appears in Collections: | Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) |
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