Articles producció científica> Química Física i Inorgànica

Size and charge effect of guest cations in the formation of polyoxopalladates: a theoretical and experimental study

  • Dades identificatives

    Identificador: imarina:3672570
    Autors:
    Lang, ZhonglingYang, PengLin, ZhengguoYan, LikaiLi, Ming-XingCarbo, Jorge J.Kortz, UlrichPoblet, Josep M.
    Resum:
    The development of rational synthetic procedures with desired nuclearity and high selectivity is a critical issue in inorganic chemistry. Here we demonstrate a comprehensive understanding of the template effect induced by metal cations in the formation mechanism of the class of polyoxopalladates ({MPd12L8} nanocube and {MPd15L10} nanostar) by combining computational and experimental techniques. The capture of a Mn+ guest ion by a peripheral palladium(II)-oxo shell leads to a competition between the parent Pd2+ addenda ion and the respective guest metal ion. The present study reveals that (i) the selection of the incorporated guest ion has a thermodynamic control, (ii) the main factors governing the formation of a particular polyanion are the charge and size of the guest cation, (iii) the electrostatic interaction between the cation and the surrounding oxo ligands and (iv) the dehydration ability of the cation. As expected from the number of observed {Mn+Pd12L8} species, trivalent cations M3+ were found to be good templates resulting in several examples of {M3+Pd12L8}, whereas monovalent cations M+ are much less prone to form {M+Pd12L8}. For tetravalent cations the dehydration energies are very large, however, the formation of {M4+Pd12L8} nanocubes is found to be still energetic favourable. Fully consistent with computational predictions, four novel polyoxo-12-palladates were synthesized: the La3+- centered nanocube [LaPd12O8(PhAsO3)8]5 (LaPd12-closed), the La3+-centered 'open' nanocube [LaPd12O6(OH)3(PhAsO3)6(OAc)3]3 (LaPd12-open), the Ga3+-centered [GaPd12O8(PhAsO3)8]5 (GaPd12), and the In3+-analogue [InPd12O8(PhAsO3)8]5 (InPd12). All four compounds were fully characterized in the solid state and in solution by a multitude of physicochemical techniques, including 71Ga
  • Altres:

    Autor segons l'article: Lang, Zhongling; Yang, Peng; Lin, Zhengguo; Yan, Likai; Li, Ming-Xing; Carbo, Jorge J.; Kortz, Ulrich; Poblet, Josep M.;
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria
    Resum: The development of rational synthetic procedures with desired nuclearity and high selectivity is a critical issue in inorganic chemistry. Here we demonstrate a comprehensive understanding of the template effect induced by metal cations in the formation mechanism of the class of polyoxopalladates ({MPd12L8} nanocube and {MPd15L10} nanostar) by combining computational and experimental techniques. The capture of a Mn+ guest ion by a peripheral palladium(II)-oxo shell leads to a competition between the parent Pd2+ addenda ion and the respective guest metal ion. The present study reveals that (i) the selection of the incorporated guest ion has a thermodynamic control, (ii) the main factors governing the formation of a particular polyanion are the charge and size of the guest cation, (iii) the electrostatic interaction between the cation and the surrounding oxo ligands and (iv) the dehydration ability of the cation. As expected from the number of observed {Mn+Pd12L8} species, trivalent cations M3+ were found to be good templates resulting in several examples of {M3+Pd12L8}, whereas monovalent cations M+ are much less prone to form {M+Pd12L8}. For tetravalent cations the dehydration energies are very large, however, the formation of {M4+Pd12L8} nanocubes is found to be still energetic favourable. Fully consistent with computational predictions, four novel polyoxo-12-palladates were synthesized: the La3+- centered nanocube [LaPd12O8(PhAsO3)8]5 (LaPd12-closed), the La3+-centered 'open' nanocube [LaPd12O6(OH)3(PhAsO3)6(OAc)3]3 (LaPd12-open), the Ga3+-centered [GaPd12O8(PhAsO3)8]5 (GaPd12), and the In3+-analogue [InPd12O8(PhAsO3)8]5 (InPd12). All four compounds were fully characterized in the solid state and in solution by a multitude of physicochemical techniques, including 71Ga and 115In NMR as well as mass spectrometry. The experimentally observed selective incorporation of only In3+ ions in the presence of Ga3+ and In3+ confirmed the thermodynamic control of the formation mechanism, which we had predicted by theory.
    Àrees temàtiques: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: josepmaria.poblet@urv.cat j.carbo@urv.cat
    Identificador de l'autor: 0000-0002-4533-0623 0000-0002-3945-6721
    Data d'alta del registre: 2024-09-07
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2017/sc/c7sc03441e
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Chemical Science. 8 (11): 7862-7872
    Referència de l'ítem segons les normes APA: Lang, Zhongling; Yang, Peng; Lin, Zhengguo; Yan, Likai; Li, Ming-Xing; Carbo, Jorge J.; Kortz, Ulrich; Poblet, Josep M.; (2017). Size and charge effect of guest cations in the formation of polyoxopalladates: a theoretical and experimental study. Chemical Science, 8(11), 7862-7872. DOI: 10.1039/c7sc03441e
    DOI de l'article: 10.1039/c7sc03441e
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2017
    Tipus de publicació: Journal Publications
  • Paraules clau:

    Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Farmacia
    Ciências biológicas iii
    Ciências biológicas i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Astronomia / física
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