Encapsulation of Keggin-type anions in reduced molybdenum–iron-type Keplerates as a general phenomenon

• Published in: Inorganica Chimica Acta Vol. 389; pp. 107 - 111
• Main Authors: Todea, Ana Maria, Al-Karawi, Ahmed Jasim M., Glaser, Thorsten, Walleck, Stephan, Chamoreau, Lise-Marie, Thouvenot, René, Gouzerh, Pierre, Müller, Achim
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.07.2012
• Subjects: Core–shell clusters; Host–guest chemistry; Keggin ions; Keplerate; Keplerate; Core–shell clusters; Host–guest chemistry; Keggin ions
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2012.01.062

Reduced core–shell hybrids exhibiting non-reduced dodecatungstoborate ions encapsulated in reduced {Mo72Fe30} Keplerate-type capsules have been prepared and characterized by different physical methods. The related ‘cluster in a cluster’ encapsulation allows further interesting host–guest-type studies. [Display omitted] ► Cluster in a cluster. ► Encapsulation of a Keggin-type tungstoborate ion in a reduced Keplerate-type shell. ► Non-covalent host–guest interactions. ► “Blue” electrons are delocalized on the shell. Upon standing in air at room temperature, acidified aqueous solutions (pH 2) obtained by dissolving sodium molybdate, iron(II) chloride, acetic acid and potassium dodecatungstoborate led to the formation of greenish thin plate crystals (1) containing discrete clusters. Upon drying 1 at room temperature crosslinking of the clusters occurs in a solid-state reaction which leads to compound 2. Based on crystallographic studies of 1 and on extensive physical characterization (vibrational, NMR, Mössbauer spectra and magnetic susceptibility measurements) of 2, it was shown that compounds 1 and 2 contain reduced spherical {Mo72Fe30} Keplerate-type shells encapsulating non-reduced tungstoborate Keggin-type anions. The properties and structures of these compounds are compared to related hybrid structures containing in principle easier reducible molybdophosphate or molybdosilicate cores. According to the results the present type of encapsulation can be considered as a general phenomenon.