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Inorganic Superspheres

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Book cover Clusters – Contemporary Insight in Structure and Bonding

Part of the book series: Structure and Bonding ((STRUCTURE,volume 174))

Abstract

An intriguing inorganic analog of ferrocene, pentaphosphaferrocene [CpRFe(η5-P5)] (R=Me, Et, CH2Ph, PhC4H9), has the ability to coordinate Cu(I) moieties resulting in giant superspheres of 2.1–4.6 nm in diameter. Smaller hollow supramolecules follow icosahedral C80 or C140 fullerene topology being constructed of adjacent pentagonal cyclo-P5 moieties and hexagonal Cu2P4 or P2Cu3Br rings. The same building units can also assemble to spherical and ellipsoid inorganic cores with different fullerene-related topologies. Larger supramolecules based on extended copper halide frameworks possess multilayered structures and form non-fullerene topologies. The size and solubility of the superspheres can be controlled through the variation of the steric demand of the cyclopentadienyl ligands at the pentaphosphaferrocene. The interconversion of supramolecules can be enabled in solution by changing the solvent mixtures. The quasi-spherical voids inside the supramolecules encapsulate various organic, inorganic, and organometallic guest molecules. Furthermore, the metallocene guests are involved in π-stacking with aromatic cyclo-P5 systems of the supramolecular host. The crystals of the obtained supramolecules consist of similar co-crystallized forms, in which different isomerism and porosity can occur. The mutual arrangement of the supramolecules in the crystals is essentially controlled by halogen–Cp* σ–π and Cp*–Cp* π–π stacking interactions. This allows to regard these interactions as the supramolecular synthons. Besides the expected structural motifs typical for close sphere packings, such superspheres form also unusual and low-dense packing motifs.

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Notes

  1. 1.

    The inner diameters of the cavities were calculated as geometrically opposing atomic distances, minus the van der Waals radii of the respective atoms (e.g., P, 1.80 Å; Cu, 1.40 Å). The term “diameter” is defined here as the diameter of the largest spherical form that is geometrically allowed inside the cavity by the given atoms. The outer diameter is taken as twice the largest distance from the theoretical center of the molecule to the farthest atom, plus twice the van der Waals radius for the respective atom (e.g., H, 1.2 Å).

  2. 2.

    Hereinafter bold-typed symbols correspond to the notation used in RCSR database, http://rcsr.net [144, 145]

  3. 3.

    In these notations, common packings as face-centered cubic (f.c.c.) are also known as fcu net, hexagonal close packing (h.c.p.) as hcp, and body-centered cubic as bcu-x type.

  4. 4.

    With additional four edges taken into account, the cco net transforms to bcu-x (b.c.c.).

  5. 5.

    Calculated from the crystallographic data for an idealized net stored in RCSR database, http://rcsr.net/nets/ild

  6. 6.

    Arrangement of oxygen atoms in the ReO3 or cubic perovskite structures

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Acknowledgments

The European Research Council (ERC) is acknowledged for the support in the SELFPHOS AdG339072 project. C.H. is grateful for a Ph.D. fellowship of the Fonds der Chemischen Industrie.

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Authors and Affiliations

  1. Institut für Anorganische Chemie, Universität Regensburg, Universitätsstr. 31, 93053, Regensburg, Germany

    Eugenia Peresypkina, Claudia Heindl, Alexander Virovets & Manfred Scheer

  2. Nikolaev Institute of Inorganic Chemistry SB RAS, Ak. Lavrentiev prosp. 3, Novosibirsk, 630090, Russia

    Eugenia Peresypkina & Alexander Virovets

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  4. Manfred Scheer
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Correspondence to Manfred Scheer .

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  1. Fachbereich Chemie, Philipps-Universität Marburg and Wissenschaftliches Zentrum für Materialwissenschaften, Marburg, Germany

    Stefanie Dehnen

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Dedicated to Prof. Dr. Hansgeorg Schnöckel on the occasion of his 75th birthday

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Peresypkina, E., Heindl, C., Virovets, A., Scheer, M. (2016). Inorganic Superspheres. In: Dehnen, S. (eds) Clusters – Contemporary Insight in Structure and Bonding. Structure and Bonding, vol 174. Springer, Cham. https://doi.org/10.1007/430_2016_2

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