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Issue 3, 2015
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Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations, unique structures and record 7Li NMR shifts

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Abstract

Self-assembly processes of the highly reduced bowl-shaped corannulene generated by the chemical reduction with a binary combination of alkali metals, namely Li–Rb, have been investigated by variable-temperature 1H and 7Li NMR spectroscopy. The formation of several unique mixed metal sandwich products based on tetrareduced corannulene, C20H104− (14−), has been revealed followed by investigation of their dynamic transformations in solutions. Analysis of NMR data allowed to propose the mechanism of stepwise alkali metal substitution as well as to identify experimental conditions for the isolation of intermediate and final supramolecular products. As a result, two new triple-decker aggregates with a mixed Li–Rb core, [{Rb(THF)2}2]//[Li3Rb2(C20H10)2{Li+(THF)}] (2) and [{Rb(diglyme)}2]//[Li3Rb3(C20H10)2(diglyme)2]·0.5THF (3·0.5THF), have been crystallized and structurally characterized. The Li3Rb2-product has an open coordination site at the sandwich periphery and thus is considered transient on the way to the Li3Rb3-sandwich having the maximized intercalated alkali metal content. Next, the formation of the LiRb5 self-assembly with 14− has been identified by 7Li NMR as the final step in a series of dynamic transformations in this system. This product was also isolated and crystallographically characterized to confirm the LiRb5 core. Notably, all sandwiches have their central cavities, located in between the hub-sites of two C20H104− decks, occupied by an internal Li+ ion which exhibits the record high negative shift (ranging from −21 to −25 ppm) in 7Li NMR spectra. The isolation of three novel aggregates having different Li–Rb core compositions allowed us to look into the origin of the unusual 7Li NMR shifts at the molecular level. The discussion of formation mechanisms, dynamic transformations as well as unique electronic structures of these remarkable mixed alkali metal organometallic self-assemblies is provided and supported by DFT calculations.

Graphical abstract: Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations, unique structures and record 7Li NMR shifts

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Publication details

The article was received on 11 Nov 2014, accepted on 16 Dec 2014 and first published on 16 Dec 2014


Article type: Edge Article
DOI: 10.1039/C4SC03485F
Citation: Chem. Sci., 2015,6, 1959-1966
  • Open access: Creative Commons BY license
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    Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations, unique structures and record 7Li NMR shifts

    A. S. Filatov, S. N. Spisak, A. V. Zabula, J. McNeely, A. Yu. Rogachev and M. A. Petrukhina, Chem. Sci., 2015, 6, 1959
    DOI: 10.1039/C4SC03485F

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