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. 2017 May 19:8:15476.
doi: 10.1038/ncomms15476.

Self-assembly of a supramolecular hexagram and a supramolecular pentagram

Zhilong Jiang  1 , Yiming Li  1 , Ming Wang  2   3 , Bo Song  3   4 , Kun Wang  5 , Mingyu Sun  5 , Die Liu  1 , Xiaohong Li  6 , Jie Yuan  1 , Mingzhao Chen  1 , Yuan Guo  1 , Xiaoyu Yang  1 , Tong Zhang  5 , Charles N Moorefield  7 , George R Newkome  7 , Bingqian Xu  5 , Xiaopeng Li  3   4 , Pingshan Wang  1
Affiliations

Self-assembly of a supramolecular hexagram and a supramolecular pentagram

Zhilong Jiang et al. Nat Commun. .

Abstract

Five- and six-pointed star structures occur frequently in nature as flowers, snow-flakes, leaves and so on. These star-shaped patterns are also frequently used in both functional and artistic man-made architectures. Here following a stepwise synthesis and self-assembly approach, pentagonal and hexagonal metallosupramolecules possessing star-shaped motifs were prepared based on the careful design of metallo-organic ligands (MOLs). In the MOL design and preparation, robust ruthenium-terpyridyl complexes were employed to construct brominated metallo-organic intermediates, followed by a Suzuki coupling reaction to achieve the required ensemble. Ligand LA (VRu2+X, V=bisterpyridine, X=tetraterpyridine, Ru=Ruthenium) was initially used for the self-assembly of an anticipated hexagram upon reaction with Cd2+ or Fe2+; however, unexpected pentagonal structures were formed, that is, [Cd5LA5]30+ and [Fe5LA5]30+. In our redesign, LB [V(Ru2+X)2] was synthesized and treated with 60° V-shaped bisterpyridine (V) and Cd2+ to create hexagonal hexagram [Cd12V3LB3]36+ along with traces of the triangle [Cd3V3]6+. Finally, a pure supramolecular hexagram [Fe12V3LB3]36+ was successfully isolated in a high yield using Fe2+ with a higher assembly temperature.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Figure 1
Figure 1. Chemical structures of supramolecular pentagram and hexagram.
Star-shaped pentagram and hexagram contained five or six 1,2-bisterpyridines, five or six 1,2,4,5-tetraterpyridines and fifteen or eighteen metals, respectively.
Figure 2
Figure 2. Illustration of an initial molecular hexagram designation.
Self-assembly of unexpected pentagram and multiple triangular assemblies in the initial design of hexagram.
Figure 3
Figure 3. ESI/TWIM-MS spectrum.
(a) ESI-MS and (b) TWIM-MS of pentagonal [Cd10LA5)]30+; (c) ESI-MS and (d) TWIM-MS of pentagonal [Fe10LA5]30+.
Figure 4
Figure 4. 1H NMR spectrum.
(a) LA and (b) molecular pentagram [Fe10LA5)]; (c) DOSY of [Fe10LA5)] (500 MHz, 25 °C, CDCl3 for ligands and CD3CN for supramolecule).
Figure 5
Figure 5. Self-assembly of supramolecular hexagram [Fe12V3LB3]36+.
(a) Schematic illustration of synthesizing molecular Star of David by using metallo-ligand LB, V and metals. (b) ESI-MS and (c) TWIM-MS of metallo-hexagram.
Figure 6
Figure 6. Comparison of 1H NMR spectrum.
(a) bisterpyridine ligand (500 MHz, 25 °C, CDCl3), (b) molecular Star of David [Fe12V3LB3] (500 MHz, 25 °C, CD3CN), (c) metallo-ligand LB (500 MHz, 25 °C, CD3CN) and (d) DOSY of [Fe12V3LB3] (500 MHz, 25 °C, CD3CN).
Figure 7
Figure 7. AFM and STM images of metallo-hexagram.
(a,b) AFM images on mica (scale bar, 40 and 9.3 nm, respectively). (c,d) STM images on HOPG at ambient condition (scale bar, 5 and 25 nm, respectively).
See this image and copyright information in PMC

References

    1. Lehn J.-M. Toward self-organization and complex matter. Science 295, 2400–2403 (2002). - PubMed
    1. Hasenknopf B., Lehn J.-M., Kneisel B. O., Baum G. & Fenske D. Self-assembly of a circular double helicate. Angew. Chem. Int. Ed. 35, 1838–1840 (1996).
    1. Hasenknopf B. et al.. Self-assembly of tetra- and hexanuclear circular helicates. J. Am. Chem. Soc. 119, 10956–10962 (1997).
    1. Olenyuk B., Whiteford J. A., Fechtenkotter A. & Stang P. J. Self-assembly of nanoscale cuboctahedra by coordination chemistry. Nature 398, 796–799 (1999). - PubMed
    1. Yan X., Cook T. R., Wang P., Huang F. & Stang P. J. Highly emissive platinum(II) metallacages. Nat. Chem. 7, 342–348 (2015). - PubMed

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