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Nat Commun. 2017 May 19;8:15476. doi: 10.1038/ncomms15476.

Self-assembly of a supramolecular hexagram and a supramolecular pentagram.

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Department of Organic and Polymer Chemistry, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China.
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin 130012, China.
Department of Chemistry and Biochemistry, Materials Science, Engineering, and Commercialization Program, Texas State University, San Marcos, Texas 78666, USA.
Department of Chemistry, University of South Florida, Tampa, Florida 33620, USA.
Single Molecule Study Laboratory, College of Engineering and Nanoscale Science and Engineering Center, University of Georgia, Athens, Georgia 30602, USA.
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Departments of Polymer Science and Chemistry, University of Akron, Akron, Ohio 44325, USA.


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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