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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.

Author information

1
Department of Organic and Polymer Chemistry, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China.
2
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin 130012, China.
3
Department of Chemistry and Biochemistry, Materials Science, Engineering, and Commercialization Program, Texas State University, San Marcos, Texas 78666, USA.
4
Department of Chemistry, University of South Florida, Tampa, Florida 33620, USA.
5
Single Molecule Study Laboratory, College of Engineering and Nanoscale Science and Engineering Center, University of Georgia, Athens, Georgia 30602, USA.
6
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
7
Departments of Polymer Science and Chemistry, University of Akron, Akron, Ohio 44325, USA.

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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