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J Am Chem Soc. 2016 Aug 10;138(31):10041-6. doi: 10.1021/jacs.6b06021. Epub 2016 Aug 1.

Giant, Hollow 2D Metalloarchitecture: Stepwise Self-Assembly of a Hexagonal Supramolecular Nut.

Author information

1
Department of Organic and Polymer Chemistry, College of Chemistry and Chemical Engineering, Central South University , Changsha, Hunan 410083, P. R. China.
2
Department of Chemistry and Biochemistry and Materials Science, Engineering, and Commercialization Program, Texas State University , San Marcos, Texas 78666, United States.

Abstract

A polyterpyridinyl building block-based nutlike hexagonal bismetallo architecture with a central hollow Star of David was assembled by a stepwise strategy. This nanoarchitecture can be viewed as a recursive mathematical form that possesses a supramolecular corner-connected cyclic structure, i.e., a triangle or rhombus at various levels of scale or detail. The key metallo-organic ligand (MOL) with four uncomplexed free terpyridines was obtained by a final Suzuki cross-coupling reaction with a tetrabromoterpyridine Ru dimer. The molecular metallorhombus was prepared by reacting the MOL with a 60° bis-terpyridine and Fe(2+). The giant hollow hexagonal nut with a diameter of more than 11 nm and a molecular weight of ca. 33 kDa was obtained in near-quantitative yield by mixing the two types of multi-terpyridine ligands with Fe(2+). The supramolecular architecture was characterized by NMR ((1)H and (13)C), 2D NMR (COSY and ROESY), and DOSY spectroscopies, high-resolution electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy.

PMID:
27447878
DOI:
10.1021/jacs.6b06021

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