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Self-Assembly of Concentric Hexagons and Hierarchical Self-Assembly of Supramolecular Metal–Organic Nanoribbons at the Solid/Liquid Interface
journal contribution
posted on 2016-07-05, 00:00 authored by Ming Wang, Kun Wang, Chao Wang, Mingjun Huang, Xin-Qi Hao, Ming-Zhan Shen, Guo-Qing Shi, Zhe Zhang, Bo Song, Alejandro Cisneros, Mao-Ping Song, Bingqian Xu, Xiaopeng LiIn
an effort to exert more precise control over structural features
of supramolecules, a series of giant concentric hexagons were assembled
as discrete structures using tetratopic terpyridine (tpy) ligands.
In preparation of tetratopic ligand, pyrylium and pyridinium salts
chemistry significantly facilitated synthesis. The key compounds were
obtained by condensation reactions of pyrylium salts with corresponding
primary amine derivatives in good yields. These discrete metallo-supramolecular
concentric hexagons were fully characterized by NMR, ESI–MS,
TWIM–MS, and TEM, establishing their hexagon-in-hexagon architectures.
The combination of different tetratopic ligands also assembled hybrid
concentric hexagons with increasing diversity and complexity. Furthermore,
these concentric hexagon supramolecules with precisely controlled
shapes and sizes were utilized as building blocks to hierarchically
self-assemble supramolecular metal–organic nanoribbons (SMON)
at solid–liquid interfaces. Ambient STM imaging showed the
formation of long 1D SMON rather than 2D assembly on the basal plane
of highly oriented pyrolytic graphite (HOPG) surface after simple
dropcasting of the solution of preassembled concentric hexagons onto
a freshly cleaved surface of HOPG. This wet chemical method based
on self-assembly may offer simple, economical, and scalable routes
to deliver complex materials.
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condensation reactionsConcentric Hexagons2 D assemblyhexagon supramoleculeschemical methodAmbient STM imagingtetratopic terpyridinetetratopic ligandpyridinium salts chemistryTWIMHOPGbuilding blockspyrolytic graphitepyrylium saltsTEMamine derivatives1 D SMONNMRbasal planescalable routessurfaceESItetratopic ligands
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