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Bending Nanofibers into Nanospirals: Coordination Chemistry as a Tool for Shaping Hydrophobic Assemblies
Author(s) -
Kossoy Elizaveta,
Weissman Haim,
Rybtchinski Boris
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404263
Subject(s) - supramolecular chemistry , coordination complex , coordination geometry , cobalt , chemistry , amphiphile , aqueous solution , self assembly , nickel , crystallography , terpyridine , hydrophobic effect , nanotechnology , metal , materials science , molecule , inorganic chemistry , organic chemistry , hydrogen bond , copolymer , polymer , crystal structure
In the current work, we demonstrate how coordination chemistry can be employed to direct self‐assembly based on strong hydrophobic interactions. To investigate the influence of coordination sphere geometry on aqueous self‐assembly, we synthesized complexes of the amphiphilic perylene diimide terpyridine ligand with the first‐row transition‐metal centers (zinc, cobalt, and nickel). In aqueous medium, aggregation of these complexes is induced by hydrophobic interactions between the ligands. However, the final shapes of the resulting assemblies depend on the preferred geometry of the coordination spheres typical for the particular metal center. The self‐assembly process was characterized by UV/Vis spectroscopy, zeta potential measurements, and cryogenic transmission electron microscopy (cryo‐TEM). Coordination of zinc(II) and cobalt(II) leads to the formation of unique nanospiral assemblies, whereas complexation of nickel(II) leads to the formation of straight nanofibers. Notably, coordination bonds are utilized not as connectors between elementary building blocks, but as directing interactions, enabling control over supramolecular geometry.