Diastereoselective Control of Tetraphenylethene Reactivity by Metal Template Self-Assembly
Journal article, 2019
The reaction of 4,4′,4′′,4′′′-(ethene-1,1,2,2-tetrayl)tetraaniline with 2-pyridinecarboxaldehyde and iron(II) chloride resulted, after aqueous workup, in the diastereoselective formation of an [Fe 2 L 3 ] 4+ triple-stranded helicate structure, irrespective of the stoichiometry employed. The helicate structure was characterized in solution by multinuclear NMR spectroscopy, and in the solid state by single-crystal X-ray crystallography. The reaction of iron(II) tetrafluoroborate or iron(II) bistriflimide with the tetraaniline and 2-pyridinecarboxaldehyde allowed the formation of an [Fe 8 L 6 ] 16+ cube when the appropriate stoichiometry was used, but these structures were unstable with respect to hydrolysis. The pendant amine groups on the helicate can be functionalized by reaction with acid chlorides or anhydrides, and the resulting functionalized tetraphenylethene (TPE) units were isolated by the reaction of the helicate with tris(2-aminoethyl)amine. The emission properties of the TPE units were studied in THF/water mixtures, and they were found by dynamic light scattering to self-assemble into large (av. diameter 250 nm) structures.
metal template synthesis
helicates
fluorescence
self-assembly
iron
Author
Aaron D.W. Kennedy
University of New South Wales (UNSW)
Nicholas de Haas
University of New South Wales (UNSW)
Hasti Iranmanesh
University of New South Wales (UNSW)
Ena T. Luis
University of New South Wales (UNSW)
Chao Shen
University of New South Wales (UNSW)
Pi Wang
Zhejiang University
University of New South Wales (UNSW)
Jason R. Price
Australian Synchrotron (ANSTO)
William A. Donald
University of New South Wales (UNSW)
Joakim Andreasson
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Feihe Huang
Zhejiang University
J. E. Beves
University of New South Wales (UNSW)
Chemistry - A European Journal
0947-6539 (ISSN) 1521-3765 (eISSN)
Vol. 25 22 5708-5718Areas of Advance
Nanoscience and Nanotechnology
Subject Categories
Chemical Sciences
DOI
10.1002/chem.201806259
PubMed
30775812