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Issue 11, 2018
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Phosphate–phosphate oligomerization drives higher order co-assemblies with stacks of cyanostar macrocycles

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Abstract

The importance of phosphate in biology and chemistry has long motivated investigation of its recognition. Despite this interest, phosphate's facile oligomerization is only now being examined following the discovery of complexes of anion–anion dimers of hydroxyanions. Here we address how oligomerization dictates phosphate's recognition properties when engaged with planar cyanostar macrocycles that can also oligomerize by stacking. The crystal structure of cyanostar with phosphate shows an unprecedented tetrameric stack of cyanostar macrocycles threaded by a phosphate trimer, [H2PO4⋯H2PO4⋯H2PO4]3−. The solution behaviour, studied as a function of solvent quality, highlights how dimers and trimers of phosphate drive formation of higher order stacks of cyanostar into dimer, trimer and tetramer co-assemblies. Solution behaviors differ significantly from simpler complexes of bisulfate hydroxyanion dimers. Phosphate oligomerization is: (1) preferred over ion pairing with tetrabutylammonium cations, (2) inhibits disassembly of the complexes upon dilution, and (3) resists interference from competitive anion solvation. The phosphate oligomers also appear critical for stability; complexation of just one phosphate with cyanostars is unfavored. The cyanostar's ability to self-assemble is found to create a tubular, highly electropositive cavity that complements the size and shape of the phosphate oligomers as well as their higher charge. When given the opportunity, phosphate will cooperate with the receptor to form co-assembled architectures.

Graphical abstract: Phosphate–phosphate oligomerization drives higher order co-assemblies with stacks of cyanostar macrocycles

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Publication details

The article was received on 13 Dec 2017, accepted on 09 Feb 2018 and first published on 20 Feb 2018


Article type: Edge Article
DOI: 10.1039/C7SC05290A
Citation: Chem. Sci., 2018,9, 2863-2872
  • Open access: Creative Commons BY license
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    Phosphate–phosphate oligomerization drives higher order co-assemblies with stacks of cyanostar macrocycles

    E. M. Fatila, M. Pink, E. B. Twum, J. A. Karty and A. H. Flood, Chem. Sci., 2018, 9, 2863
    DOI: 10.1039/C7SC05290A

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