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Open AccessArticle

Complementarity in Cyclotricatechylene Assemblies: Symmetric Cages Linked within 3D Cubic Hydrogen Bonded Networks

1
School of Chemistry, University of Melbourne, Parkville VIC 3010, Australia
2
School of Molecular Science, La Trobe University, Wodonga VIC 3690, Australia
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Author to whom correspondence should be addressed.
Chemistry 2020, 2(2), 577-590; https://doi.org/10.3390/chemistry2020035
Received: 30 April 2020 / Revised: 23 May 2020 / Accepted: 26 May 2020 / Published: 11 June 2020
(This article belongs to the Special Issue Supramolecular Chemistry in the 3rd Millennium)
A serendipitous discovery has led to the generation of a family of four compounds in which six components combine to form symmetric metal-cyclotricatechylene (H6ctc) cages. The four compounds, which have the compositions, [Cs((CH3)2CO)6][K4(H6ctc)4(H2O)8][Cs4(H2O)6](PO4)3, [Rb((CH3)2CO)6][Rb2K2(H6ctc)4(H2O)6][Rb4(H2O)6](PO4)3, [Cs((CH3)2CO)6][K4(H6ctc)4(H2O)8]-[Cs(H2O)9](SO4)3 and [Rb((CH3)2CO)6][Rb2K2(H6ctc)4(H2O)6][Rb(H2O)9](SO4)3 possess cubic symmetry that arises from the complementary interactions that govern the assembly of the components. The cage cavities contain water molecules and either one or four large alkali metal ions (either Rb+ or Cs+) which interact with the internal aromatic surfaces of the cage. Each cage is linked to six tetrahedral anions (PO43− or SO42−) through 24 equivalent hydrogen bonds and each anion bridges a pair of cages through eight such hydrogen bonds. An unusual octahedral complex M((CH3)2CO)6+ (M = Rb or Cs), in which the M-C=O link is linear, appears to be a key structural component. A feature of this family of crystalline compounds is the presence of a range of complementary interactions which combine to generate materials that exhibit high crystallographic symmetry. View Full-Text
Keywords: complementarity; hydrogen bonding; crystal engineering; cyclotricatechylene complementarity; hydrogen bonding; crystal engineering; cyclotricatechylene
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Holmes, J.L.; Russell, S.M.; Abrahams, B.F.; Hudson, T.A.; White, K.F. Complementarity in Cyclotricatechylene Assemblies: Symmetric Cages Linked within 3D Cubic Hydrogen Bonded Networks. Chemistry 2020, 2, 577-590.

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