A1 Refereed original research article in a scientific journal
Self-Assembly of Water-Mediated Supramolecular Cationic Archimedean Solids
Authors: Peuronen A, Lehtimaki E, Lahtinen M
Publisher: AMER CHEMICAL SOC
Publication year: 2013
Journal: Crystal Growth and Design
Journal name in source: CRYSTAL GROWTH & DESIGN
Journal acronym: CRYST GROWTH DES
Volume: 13
Issue: 10
First page : 4615
Last page: 4622
Number of pages: 8
ISSN: 1528-7483
DOI: https://doi.org/10.1021/cg401246n(external)
Abstract
Understanding the self-assembly of small structural units into large supramolecular assemblies remains one of the great challenges in structural chemistry. We have discovered that tetrahedral, supramolecular cages, exhibiting the shapes of Archimeclean solids, can be self assembled by hydrogen bonding interactions using tricationic N-donors (1 or 2) in cooperation with water (W). Single crystal X-ray analysis shows that cage (2)4(W)6, assembled in an aqueous solution of cation 2 and KPF6, consists of four tripodal trications linked by six water monomers and resembles the shape of a truncated tetrahedron. Similarly, cage (1)4(W-6)4 spontaneously self assembles in an aqueous solution of cation 1 and NH4PF6 and consists of four tripodal cations and four water hemmers. Here, each of the four (H2O)6 units act as tritopic nodes between three distinct tripodal cations forming a polyhedron similar to the cantellated tetrahedron. These two well-defined cages are assembled via total of 12 and 36 hydrogen bonds, respectively. Both cages possess interior solvent accessible volumes exceeding 1000 angstrom(3). Furthermore, each one of the (H2O)(6) clusters in face centered cubic structure lb acts as a node between two distinct (1)4(W6)4 units, and thus a solvent filled tubular three-dimensional network (tube diameter of similar to,6.5 A) is generated that mimics the structure of diamond at the nanorneter scale. To our knowledge, this is the first example of such species being formed entirely via hydrogen bonding interactions.
Understanding the self-assembly of small structural units into large supramolecular assemblies remains one of the great challenges in structural chemistry. We have discovered that tetrahedral, supramolecular cages, exhibiting the shapes of Archimeclean solids, can be self assembled by hydrogen bonding interactions using tricationic N-donors (1 or 2) in cooperation with water (W). Single crystal X-ray analysis shows that cage (2)4(W)6, assembled in an aqueous solution of cation 2 and KPF6, consists of four tripodal trications linked by six water monomers and resembles the shape of a truncated tetrahedron. Similarly, cage (1)4(W-6)4 spontaneously self assembles in an aqueous solution of cation 1 and NH4PF6 and consists of four tripodal cations and four water hemmers. Here, each of the four (H2O)6 units act as tritopic nodes between three distinct tripodal cations forming a polyhedron similar to the cantellated tetrahedron. These two well-defined cages are assembled via total of 12 and 36 hydrogen bonds, respectively. Both cages possess interior solvent accessible volumes exceeding 1000 angstrom(3). Furthermore, each one of the (H2O)(6) clusters in face centered cubic structure lb acts as a node between two distinct (1)4(W6)4 units, and thus a solvent filled tubular three-dimensional network (tube diameter of similar to,6.5 A) is generated that mimics the structure of diamond at the nanorneter scale. To our knowledge, this is the first example of such species being formed entirely via hydrogen bonding interactions.
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