Supramolecular Archimedean Cages Assembled with 72 Hydrogen Bonds

Crystalline cages held together by hydrogen bonds can trap a wide range of molecules based on their size. Self-assembly of multiple components into well-defined and predictable structures remains one of the foremost challenges in chemistry. Here, we report on the rational design of a supramolecular cage assembled from 20 ions of three distinct species through 72 hydrogen bonds. The cage is constructed from two kinds of hexagonal molecular tiles, a tris(guanidinium)nitrate cluster and a hexa(4-sulfonatophenyl)benzene, joined at their edges through complementary and metrically matched N-H···O-S hydrogen bonds to form a truncated octahedron, one of the Archimedean polyhedra. The truncated octahedron, with an interior volume of 2200 cubic angstroms, serves as the composite building unit of a body-centered cubic zeolite-like framework, which exhibits an ability to encapsulate a wide range of differently charged species, including organic molecules, transition metal complexes, and “ship-in-a-bottle” nanoclusters not observed otherwise.

[1]  J. Ashby.  References and Notes , 1999 .

[2]  M. Pemble,et al.  Growth of Quantum-Confined Indium Phosphide inside MCM-41 , 1998 .

[3]  J. Atwood,et al.  A chiral spherical molecular assembly held together by 60 hydrogen bonds , 1997, Nature.

[4]  N. Heo,et al.  Synthesis and crystal structure of Ag4I4 nanoclusters in the sodalite cavities of fully K+-exchanged zeolite A , 2004 .

[5]  Michael D. Pluth,et al.  Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis , 2007, Science.

[6]  M. Fujita,et al.  Self-Assembled M24L48 Polyhedra and Their Sharp Structural Switch upon Subtle Ligand Variation , 2010, Science.

[7]  Zikang Tang,et al.  Quantum Size Effect on the Excited State of HgI2,PbI2 and BiI3 Clusters and Molecules in Zeolite LTA , 1992 .

[8]  Xin-Yi Wang,et al.  Hydrogen-bonded metal-complex sulfonate (MCS) inclusion compounds: effect of the guest molecule on the host framework. , 2007, Inorganic chemistry.

[9]  Anthony L. Spek,et al.  Journal of , 1993 .

[10]  J. Ruíz,et al.  Application of Radiogenic Isotopes to Ore Deposit Research and Exploration , 1999 .

[11]  M. Ward,et al.  Architectural diversity and elastic networks in hydrogen-bonded host frameworks: from molecular jaws to cylinders. , 2007, Journal of the American Chemical Society.

[12]  Michael J Zaworotko,et al.  Bottom up synthesis that does not start at the bottom: quadruple covalent cross-linking of nanoscale faceted polyhedra. , 2007, Journal of the American Chemical Society.

[13]  M. Ward,et al.  Controlled orientation of polyconjugated guest molecules in tunable host cavities. , 2010, Journal of the American Chemical Society.

[14]  V. Vassileva.  Synthesis and characterization of dibarium iron(II) formate tetrahydrate , 2003 .

[15]  G. Shimizu,et al.  Phosphonate and sulfonate metal organic frameworks. , 2009, Chemical Society reviews.

[16]  C. Baerlocher,et al.  Crystal structures of the hydro-sodalite Na6[AlSiO4]6 8H2O and of the anhydrous sodalite Na6[AlSiO4]6 , 1986 .

[17]  G. Stucky,et al.  Quantum Confinement and Host/Guest Chemistry: Probing a New Dimension , 1990, Science.

[18]  M. Mastalerz.  Shape-persistent organic cage compounds by dynamic covalent bond formation. , 2010, Angewandte Chemie.

[19]  Steven M. Cramer,et al.  Synthesis and Characterization of High-Affinity, Low-Molecular-Mass Displacers for Anion-Exchange Chromatography , 1998 .

[20]  Songping D. Huang,et al.  Self-assembly of nanoscopic coordination cages of D3h symmetry , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[21]  J. Rebek,et al.  Compressed alkanes in reversible encapsulation complexes. , 2009, Nature chemistry.

[22]  D. Meisel,et al.  Formation of small particles of lead iodide, mercuric iodide, and bismuth iodide layered semiconductors , 1987 .

[23]  A. Yassar,et al.  Porous metal-organic truncated octahedron constructed from paddle-wheel squares and terthiophene links. , 2005, Journal of the American Chemical Society.

[24]  M. Fujita,et al.  Functional molecular flasks: new properties and reactions within discrete, self-assembled hosts. , 2009, Angewandte Chemie.

[25]  Michael D. Ward,et al.  Guanidinium Para-Substituted Benzenesulfonates: Competitive Hydrogen Bonding in Layered Structures and the Design of Nonlinear Optical Materials , 1994 .

[26]  D. Stuart,et al.  The atomic structure of the bluetongue virus core , 1998, Nature.

[27]  Yan Liu,et al.  Chiral nanoscale metal-organic tetrahedral cages: diastereoselective self-assembly and enantioselective separation. , 2010, Angewandte Chemie.

[28]  Jurriaan Huskens,et al.  Complete asymmetric chirality in a hydrogen-bonded assembly , 1999 .

[29]  K. Rissanen,et al.  White Phosphorus Is Air-Stable Within a Self-Assembled Tetrahedral Capsule , 2009, Science.

[30]  M. Ward,et al.  The generality of architectural isomerism in designer inclusion frameworks. , 2001, Journal of the American Chemical Society.

[31]  Xintao Wu,et al.  Structural overview and structure–property relationships of iodoplumbate and iodobismuthate , 2009 .

[32]  K. B. Yoon,et al.  Very high third-order nonlinear optical activities of intrazeolite PbS quantum dots. , 2006, Journal of the American Chemical Society.

[33]  G. Desiraju,et al.  MOLECULAR NETWORKS IN THE CRYSTAL STRUCTURES OF TETRAKIS(4-IODOPHENYL)METHANE AND (4-IODOPHENYL)TRIPHENYLMETHANE , 1998 .