Anion-Templated Assembly of a Supramolecular Cage Complex

Fleming, James S.; Mann, Karen L. V.; Carraz, Charles-Antoine; Psillakis, Elefteria; Jeffery, John C.; McCleverty, Jon A.; Ward, Michael D.

doi:10.1002/(sici)1521-3773(19980518)37:9<1279::aid-anie1279>3.0.co;2-q

Cited by 297 publications

(94 citation statements)

References 12 publications

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“…Once assembled, many of the hollow structures have been shown to be capable of encapsulating molecules through electrostatic and͞or dispersion forces. Often times, ions will template the formation of an assembly (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21). When considering that metal-containing assemblies often possess magnetic, photophysical, and͞or redox properties not accessible from purely organic systems, studies in basic host-guest chemistry hold new promise for technologies in molecular sensing (22)(23)(24)(25)(26)(27)(28), separations, and catalysis (29,30).…”

mentioning

confidence: 99%

Self-assembly of nanoscopic coordination cages of D _3h symmetry

Kuehl

Kryschenko

Radhakrishnan

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

155

101

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A family of nanoscale-sized supramolecular cage compounds with a trigonal prismatic framework was prepared by means of spontaneous self-assembly from the combination of a predesigned molecular ''clip'' with tritopic pyridyl subunits. As confirmed by x-ray crystallography, the smallest structure of the reported series is Ϸ1 ؋ 2 nm and possesses a nitrate anion incarcerated inside its molecular cavity. The largest structure has dimensions of Ϸ 1 ؋ 4 nm. T he formation of discrete supramolecular entities driven and held together by metal coordination is an intense new area of investigation at the forefront of supramolecular chemistry (1-10). Because self-assembly is guided by the chemical information encoded into the molecular subunits, diverse structures with predetermined shape, size, and functionality can readily be designed. Indeed, a wide variety of aesthetic structures have been realized, such as molecular grids, helicates, rings, catenanes, tetrahedra, cubes, cuboctahedra, etc. Once assembled, many of the hollow structures have been shown to be capable of encapsulating molecules through electrostatic and͞or dispersion forces. Often times, ions will template the formation of an assembly (11-21). When considering that metal-containing assemblies often possess magnetic, photophysical, and͞or redox properties not accessible from purely organic systems, studies in basic host-guest chemistry hold new promise for technologies in molecular sensing (22-28), separations, and catalysis (29,30).Because lower-symmetry hosts can ultimately be expected to show enhanced guest selectivity, especially toward planar aromatic guests, prismatic cages represent a natural progression in the development of this area. Although M 3 L 2 -type cages are relatively simple three-dimensional constructs, they remain uncommon. Of those that have been reported (31-40), most usually either require the use of templates to assemble in solution, or assemble only in the solid state. Part of the reason for this limitation is possibly the fact that, in most cases, flexible ligands were used. By contrast, structures derived from rigid tritopic linkers with cis-metal ions are either: (i) tetrahedral M 6 L 4 cages (41) where L is a planar ligand, or (ii) double-square M 6 L 4 cages (42) where L is a 109°linker ligand. Construction of the M 3 L 2 , D 3h species is complicated by the fact that rigid tritopic linkers with ideal mutual angles of 60°are not easily accessible. A noteworthy trigonal bipyramidal structure (35), made from Pd(II) ions and a calix[3]arene subunit, was shown to be able to reversibly bind a molecule of C 60 .By exploiting incommensurate symmetry requirements for differing metallic subunits, an alternative approach to structures of this general topology was recently reported. Raymond and Wong (43-45) successfully prepared a series of M 2 MЈ 3 L 6 supramolecular clusters where a multifunctionalized ligand (L) was cleverly designed to selectively interact with two types of metal ions (one hard and one soft).Double oxidative addition ...

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mentioning

confidence: 99%

Self-assembly of nanoscopic coordination cages of D _3h symmetry

Kuehl

Kryschenko

Radhakrishnan

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

155

101

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“…63) reacts with cobalt(II) acetate in the presence of sodium tetrafluorborate resulting in the tetrahedral structure 64 (Fig. 64), into whose cavity a tetrafluorborate ion is encapsulated [62].…”

Section: Geometric Figuresmentioning

confidence: 99%

Coordination motifs in modern supramolecular chemistry

Alexeev

Kharisov

García

et al. 2010

Coordination Chemistry Reviews

117

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“…However, it is still difficult to design and synthesize architectures with predicted structure and properties when the ligands have more than two donors. Because the formation of architecture depends on factors such as the nature of the ligand, the coordination geometry of the metal centers, the ratio of the ligand and metal ion, the counter ions, the solvent system, and even the pH value of the solution and crystallization conditions [7]. Recently, extensive studies have been carried out to give many new 1D, 2D, and 3D frameworks through the coordination of metal atoms with pyridone-or pyridine-based bridge ligands for example 4,4 0 -bipyridine and its derivatives like 1,2-bis(4-pyridyl)ethane, 1,2-bis(4-pyridyl)ethylene, and 1, 3-bis(4-pyridyl)propane [8].…”

Section: Introductionmentioning

confidence: 99%

Syntheses, crystal structures and properties of Co(II) complexes with N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine (bpb), and Cd(II), Hg(II) complexes with reduced bpb

Kong¹,

Zhu²,

Okamura³

et al. 2004

Journal of Solid State Chemistry

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Anion-Templated Assembly of a Supramolecular Cage Complex

Cited by 297 publications

References 12 publications

Self-assembly of nanoscopic coordination cages of D _3h symmetry

Self-assembly of nanoscopic coordination cages of D _3h symmetry

Coordination motifs in modern supramolecular chemistry

Syntheses, crystal structures and properties of Co(II) complexes with N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine (bpb), and Cd(II), Hg(II) complexes with reduced bpb

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Anion-Templated Assembly of a Supramolecular Cage Complex

Cited by 297 publications

References 12 publications

Self-assembly of nanoscopic coordination cages of D 3h symmetry

Self-assembly of nanoscopic coordination cages of D 3h symmetry

Coordination motifs in modern supramolecular chemistry

Syntheses, crystal structures and properties of Co(II) complexes with N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine (bpb), and Cd(II), Hg(II) complexes with reduced bpb

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Self-assembly of nanoscopic coordination cages of D _3h symmetry

Self-assembly of nanoscopic coordination cages of D _3h symmetry