1. Fujita et al., 1994

2. Fujita et al. Nature, 1994

5. molecular "magic rings" Fujita et al.

6. The stoichiometry will induce the right selection of the fragments so as to afford a catenane quantitatively Fujita et al.

8. The complexes contain two identical ligands but each ligand is asymmetric: the ring is oriented

9. a catenane with two oriented rings Is it a chiral compound?

11. a catenane with two 36-membered rings

12. Angew. Chem. Int. Ed. 2005, 44, 4896 –4899

13. Double-loop compound 2a was obtained by treating ligand 4 with bimetallic linker 5 in dimethyl sulfoxide (DMSO). Typically, ligand 4 (7.1 mg, 10 mmol) was treated with 5 (4.6 mg, 5.0 mmol) in DMSO (0.50 mL) for a few minutes at ambient temperature.

14. Subsequently, the catenation of 2a at both loops by adding water to the solution in DMSO was examined. The newly formed product was cyclic dimer 3, which contains two catenated frameworks. 3 : Why do we need to add water???

15. CPK modeling showed that an expanded conformation of 3 has an external diameter of approximately 4 nm (Figure 5). The backbone of 3 comprises 238 non-hydrogen atoms

27. Guest = o-Carborane

42. three very simple bridging ligands

43. Analogy with C 60 Schematic representation of the self-assembly of coordination networks from metal ions which favor a square-planar coordination geometry and different bridging ligands. a) Linear ligands are expected to give 2D grid complexes. b) Slightly bent ligands are expected to lead to spherical finite complexes.

44. The 1 H NMR spectrum (aromatic region) of the product Assembled from Pd(NO 3 ) 2 and ligand 1a (2 equiv; 500 MHz, [D 6 ]DMSO, 258°C, TMS).

45. CSI-MS spectrum showing the formation of M 12 L 24 product (PF 6 salt).

46. a) Molecular structure 2a assembled from 24 bidentate ligands 1a and12 metal ions. b) Schematic representation of the cuboctahedral frameworks of 2a.

47. a) STM image of individual spheres 2a on the graphite at room temperature. b) Height profile of the STM image.

48. The crystal structure of 2b. Counterions and solvent molecules are omitted for clarity (green Pd, red O, blue N, gray C).

49. By attaching a functional group on each ligand, 24 functional groups are aligned equivalently at the periphery of the sphere. Metal–porphyrins are known to collect light energy when they are aggregated as in light harvesting proteins or chlorophylls.

50. A molecular modeling study of 2d : Pd yellow, the porphyrin-based and pyridine- based units are green and purple, respectively

51. JACS, 2009 square planar Ni(II) and Co(II) complexes show spin crossover upon encapsulation by coordination cages of the general structure 1

52. The confined cavity of the hosts inhibits changes in the metal coordination number or geometry and promotes configuration change presumably via electronic interactions between the metal dz 2 orbital and the π orbitals of the aromatic cage panels.

53. UV-vis spectra of 1a ⊃ 2 and 2 in solid state  M T vs T plots for 1a ⊃ 2 and 2 (~16% of the value expected for pure HS configuration of Ni(II) : S=1)

56. Angew. Chem. Int. Ed., 2009, 48, 3418-3438 in this review article the contributions of Raymond, Rebek, Stang, Saalfrank and others are also discussed

57. , 251

58. The Diels-Alder reaction of anthracenes in the absence of hosts is extremely well studied and generally yields an adduct bridging the centre ring (9,10-position) of the anthracene framework as a consequence of the high localization of p-electron density at that site Coordination cages (1 and 2), prepared by simple mixing of an exo- tridentate organic ligand and an end-capped Pd(II) ion in a 4:6 ratio in water.

59. Pair-selective encapsulation of two types of reactants, 9- hydroxymethylanthrancene (3a) and N-cyclohexylphthalimide(4a), within cage 1 and the subsequent Diels-Alder reaction leading to syn isomer of 1,4-adduct 5 within the cavity of 1

60. crystal structure of 1 ⊃ 5

61. with the "bowl" as container, the reaction pathway is totally different experimental conditions : 10 mol % of 2, aqueous solution, r.t., 5 hours ➞ >99% yield of 6

62. Schematic representation of the catalytic Diels-Alder reaction of anthracenes and phthalimide in the presence of bowl 2. Autoinclusion of substrates into 2 (step a) and autoexclusion of the product from 2 (step c)

63. 6 / 2/ 3

64. formation of homotopic compounds must be avoided TEMPLATE

65. without template, 5 and 6 are obtained X-ray structure of 6

66. X-ray structure of the host-guest complex: the triphenylene derivative forms an A-D complex with the cage (stacking)

69. 1 : M 12 L A 24 2 : M 12 L B 24 L A : -R = -O-n-C 3 H 7 L B : -R = -O-n-C 6 H 13

70. When a fresh 1:1 mixture of 1 and 2 was immediately subjected to MS analysis, the peak intensities were equivalent When a 1:1 mixture of 1 and 2 in acetonitrile was allowed to stand at 23 °C overnight, the formation of mixed products M 12 L A 23 L B (3) and M 12 L A L B 23 (4) was not observed

71. Ligand exchange slowly occurs over 3 days at room temperature, and new peaks, corresponding to 3 and 4, gradually appeared in the Mass spectrum. The mixed species 3 and 4 only appeared after 35 hours L A : -R = -O-n-C 3 H 7 L B : -R = -O-n-C 6 H 13

72. The 1 H NMR signals of free and coordinated pyridine are sharp and independently observed. However, using saturation transfer NMR spectroscopy, ligand equilibration can be observed. The exchange rate, k obs, was determined to be 1.9x10 -2 s -1, and the half-life was 36 s. The half-life of the mononuclear complex is thus smaller than that of the M 12 L 24 complex by a factor of ∼ 10 5

73. pp. 53-56 Short nucleotide fragments such as mono- and dinucleotides are generally unable to form stable hydrogen-bonded base pairs or duplexes in water. Within the hydrophobic pockets of enzymes, however, even short fragments form stable duplexes to transmit genetic information. Here, we demonstrate the efficient formation of hydrogen bonded base pairs from mononucleotides in water through enclathration in the hydrophobic cavities of self-assembled cages.

74. The stable formation of DNA duplexes in water requires the association of at least four complementary nucleotide base pairs. complementary base pair formation of mononucleotides is however possible within an artificial hydrophobic pocket.

75. the pyrazine-pillared coordination cage 1 provides a flat, hydrophobic pocket with an ideal interplanary distance (6.6A˚ ) for the binding of planar aromatic molecules

76. Stirring an aqueous solution of 5'-adenosine monophosphate (5, 2.0 mmol) and 5'-uridine monophosphate (6, 2.0 mmol) in the presence of cage 1 (2.0 mmol) resulted in the formation of the host–guest complex 1.(5 ⊃ 6) AU

77. Molecular container compounds provide a new space for reaction chemistry, both literally and figuratively, through the encapsulation of smaller guest molecules M 4 L 6 tetrahedral assemblies constructed from metal and ligand components

78. The tetrahedron assembles exclusively as the homochiral stereoisomer (that is, ΔΔΔΔ or ΛΛΛΛ), with its chirality generated by the tris(bidentate) chelation of each of the four metal centers. Left : schematic representation of the tetrahedral assembly. One ligand only is drawn Right : CAChe model of [CpRu(η 6 -C 6 H 6 ) ⊂ Fe 4 L 6 ] 11- with the guest molecule shown in a space-filling view

79. Acid Catalysis in Basic Solution : A Supramolecular Host Promotes Orthoformate Hydrolysis Michael D. Pluth, Robert G. Bergman,* Kenneth N. Raymond* SCIENCE, VOL. 316, 6 APRIL 2007, 85-88 Here, we report a highly charged, water-soluble, metalligand assembly with a hydrophobic interior cavity that thermodynamically stabilizes protonated substrates and consequently catalyzes the normally acidic hydrolysis of orthoformates in basic solution, with rate accelerations of up to 890-fold.

80. The naphthalene walls render the interior hydrophobic, whereas the tetra-anionic ligands, in combination with the trivalent metal centers, confer a 12 – overall charge to the assembly. M : Ga III 11-

81. A model of [2-H + ⊂ 1] 11– 2 : N,N,N′,N′-tetramethyl-1,4-diaminobutane pK a shift : ΔpK a ~ 3.5 units free amine : pK a ~11 complexed amine : pK a ~14.5

82. In the presence of a catalytic amount of 1 in basic solution, triethyl orthoformate is quickly hydrolyzed (t 1/2 ~ 12 min, pH = 11.0, 22°C) to the corresponding formate ester, HC(O)(OR), and finally to formate, HCO 2 –