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Copyright Wiley-VCH Verlag GmbH, 69451 Weinheim, 2001.

Chem. Eur. J. 2002.

Supporting Information for:

Transition Metal Ion-Directed SupramolecularAssembly of One- and Two-dimensional Polyrotaxanes

Incorporating Cucurbituril.

Ki-Min Park, Dongmok Whang, Eunsung Lee, Jungseok Heo andKimoon Kim*

Contribution from the National Creative Research Initiative Center for SmartSupramolecules, and Department of Chemistry, Division of Molecular and LifeSciences, Pohang University of Science and Technology (POSTECH), San 31

Hyojadong, Pohang 790-784, Republic of Korea

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Table S1. Crystallographic data for polyrotaxanes 1-11.

1 2 3 4 5 6

CCDC no. TUBVUH 167483 167484 167638 167639 REKHOEformula C52H94N32O41Cu C52H92N32O40Co C52H93N32O40.5Ni C52H98N32O43Co C40H100N30O20Ni C74H103N28O32AgS3fw 1887.13 1864.51 1873.29 1918.55 1380.21 2100.89crystal system triclinic monoclinic monoclinic triclinic triclinic triclinicspace group P-1 P21/c P21/c P-1 P-1 P-1a (Å) 14.690(2) 12.4455(3) 12.430(3) 14.3871(1) 14.1675(3) 15.001(2)b (Å) 14.923(2) 21.3242(5) 21.318(4) 14.7087(2) 14.5505(2) 15.491(2)c (Å) 19.665(3) 29.0398(4) 29.012(6) 21.9769(3) 21.5450(5) 23.580(2) α (deg) 84.963(11) 90 90 97.1690(10) 99.0460(10) 90.896(10)β (deg) 74.983(10) 91.4160(10) 91.80(3) 97.3420(10) 94.6760(10) 105.538(9)γ (deg) 68.898(11) 90 90 115.9440(10) 114.82(10) 116.707(13)V (Å3); Z 3884.4(9); 2 7704.5(3); 4 7684(3); 4 4061.65(8); 2 3926.84(13); 2 4640.5(11); 2ρcalcd (g/cm3) 1.613 1.607 1.619 1.569 1.167 1.504[a] no. of obs. refl. 8965 10993 5634 12051 11692 9913[b] R1; wR2 0.100; 0.243 0.080; 0.203 0.083; 0.214 0.074; 0.229 0.132; 0.369 0.111; 0.288

7 8 9 10 11

CCDC no PAPQUS 167485 REKHIY 167486 167487formula C53H86N31O33Ag C53H85N32O31.5Cd C156H260N92O100Ag2 C56H76N28O20Ag2F12S4 C124H178N61O36Cufw 1793.32 1786.93 5240.30 2033.42 3738.80crystal system monoclinic orthorhombic orthorhombic tetragonal tetragonalspace group P21/n Pcca Cmca P4/n P4/na (Å) 16.680(4) 50.8087(7) 31.408(3) 24.4530(2) 23.7507(3)b (Å) 17.889(2) 15.4474(3) 32.508(4) 24.4530(2) 23.7507(3)c (Å) 24.335(4) 19.1638(4) 22.479(3) 12.6911(2) 14.11560(10)β (deg) 101.355(8) 90 90 90 90V (Å3); Z 7119(2); 4 15040.9(5); 8 22951(5); 4 7588.63(15), 2 7962.55(15); 2ρcalcd (g/cm3) 1.673 1.578 1.517 1.780 1.560[a] no. of obs. refl. 7126 11614 6266 5935 6244[b] R1; wR2 0.063; 0.169 0.141; 0.428 0.118; 0.322 0.056; 0.165 0.126; 0.344

[a] obs. relf. criterion: I > 2σ(I).[b] R1 = Σ||F0| - |Fc||/Σ|F0|. wR2 = [Σw(F02 - Fc2)2/ΣwF04]1/2; weighting: w = 1/[σ2(F02) + (aP)2 + bP], where P = (F02 + 2Fc2)/3.

Figure S1. Asymmetric unit of 1. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Cu-N(25), 2.005(8); Cu-N(27), 2.009(9); Cu-O(13), 1.968(7); Cu-O(14), 1.979(7); Cu-O(15), 2.279(9); N(25)-Cu-N(27),89.5(3); N(25)-Cu-O(13), 173.5(4); N(25)-Cu-O(14), 91.7(3); N(25)-Cu-O(15), 91.1(3); N(27)-Cu-O(13), 87.8(3); N(27)-Cu-O(14), 170.8(4); N(27)-Cu-O(15), 99.3(4); O(13)-Cu-O(14),90.1(3); O(13)-Cu-O(15), 95.2(4); O(14)-Cu-O(15), 89.8(3). Hydrogen bonding interactions:N(26)∙∙∙O(1), 2.960(12); N(26)∙∙∙O(2), 2.786(10); N(26)∙∙∙O(3), 2.825(12); N(28)∙∙∙O(7),2.954(12); N(28)∙∙∙O(8), 2.847(11); N(28)∙∙∙O(9), 2.933(12).

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Figure S2. Packing diagram of the polyrotaxane in 1.

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Figure S3. Asymmetric unit of 2. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Co-N(25), 2.148(5);Co-N(28), 2.156(5); Co-O(13), 2.096(4); Co-O(14), 2.077(4); Co-O(15), 2.109(4); Co-O(16),2.109(4); N(25)-Co-N(28), 178.2(2). Hydrogen bonding interactions: N(26)···O(1),2.810(6); N(26)···O(2), 2.841(6); N(26)···O(3), 3.002(7); N(27)···O(10), 2.833(6);N(27)···O(11), 2.853(6); N(27)···O(12), 2.967(7).

Figure S4. Asymmetric unit of 6. Tosylate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Ag-N(25), 2.203(9);Ag-N(27), 2.192(12); N(25)-Ag-N(27), 170.1(5). Hydrogen bonding interactions:N(26)···O(1), 2.844(11); N(26)···O(2), 2.822(11); N(28)···O(7), 2.935(11); N(28)···O(9),2.935(11); N(28)···O(9), 3.036(13).

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a

c

b

ac

b

a) b)

Figure S5. Packing diagrams showing hydrogen bonding interactions betweenthe adjacent polyrotaxanes in a) 2 and b) 6. Counter ions and solvated watermolecules in the lattice are omitted for clarity.

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Figure S6. Asymmetric unit of 4. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Co-N(114), 2.130(4); Co-N(214), 2.148(4); Co-O(1W), 2.130(3); Co-O(2W), 2.116(3); Co-O(3W), 2.115(3); Co-O(4W),2.123(3); N(114)-Co-N(214), 92.67(9); O(1W)-Co-N(214), 174.75(10); N(114)-Co-O(1W),92.39(13); O(2W)-Co-N(214), 92.12(10); O(3W)-Co-N(114), 90.73(14); O(4W)-Co-N(214),90.85(10); O(2W)-Co-O(1W), 86.72(14); O(3W)-Co-O(4W), 175.80(14); O(3W)-Co-O(2W),88.38(15). Hydrogen bonding interactions: N(113)∙∙∙O(101), 2.903; N(113)∙∙∙O(102), 3.006;N(113)∙∙∙O(103), 2.917; N(213)∙∙∙O(20E), 2.907; N(213)∙∙∙O(20F), 2.848.

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Figure S7. Asymmetric unit of 5. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Ni-N(124), 2.069(8); Ni-N(224), 2.082(10); Ni-O(1W), 2.074(8); Ni-O(2W), 2.090(9); Ni-O(3W), 2.088(8); Ni-O(4W),2.071(9); N(124)-Ni-N(224), 94.1(3); O(1W)-Ni-N(224), 91.1(3); N(124)-Ni-O(1W), 94.1(3);O(2W)-Ni-N(224), 91.2(4); O(3W)-Ni-N(124), 89.9(3); O(4W)-Ni-N(224), 87.8(4); O(2W)-Ni-O(1W), 173.7(4); O(3W)-Ni-O(4W), 88.2(4); O(3W)-Ni-O(2W), 88.1(3). Hydrogen bondinginteractions: N(113)∙∙∙O(2), 2.897; N(113)∙∙∙O(3), 2.940; N(4)∙∙∙O(103), 2.873; N(223)∙∙∙O(7),2.856; N(223)∙∙∙O(8), 2.853; N(223)∙∙∙O(9), 3.071.

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Figure S8. Asymmetric unit of 7. Nitrate ions and water molecules in the lattice are omittedfor clarity. Selected bond distances (Å) and angles (deg): Ag-N(25), 2.132(7); Ag-N(28),2.137(7); N(25)-Ag-N(28), 177.9(3). Hydrogen bonding interactions: N(26)...O(1), 2.914(10);N(26)...O(2), 3.082(10); N(26)...O(6), 2.893(10); N(27)...O(8), 2.793(9); N(27)...O(9), 2.754(9);N(27)...O(10), 3.089(10).

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Cd(2)

Figure S9. Asymmetric unit of 8. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Cd(1)-N(25), 2.328(8);Cd(1)-O(21), 2.390(6); Cd(1)-O(22), 2.356(10); Cd(1)-O(35), 2.564(9); N(25)-Cd(1)-N(25)’,168.8(3); Cd(2)-N(28), 2.508(14); Cd(2)-O(23), 2.36(3); Cd(1)-O(24), 2.256(18); N(28)-Cd(2)-N(28)’, 84.9(5). Hydrogen bonding interactions: N(26)∙∙∙O(7), 3.050(11);N(26)∙∙∙O(11), 3.054(11); N(28)∙∙∙O(7), 2.875(11); N(27)∙∙∙O(4), 2.797(11); N(27)∙∙∙O(95),3.135(13).

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Figure S10. Asymmetric unit of 9. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Ag-N(19), 2.256(10);Ag-N(21), 2.343(15); Ag-O(11), 2.53(3); N(19)-Ag-N(19A), 124.3(5); N(19)-Ag-N(21),111.2(3).

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Figure S11. Schematic representation of stacking of the 2D polyrotaxane layers in9. Small circles represent silver ions and lines represent pseudorotaxane PR442+linking two silver ions. The mean separation between the layers is 9.8 Å.

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Figure S12. Asymmetric unit of 10. Counter ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Ag-N(14), 2.364(3);N(14)-Ag(1)-N(14A), 113.49(9); N(14)-Ag(1)-N(14B), 101.70(16).

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Figure S13. Asymmetric unit of 11. Nitrate ions and water molecules in the lattice areomitted for clarity. Selected bond distances (Å) and angles (deg): Cu-N(14), 2.041(6);Cu-O(1W), 2.178(14); N(14)-Ag(1)-N(14B), 89.18(4); N(14)-Ag(1)-N(14A), 166.2(4); N(14)-Ag(1)-O(1W), 96.9(2).

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CCDC no.TUBVUH167483167484167638167639REKHOEformulaC52H94N32O41CuC52H92N32O40CoC52H93N32O40.5NiC52H98N32O43CoC40H100N30O20NiC74H103N28O32AgS3CCDC noPAPQUS167485REKHIY167486167487formulaC53H86N31O33AgC53H85N32O31.5CdC156H260N92O100Ag2C56H76N28O20Ag2F12S4C124H178N61O36Cufw1793.321786.935240.302033.423738.80