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www.sciencemag.org/cgi/content/full/333/6041/436/DC1 Supporting Online Material for Supramolecular Archimedean Cages Assembled with 72 Hydrogen Bonds Yuzhou Liu, Chunhua Hu, Angiolina Comotti, Michael D. Ward* *To whom correspondence should be addressed. E-mail: [email protected] Published 22 July 2011, Science 333, 436 (2011) DOI: 10.1126/science.1204369 This PDF file includes: Materials and Methods SOM Text Figs. S1 to S10 Tables S1 and S2 References

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www.sciencemag.org/cgi/content/full/333/6041/436/DC1

Supporting Online Material for

Supramolecular Archimedean Cages Assembled with 72 Hydrogen Bonds

Yuzhou Liu, Chunhua Hu, Angiolina Comotti, Michael D. Ward*

*To whom correspondence should be addressed. E-mail: [email protected]

Published 22 July 2011, Science 333, 436 (2011) DOI: 10.1126/science.1204369

This PDF file includes:

Materials and Methods SOM Text Figs. S1 to S10 Tables S1 and S2 References

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 1

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds

Yuzhou Liu,1 Chunhua Hu,1 Angiolina Comotti2 and Michael D. Ward*,1

Contribution from the Department of Chemistry and the Molecular Design Institute, New York University, 100 Washington Square East, New York, NY 10003-6688 and the Department of Materials Science,

University of Milano Bicocca, Via R. Cozzi 53, 20125 Milan

Supporting Online Material (Science Magazine)

Section S1. Materials and methods Section S2. Polyhedra engineering from Archimedean principles

Figure S2.1. Schematic representation of an unfolded quasi-truncated octahedron Table S1. Archimedean polyhedra and criteria for eliminating polyhedron candidates

Section S3. Synthesis of q-TO compounds and Scheme 1: Guests encapsulated in q-TO framework

Figure S3.1. Single crystals of the q-TO framework containing various guests. Figure S3.2. Optical and scanning electron microscopy of crystals of 1 Figure S3.3. Assignment of the faces for a single crystal of 1

Section S4. Three dimensional structures of the q-TO framework Figure S4.1 Comparison of the q-TO and zeolites A frameworks: {100} and {111} views. Figure S4.2 Packing views of q-TO framework: {100} and {111} views.

Figure S4.3. Space-filling views of the orientation of the metal iodide clusters with respect to the HSPB6- tile in compound 13 Figure S4.4. Space-filling views of the orientation of the metal iodide clusters with respect to the HSPB6- tile in compound 14 Figure S4.5. Space-filling views of the orientation of the metal iodide clusters with respect to the HSPB6- tile in compound 15 Figure S4.6. Overview of q-TO framework crystal structures illustrating various encapsulated metal complexes.

Section S5. NMR spectra and verification of guest stoichiometry Section S6. Infrared data and verification of guests Section S7. Absorption of iodine by q-TO framework

Figure S7.1. Photographs and powder X-ray diffraction of compound 1 during exposure to iodine

Section S8. X-ray crystallographic details (including Table S2) Section S9. Thermal gravimetric analysis

Figure S9.1. Thermogravimetric analysis (TGA) spectrum of compound 1 Section S10. Powder X-ray diffraction

Figure S10.1. Powder X-ray diffraction data of compound 1 and its simulated data Figure S10.2. Powder X-ray diffraction data for compound 1 recorded at increasing temperatures 1 New York University 2 University of Milano Bicocca

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 2

Section S1. Materials and Methods Sodium hexa(4-sulfonatophenyl)benzene Na6(HSPB6-) was synthesized according to literature procedures (33). The corresponding sulfonic acid was obtained by passing Na6(HSPB6-) through an Amberlyst 36 ion-exchange column. All other chemicals are purchased from Sigma-Aldrich and used without further purification. Crystallization of compounds 1-15 was achieved by slow evaporation of the solvent upon standing at ambient conditions. Formic acid was used as the solvent for the crystallization of compounds 7 and 8 in order to prevent the oxidation of Co(II) and Fe(II) (34).

Single crystal X-ray diffraction was performed with either a Bruker APEX II single crystal diffractometer at 100 K or with synchrotron radiation at the APS ChemMatCARS Station (http://cars9.uchicago.edu/chemmat/pages/microxtallography.html) Crystal structure determination details are described below in section S8. Powder X-ray diffraction was recorded on a Bruker AXS D8 Discover with GADDS equipped with a 2D Vantec-2000 detector. 1H Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker 400 MHz spectrometer at room temperature, and chemical shifts were reported in ppm using the solvent resonance as the internal standard. NMR spectra for compounds 6 - 10 exhibited broad peaks due to the presence of paramagnetic ions or molecules, which precluded detailed analysis. Infrared spectra (IR) were collected on a Thermo Electron Magna 550 FT-IR using KBr pellets at room temperature. The very small crystallization yields of compounds 7 and 8 precluded acquisition of IR spectra. Thermogravimetric analysis was performed on Perkin Elmer Pyris 1 TGA under nitrogen. Scanning electron microscopy was performed with a Hitachi S-3500 scanning electron microscope. Deionized water was obtained from a MilliporeDirect Q apparatus. Element analysis of compounds 12 – 15 to confirm the occupancy of the encapsulated clusters were performed by Galbraith Laboratories, Inc. using inductively coupled plasma-optical emission spectroscopy (ICP-OES; for Mo, P, S, Pb, Hg and Bi). Element analysis of the metal:sulfur ratio typically was consistent with X-ray diffraction analysis. Analysis for iodine, performed with an ion-selective electrode, was typically unreliable owing to the presence of an unidentified powder substance that forms concomitantly with these compounds. Therefore, only the metal:sulfur ratios are reported here.

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 3

Section S2. Polyhedra engineering from Archimedean principles

Figure S2.1. Schematic representation of an unfolded quasi-truncated octahedron, in which the green and yellow

hexagonal tiles represent hexa(4-sulfonatophenyl)benzene (HSPB) and [G3NO3]2+, respectively.

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 4

Table S1. Archimedean polyhedra and criteria for eliminating polyhedron candidates It can be shown that four HSPB6- tiles and four [G3NO3]2+ tiles can fold into a quasi-truncated octahedron (q-TO), a lower symmetry form of a truncated octahedron (See Figure S1). Other Archimedean polyhedra with six-membered tiles – the truncated tetrahedron [34.64], truncated icosahedron [512.620], truncated cuboctahedron [412.86.68], and truncated icosidodecahedron [430.620.812] – can be ruled out by consideration of the structural features of the HSPB6- and [G3NO3]2+ tiles. The truncated tetrahedron and truncated icosahedron would not support N-H…O-S hydrogen bonding along all edges. The truncated cuboctahedron and truncated icosidodecahedron are not possible because their hexagonal tiles do not share edges. Below follows all the Archimedean polyhedra, including those containing hexagonal tiles. The five platonic solids are not considered here because none of the Platonic solids have hexagonal tiles. The illustrations of the Archimedean polyhedra were obtained courtesy of S. Torquato and Y. Jiao, Princeton University (35). Name Tiling description Figure Comment Cuboctahedron 3846

No hexagons

Snub dodecahedron 380512

No hexagons

Icosidodecahedron 320512

No hexagons

Snub cube 33246

No hexagons

Truncated dodecahedron 3201012

No hexagons

Rhombicuboctahedron 38418

No hexagons

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 5

Rhombicosidodecahedron 320430512

No hexagons

Truncated cube 3886

No hexagons

Truncated tetrahedron 3464

Non-complementary tiles sharing edges

Truncated cuboctahedron 4126886

Complementary tiles cannot share edges

Truncated icosidodecahedron

4306201012

Complementary tiles cannot share edges

Truncated icosahedron 512620

Non-complementary tiles sharing edges

Truncated octahedron 4668

OK

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 6

Section S3. Synthesis of q-TO compounds

Compounds 1 - 6. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (12.8 mg, 0.15 mmol), and HSPB (acid form; 101.5 mg, 0.1 mmol) were dissolved in dimethylformamide (DMF)/water (v:v = 1:1; 1.5 mL total). The resulting solution, which was acidic (pH ~ 2.5), was allowed to stand under ambient conditions so that the solvent evaporated slowly, affording block-shaped crystals of compound 1 after several weeks, with readily apparent square and hexagonal facets. Crystallization of the same mixture in 1-formylpiperidine/water (v:v=1:1; 1.5 mL total) instead of DMF/water afforded crystals of compound 2 that were identical in appearance and adopted the same framework architecture (by X-ray diffraction). Crystallization in the presence of various additives (0.2 mmol) under the same conditions in DMF/H2O produced compounds 3 (additive = phenol), 4 (additive = benzamide), 5 (additive = acetylsalicylic acid) or 6 (additive = 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, also known as 4-oxo-TEMPO) in which the additives were encapsulated as guests in various amounts (the number of guests encapsulated in each quasi-truncated octahedron are denoted in parentheses next to each compound number in Scheme 1). In the case of compound 5 the crystallization was performed in either DMF or DMF/water to determine the proclivity of acetylsalicylic acid toward hydrolysis under the acidic crystallization conditions. Crystallization in DMF results in encapsulation of acetylsalicylic acid alone, whereas crystallization in DMF/water led to encapsulation of a mixture of acetylsalicylic acid and salicylic acid in an approximately 3:7 ratio (by 1H NMR).

Single crystal X-ray diffraction confirmed the existence of the q-TO framework, each with a unit cell containing two quasi-truncated octahedrons filled with numerous species from the crystallization medium in addition to intentional additives for compounds 3 - 6. The framework was refined readily in all cases, but disorder of the guests prevented their refinement. In the case of compound 1, each unit cell contained 12 DMF molecules (81.95 Å 3 each), 16 G ions (65.39 Å 3 each), 36 water molecules (19.77 Å 3 each), 24 dimethylammonium ions from decomposition of DMF under acidic conditions (59.67 Å 3 each), 4 formic acid from decomposition of DMF under acidic conditions (56.24 Å 3 each), and 20 chloride ions (24.05 Å 3 each), resulting in a total of 4880 Å3 occupied by guest molecules (van der Waals volume). The total amount of void space (including the interior of the quasi-truncated octahedron and the connecting channels, estimated from PLATON, using a spherical probe with a radius of 1.20 Å)

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 7

equals 37% of the total volume of the crystal (unit cell volume = 19130 Å3; 7078 Å3 void space per unit cell). Each unit cell contains two quasi-truncated octahedrons. The inner volume of the quasi-truncated octahedron was calculated with DMF molecules remaining in the square channels so that the accessible volume, as calculated with a probing sphere having a diameter of 4.0 Å, was limited to the quasi-truncated octahedrons (calculated based on the Connolly surface with Material Studio 4.2; smaller values allowed the probe to pass through the square channels). The interior volume of the quasi-truncated octahedrons is calculated from the difference between the accessible volume and volume occupied by the wall of the quasi-truncated octahedron.

Compound 7. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (12.8 mg, 0.15 mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), cobalt(II) nitrate hexahydrate (116.4 mg, 0.4 mmol) and dimethylammonium chloride (81.5 mg, 1 mmol) were dissolved in formic acid (0.5 ml). The solvent was allowed to evaporate under ambient conditions for two weeks, affording a small amount of dark green block-shaped crystals accompanied by unidentified needle-shaped green crystals.

Compound 8. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (12.8mg, 0.15 mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), iron(II) chloride tetrahydrate (80.1 mg, 0.4 mmol) and dimethyl ammonium chloride (81.5 mg, 1 mmol) were dissolved in formic acid (0.5 mL). The solvent was allowed to evaporate under ambient conditions for two weeks, affording pale yellow block-shaped crystals.

Compound 9. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (23.0 mg, 0.27 mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), iron(III) chloride (64.1 mg, 0.4 mmol) and dimethyl ammonium chloride (81.5 mg, 1 mmol) were dissolved in a mixture of deionized water (0.1 mL) and acetic acid (1 mL). The solvent was allowed to evaporate under ambient conditions for two weeks, affording pale yellow block-shaped crystals during slow evaporation of solvent.

Compound 10. Guanidinium chloride (57.3mg, 0.6mmol), sodium nitrate (15.1mg, 0.175mmol) and HSPB (acid form; 101.5 mg, 0.1 mmol), copper nitrate hydrate (56.3mg, 0.3mmol) and dimethylammonium chloride (81.5mg, 1mmol) were dissolved in a mixture of deionized water (0.1 mL) and acetic acid (2 mL). The solvent was allowed to evaporate under ambient conditions for two weeks affording cube-shaped yellow crystals.

Compound 11. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (23.0 mg, 0.27 mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), and aluminum nitrate nonahydrate (150.0 mg, 0.4 mmol) was dissolved in dimethylformamide (DMF)/water (1:1) (0.5 mL) containing acetic acid (120.1 mg, 2 mmol). The solvent was allowed to evaporate under ambient conditions for two weeks in an open vial, affording colorless block-shaped crystals.

Compound 12. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (15.1 mg, 0.175 mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), and sodium phosphomolybdate hydrate (47.1 mg, 0.025 mmol) was dissolved in dimethylformamide (DMF)/water (v:v = 1:1) (1.5 mL). The resulting solution was heated at 200°C for 5 minutes, then filtered and allowed to stand under ambient conditions for two weeks to allow slow evaporation of the solvent, affording cubic-shaped green crystals. Elemental analysis to verify the amount of [Mo12O40P]3- relative to the q-TO: Mo:P:S (measured) = 12.0:1.2:24; Mo:P:S (expected based on one Keggin ion per quasi-truncated octahedron) = 12:1:24. The infrared spectrum confirmed the presence of Mo12PO40

3- (νP-O = 1062 cm-1; νMo=O = 957 cm-1). Crystals of Na3Mo12PO40 could be retrieved from aqueous solutions in which compound 12 was dissolved, verifying the presence of the Keggin ion in crystals of 12.

Compound 13. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (12.8 mg, 0.15mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), and bismuth(III) iodide (118 mg, 0.2 mmol) was dissolved in DMF (2 mL). The solvent was allowed to evaporate under ambient conditions for three weeks, affording dark yellow crystals. Elemental analysis

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 8

to verify amount of [Bi10I20]10+ cluster: Bi:S (measured) = 5.0:24; Bi:S (expected based on crystallographic data, 50% occupancy of cluster) = 5:24.

Compound 14. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (12.8 mg, 0.15mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), and lead(II) iodide (92 mg, 0.2 mmol) was dissolved in DMF/H2O (5 mL: 1 mL). The solvent was allowed to evaporate under ambient conditions for four weeks, affording light yellow crystals. Elemental analysis to verify amount of neutral [Pb10I20] cluster: Pb:S (measured) = 4.0:24; Pb:S (expected based on crystallographic data, 50% occupancy of cluster) = 5:24.

Compound 15. Guanidinium chloride (57.3 mg, 0.6 mmol), sodium nitrate (12.8 mg, 0.15mmol), HSPB (acid form; 101.5 mg, 0.1 mmol), and mercury(II) iodide (92 mg, 0.2 mmol) was dissolved in DMF/H2O (5 mL: 1 mL). The solvent was allowed to evaporate under ambient conditions for four weeks, affording light yellow crystals. Elemental analysis to verify amount of [Hg8I20]4- cluster: Hg:S (measured) = 3.4:24; Hg:S (expected based on crystallographic data, 50% occupancy of cluster): 4:24.

Figure S3.1. Single crystals of the q-TO framework containing various guests. The numbers correspond to the

compounds in Scheme 1.

Figure S3.2. (left) Optical microscopy of crystals of 1 in the crystallization media, illustrating the uniformity of phase.

(right) Scanning electron microscopy of compound 1, illustrating crystal habits with hexagonal and square faces.

(Inset) A single crystal of compound 1, highlighting further the hexagonal and square faces.

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 9

Figure S3.3. Assignment of the faces for a single crystal of 1.

Section S4. Three dimensional structures of the q-TO framework

Figure S4.1. (A, B) The q-TO framework, as viewed nearly along the [001] and [111] directions, respectively. The

q-TO framework is generated by the nodes defined by the sulfonate sulfur positions. (C, D) The sodalite framework,

as viewed along the [001] and [111] directions, respectively. The sodalite framework is generated by nodes defined by

Al and Si atoms. In both cases the truncated octahedron is the composite building unit.

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 10

Figure S4.2. The q-TO framework as viewed nearly along the [001] and [111] directions, respectively. In both cases,

the hydrogen, sodium atoms and clathrated DMF molecules are omitted for clarity.

Figure S4.3. Space-filling views of the orientation of the [Bi10I20]10+ cluster with respect to the HSPB6- tile in compound

13.

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 11

Figure S4.4. Space-filling views of the orientation of the [Pb10I20] cluster with respect to the HSPB6- tile in compound

14.

Figure S4.5. Space-filling views of the orientation of the [Hg8I20]4- cluster with respect to the HSPB6- tile in compound

15.

The surface of the interior walls of the q-TO is irregular, with the smallest diameter measuring 12 Å (see above) and largest measuring 20 Å (between opposing vertices). The exterior surface of each cluster also is irregular; the longest dimensions of the [Pb10I20], [Hg8I20]4-, and [Bi10I20]10+ clusters are 17.5 Å, 17.5 Å, and 16.5 Å. In the case of compounds 13 and 14, the four iodide ligands attached to the four metal atoms in the cube exhibit linear I…π(phenyl centroid) contacts (24) of 3.83 Å with the central rings of the HSPB6- tiles, suggesting a structure-directing role for this interaction. In addition, each external phenyl ring of HSPB6- in 14 exhibits a C-H…I contact of 3.20 Å, which collectively may influence the orientation of the [Pb10I20] cluster (the corresponding C-H…I distance in 13 is 3.56 Å, beyond contact distance). Compound 15 exhibits four I…π(phenyl centroid) contacts, measuring 3.77 Å, between the four iodide ligands extending from the mercury atoms in the cube and the central ring of each HSPB6- tile. The iodide ligands on the external HgI3

1- groups nestle into the grooves between adjacent phenyl rings of

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 12

HSPB6-. These features suggest that cluster orientation is governed by a “lock-and-key” arrangement with the corrugated walls of the q-TO. Notably, the thermal anisotropy of the Bi and I atoms in 13 was much larger than in 14 and 15, consistent with looser packing of the smaller [Bi10I20]10+ cluster in the q-TO.

Figure S4.6. Upper: (A) The body-centered cubic q-TO framework in compound 1. (B-F) The q-TO framework with

encapsulated metal complexes, identified in the lower panel. The yellow shading denotes the position of individual

q-TOs. Lower: Metal ions arranged either within the q-TO or threaded within the <100> channels. The guests are

depicted as space filling and the host as ball-and-stick. (G) Pb10I20 or [Bi10I20]10+ and (H) [Hg8I20]4- nanoclusters

encapsulated within the q-TO. The encapsulated guests are depicted as space-filling (green = chloride; orange = iron;

blue = copper, cobalt; red = aluminum; gray = carbon) and the q-TO framework as wireframe (yellow = sulfur; blue =

nitrogen; gray = carbon; red = oxygen). Hydrogen atoms have been omitted for clarity. The green lines in (G) and (H)

represent the edges of the molecular tiles. The central M4I4 core of each nanocluster is highlighted in blue.

Section S5. NMR spectra and verification of guest stoichiometry Compound 1. 1H-NMR (D2O,400 MHz): δ 8.35 (s, 1.8 H, HCOO-), 7.95 (s, 12H, C(O)-H from DMF), 7.37 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.13 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.04 (s, 36 H, CH3 from DMF), 2.88 (s, 36 H, CH3 from DMF), 2.72 (s, 71H, CH3 from dimethylammonium ions)

1H-NMR (DMSO-d6,400 MHz): 8.20 (br, N-H from dimethylammonium ions), 8.15 (s, HCOO-), 7.95 (s,

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 13

12H, C(O)-H from DMF), 7.11 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 6.92 (s, 117 H, N-H from guanidinium ions), 6.83 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 2.90 (s, 36 H, CH3 from DMF), 2.72 (s, 36 H, CH3 from DMF). The 1H-NMR spectrum of compound 1 reveal 8 G+, 12 DMF, 12 dimethylammonium ions (DMA) and 2 formic acid guests per quasi-truncated octahedron, comprising a total charge of 20+ for the encapsulated guests. Each quasi-truncated octahedron carries a charge of 16-, and the framework contains six sodium ions (6+ charge total) per quasi-truncated octahedron (by single crystal X-ray diffraction), resulting in an overall charge of 10+ per quasi-truncated octahedron. This apparent discrepancy can be explained by the presence of undetected anions and cations, with a net charge of 10-. Indeed, the addition of aqueous AgNO3 to an aqueous solution of 1 afforded a white crystalline precipitate presumed to be AgCl. If the entire 10- charge is due to encapsulated chloride, which must be highly disordered, the molecular formula of 1 would be HSPB4G20Na6Cl10(NO3)4(DMA)12(DMF)12(HCOOH)2(H2O)18. The amount of water is calculated based on TGA (see S9), based on a mass that assumes ten chloride ions. We note that this molecular formula may vary crystal-to-crystal and batch-to-batch.

Compound 2. 1H-NMR (D2O,400 MHz): 8.37 (s, 1H, HCOO-), 7.96 (s, 17 H, C(O)-H from 1-formylpiperidine), 7.37 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.13 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.44 (m, 68H, α-CH2 from 1-formylpiperidine), 3.17 (t, 48H, α-CH2 from piperidine hydrochloride), 1.8 ~ 1.5 (m, 174 H, β, γ-CH2 from 1-formylpiperidine and piperidine hydrochloride).

Compound 3. 1H-NMR (DMSO-d6,400 MHz): 9.32 (s, 7H, OH from phenol), 8.10 (br, N-H from dimethylammonium ions), 7.96 (s, 9H, C(O)-H from DMF), 7.16 (m, 63 H, C-H from HSPB and phenol), 6.94 (s, 120 H, N-H from guanidinium ions), 6.78 (m, 69 H, C-H from HSPB and phenol), 2.90 (s, 27 H, CH3 from DMF), 2.74 (s, 27 H, CH3 from DMF).

Compound 4. 1H-NMR (DMSO-d6,400 MHz): 8.29 (br, 24H, N-H from dimethylammonium ions), 7.92 (br, 7 H, N-H from benzamide), 7.83 (m, 14 H, C-H from benzamide), 7.53 (m, 7 H, C-H from benzamide), 7.51 (m, 14H, C-H from benzamide), 7.34 (br, 7H, N-H from benzamide), 7.11 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 6.95 (s, 117 H, N-H from guanidinium ions), 6.82 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 2.89 (s, 3H, CH3 from DMF), 2.73 (s, 3H, CH3 from DMF), 2.48 (s, CH3 from dimethylammonium, overlapped with CH3 from DMSO).

Compound 5. 1H-NMR (D2O,400 MHz): 8.20 (s, 3.5 H, HCOO-), 8.02 (m, 7 H, C-H), 7.90 (s, 40 H, C(O)-H from DMF), 7.65 (m, 7 H, C-H from aspirin), 7.44~7.22 (m, 63 H, C-H from HSPB and aspirin), 7.02 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 2.98 (s, 120 H, CH3 from DMF), 2.83 (s, 120 H, CH3 from DMF), 2.67 (s, CH3 from dimethylammonium), 2.33 (s, 21H, CH3 from aspirin).

Compound 6. 1H-NMR (D2O,400 MHz): 8.38 (s, 2H, HCOO-), 7.95 (s, 13 H, C(O)-H from DMF), 7.37 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.13 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.04 (s, 39H, CH3 from DMF), 2.88 (s, 39H, CH3 from DMF), 2.72 (s, 57 H, CH3 from dimethylammonium), 1.60 ~ 1.50 (br, approximately 28 H, C-H from oxo-TEMPO, broadened because of the paramagnetic electrons).

Compound 9. 1H-NMR (D2O,400 MHz): 8.0 ~ 7.0 (br), 3.05 (s, CH3 from DMF), 2.87 (s, CH3 from DMF), 2.72 (s, CH3 from dimethylammonium). The peaks were broadened by presence of paramagnetic Fe (III) ions.

Compound 11. 1H-NMR (D2O,400 MHz): 8.30 (s, 1.3H, HCOO-), 7.95 (s, 19 H, C(O)-H from DMF), 7.37 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.13 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.03 (s, 57 H, CH3 from DMF), 2.88 (s, 57 H, CH3 from DMF), 2.72 (s, 24 H, CH3 from dimethylammonium), 2.11 (s, 24 H, CH3 from CH3COOH).

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 14

Compound 12. 1H-NMR (D2O,400 MHz): 8.33 (s, 1.2H, HCOO-), 7.95 (s, 20 H, C(O)-H from DMF), 7.36 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.12 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.03 (s, 60 H, CH3 from DMF), 2.87 (s, 60 H, CH3 from DMF), 2.73 (s, 24 H, CH3 from dimethylammonium).

Compound 13. 1H-NMR (D2O,400 MHz): 7.96 (s, 14 H, C(O)-H from DMF), 7.37 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.13 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.04 (s, 42 H, CH3 from DMF), 2.88 (s, 42 H, CH3 from DMF), 2.73 (s, 54H, CH3 from dimethylammonium)

Compound 14. 1H-NMR (DMSO-d6,400 MHz): 8.16 (s, br, 20 H, N-H from dimethylammonium), 7.96 (s, 13 H, C(O)-H from DMF), 7.10 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 6.92 (s, 96 H, N-H from guanidinium ions), 6.81 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 2.90 (s, 39 H, CH3 from DMF), 2.74 (s, 39 H, CH3 from DMF). 1H-NMR (D2O,400 MHz): 7.94 (s, 13 H, C(O)-H from DMF), 7.35 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.11 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.02 (s, 39 H, CH3 from DMF), 2.86 (s, 39 H, CH3 from DMF), 2.72 (s, 60 H, CH3 from dimethylammonium)

Compound 15. 1H-NMR (D2O,400 MHz): 7.96 (s, 15 H, C(O)-H from DMF), 7.37 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 7.13 (d, J = 8.0 Hz, 48 H, C-H from HSPB), 3.04 (s, 45 H, CH3 from DMF), 2.88 (s, 45 H, CH3 from DMF), 2.73 (s, 48H, CH3 from dimethylammonium)

Section S6. Infrared data and verification of guests (Key: br = broad, vs = very strong, s = strong, m = medium, w = weak)

Compound 1. 3393(vs, br), 3181 (s, br), 1664 (s), 1384 (s), 1188(s, br), 1119 (m), 1037 (s), 1012(s), 671(s)

Compound 2. 3383 (s, br), 3152 (w, br), 2940 (w), 2858 (w), 1670 (s), 1456 (m), 1394 (m), 1225 (s), 1186 (s), 1118 (m), 1037 (s), 1012 (s), 852 (m), 668 (s), 546 (m)

Compound 3. 3389 (s, br), 3184(m, br), 2802 (w, br), 2444 (w, br), 1667 (s), 1593 (w), 1500 (w), 1471 (w), 1386 (m, br), 1222 (vs), 1170 (vs), 1120 (s), 1037 (vs), 1012 (vs), 848 (w), 755 (w), 735 (w), 670 (vs)

Compound 4. 3387 (s, br), 3187 (s, br), 2805 (w, br), 1669 (vs), 1574 (w), 1470 (w), 1391 (m), 1220 (s), 1181 (s), 1119 (s), 1037 (s), 1012 (s), 848 (w), 670 (s), 559 (w)

Compound 5. 3386 (s, br), 3185 (s, br), 2812 (w, br), 1673 (s), 1601 (w), 1485 (w), 1471 (w), 1384 (m), 1223 (s), 1180 (s), 1119 (s), 1037 (s), 1012 (s), 850 (w), 670 (s), 561 (w), 441 (w)

Compound 6. 3392 (s, br), 3187 (s, br), 2809 (w, br), 1671 (s), 1469 (w), 1390 (m), 1224 (s), 1181 (s), 1119(m), 1008 (s), 1012 (s), 849 (w), 671 (s), 561 (w)

Compound 9. 3406 (s, br), 3182 (s, br), 2785 (w, br), 2362 (s), 2336 (m), 1667 (s), 1470 (m), 1385 (m), 1225 (s), 1175 (s), 1118 (m), 1007 (s), 1011 (s), 849 (w), 670 (w)

Compound 10. 3393 (s, br), 3176 (s, br), 2800 (m, br), 2475 (w, br), 2227 (w, br), 1670 (s), 1600 (w), 1468 (m), 1390 (m), 1226 (s), 1174 (s), 1120 (m), 1036 (s), 1011 (s), 848 (m), 735 (w), 670 (s), 562 (w)

Compound 11. 3375 (s, br), 3183 (s, br), 2354 (w), 1668 (vs), 1497 (w), 1373 (s), 1222 (s), 1183 (s), 1119 (s), 1038 (s), 1012 (s), 847 (w), 734 (w), 670 (s), 639 (w), 560 (m), 477 (w)

Compound 12. 3389 (s, br), 3184 (s, br), 2809 (w, br), 1667 (s), 1470 (m), 1391 (m), 1222 (s), 1183 (s), 1120 (m), 1062 (w), 1037 (s), 1012 (s), 957 (m), 882 (w), 845 (w), 813 (s), 735 (w), 670 (s), 561 (w)

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 15

Compound 13. 3420 (m), 3179 (m), 2800 (w), 1662 (vs), 1466 (w), 1390 (m), 1217 (s), 1181 (s), 1117 (s), 1036 (s), 1010 (s), 845 (w), 670 (s), 558 (w)

Compound 14. 3426 (m, br), 3187 (m, br), 1664 (vs), 1467 (w), 1394 (w), 1218 (s), 1180 (s), 1119 (m), 1037 (m), 1011 (s), 846 (w), 735 (w), 671 (s), 559 (m)

Compound 15. 3420 (m), 3178 (w), 1664 (vs), 1498 (w), 1469 (w), 1389 (m), 1224 (s), 1186 (s), 1118 (m), 1104 (m), 1037 (s), 1011 (s), 846 (m), 735 (w), 670 (vs), 558 (m)

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 16

Section S7. Absorption of iodine by compound 1

Figure S7.1. (A) A sequence of photograph of a single crystal of 1 during diffusion of iodine vapor under ambient conditions. Cleaving of the crystal reveals a uniform distribution of iodine throughout. Powder X-ray diffraction reveals that iodine-containing compound remains crystalline indefinitely, shown here after 24 hours. Elemental analysis for iodine and sulfur indicated a molar ratio of I:S = 5.5:24, consistent with 5.5 iodine atoms per quasi-truncated octahedron. Only the framework can be located and refined, however, indicating substantial disorder of the encapsulate iodine molecules. (B) The iodine-containing crystal after evacuation (400 mbar) for six days, the black color indicating that iodine remained in the crystal. Elemental analysis for iodine and sulfur indicated a molar ratio of I:S = 3.5: 24, consistent with 3.5 iodine atoms per quasi-truncated octahedron. Powder X-ray diffraction revealed that the material was still crystalline and the framework intact. (C) Iodine exchanged crystals turned colorless upon standing in air at ambient temperature for six days, indicating loss of absorbed iodine and transformation to a new unidentified phase. (D) In-situ powder X-ray diffraction of a collection of single crystals during iodine diffusion. The sample was rotated during data collection to minimize preferred orientation. Section S8. X-ray crystallographic details Data using Mo radiation was collected on a Bruker SMART Apex II diffractometer equipped with a CCD detector and operated at 1,500W power (50KV, 30 mA) to generate Mo Kα radiation (λ = 0.71073 Å), which is graphite-monochromated and MonoCap-collimated. The crystal was mounted on a 20 micron nylon CryoLoops (Hampton Research) with Paratone-N (Hampton Research) frozen at -173°C with an

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 17

Oxford Cryosystem 700 plus cooler. Data using synchrotron radiation was collected using diamond 111-monochromated synchrotron radiation at the APS ChemMatCARS Station (λ = 0.41328 Å) with the φ scan method. A Bruker SMART APEXII CCD area detector was used, and data was collected at 115 K or 12 K, which was controlled with an Oxford Diffraction Cryojet or Helijet instrument. Preliminary lattice parameters and orientation matrices were obtained from three sets of frames. Then full data were collected using the ω scan method with the frame width of 0.5° (36). Data were processed with the SAINT+ program (37) for reduction and cell refinement. Multi-scan absorption corrections were applied by using the SADABS program for area detector (38). All structures were solved by the direct method (SHELXS-97) (39) and refined on F2 (SHELXL-97) (40). Non-hydrogen atoms were refined with anisotropic displacement parameters, and hydrogen atoms on carbons were placed in idealized positions (C-H = 0.93 or 0.96 Å) and included as riding with Uiso(H) = 1.2 or 1.5 Ueq(non-H). The PLATON/SQUEEZE procedure (41) was applied to handle the heavily disordered components (ions and solvents) in the voids of the frameworks. Crystallographic details are included in Table S2. Crystal structure data for compounds 1 to 15 can be accessed at the Cambridge Crystallographic Data Centre (https://www.ccdc.cam.ac.uk) and have been allocated the accession numbers CCDC 823027 -823041. Table S2. Crystallographic data and structure refinement results

1 2 3 4 5

Empirical formula C108H126N26Na3O48S12 C90H84N20Na3O42S12 C90H84N20Na3O42S12 C96H120N38Na3O42S12 C90H84N20Na3O42S12

Formula weight 3010.04 2571.46 2571.46 2931.99 2571.46

Temperature (K) 100(2) 100(2) 100(2) 100(2) 100(2)

X-ray wavelength (Å) 0.71073 0.71073 0.71073 0.71073 0.71073

Crystal system Cubic Cubic Cubic Cubic Cubic

Space group I

4 3m I

4 3m I

4 3m I

4 3m I

4 3m

Unit cell dimensions (Å) a = 26.7455(11) a = 26.9526(14) a = 26.8609(16) a = 26.980(3) a = 26.8888(13)

Volume (Å3) 19131.6(14) 19579.5(18) 19380(2) 19640(4) 19440.8(16)

Z 4 4 4 4 4

Density (cal.) (mg/m3) 1.045 0.872 0.881 0.992 0.879

Abs. coefficient (mm-1) 0.212 0.196 0.198 0.204 0.197

F(000) 6260 5300 5300 6092 5300

Crystal size (mm3) 0.16 × 0.16 × 0.14 0.18 × 0.16 × 0.15 0.26 × 0.16 × 0.10 0.30 × 0.30 × 0.30 0.30 × 0.28 × 0.25

Theta range (°) 1.52 to 18.76 1.51 to 18.15 1.52 to 17.21 1.07 to 20.58 1.51 to 18.72

Reflections collected 48173 44152 36744 38322 95334

Unique reflections (Rint) 1409 (0.0465) 1313 (0.0445) 1121 (0.0485) 1863 (0.0789) 1422 (0.0372)

Data completeness (%) 99.9 99.7 99.7 99.9 99.7

Goodness-of-fit on F2 1.086 1.083 1.038 1.095 1.059

R1/wR2 [I > 2sigma(I)] 0.0976/0.2651 0.0665/0.1796 0.0821/0.2401 0.0800/0.2211 0.1023/0.2869

Largest diff. peak/hole (e/Å3) 0.452/-0.343 0.374/-0.238 0.259/-0.261 0.354/-0.312 0.420/-0.344

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 18

6 7 8 9 10

Empirical formula C90H84N20Na3O42S12 C104H112Cl12Co3N32

Na3O46S12

C98H118Cl6Fe1.50N24

Na3O44S12

C96H116Cl6Fe1.50N28

Na3O44S12

C104H108Cl9Cu2.25N32

Na3O46S12

Formula weight 2571.46 3602.14 3086.33 3116.33 3457.93

Temperature (K) 100(2) 100(2) 100(2) 100(2) 12(2)

X-ray wavelength (Å) 0.71073 0.71073 0.71073 0.71073 0.41328

Crystal system Cubic Tetragonal Tetragonal Tetragonal Tetragonal

Space group I

4 3m I

4 2m I

4 2m I

4 2m I

4 2m

Unit cell dimensions (Å) a = 26.7654(12) a = 27.4332(17) a = 27.029(3) a = 27.147(4) a = 27.161(3)

c = 26.3029(18) c = 27.103(4) c = 26.802(4) c = 26.431(5)

Volume (Å3) 19174.4(15) 19795(2) 19801(4) 19752(5) 19499(5)

Z 4 4 4 4 4

Density (cal.) (mg/m3) 0.891 1.209 1.035 1.048 1.178

Abs. coefficient (mm-1) 0.200 0.612 0.387 0.389 0.110

F(000) 5300 7352 6368 6424 7069

Crystal size (mm3) 0.26 × 0.26 × 0.26 0.26 × 0.25 × 0.14 0.26 × 0.15 × 0.14 0.23 × 0.20 × 0.10 0.10 × 0.10 × 0.08

Theta range (°) 1.52 to 19.11 1.05 to 27.00 1.50 to 20.87 1.06 to 23.38 0.90 to 14.32

Reflections collected 40433 188181 59217 50993 75184

Unique reflections (Rint) 1484 (0.0428) 11130 (0.0626) 5444 (0.0674) 7432 (0.0832) 8741 (0.1252)

Data completeness (%) 99.9 100.0 99.9 99.8 97.1

Goodness-of-fit on F2 1.071 1.081 1.473 1.061 1.027

R1/wR2 [I > 2sigma(I)] 0.1342/0.3380 0.0632/0.1780 0.1298/0.3426 0.1073/0.2743 0.0873/0.2243

Largest diff. peak/hole (e/Å3) 0.428/-0.332 0.885/-0.568 0.611/-0.456 0.715/-0.445 0.838/-1.415

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 19

11 12 13 14 15

Empirical formula C117H147Al1.5N29Na3

O51S12

C90H84N20Na3O42S12 C90H84Bi2.50I5N20

Na3O42S12

C90H84I5N20Na3O42

Pb2.5S12

C90H84HgI2.5N20Na3

O42S12

Formula weight 3269.80 2571.46 3728.41 3723.94 3089.30

Temperature (K) 100(2) 100(2) 120(2) 100(2) 100(2)

X-ray wavelength (Å) 0.71073 0.71073 0.41328 0.71073 0.71073

Crystal system Cubic Cubic Cubic Cubic Cubic

Space group I

4 3m I

4 3m I m I

4 3m I

4 3m

Unit cell dimensions (Å) a = 26.8543(19) a = 26.8145(14) a = 26.7375(13) a = 26.7455(11) a = 26.7620(15)

Volume (Å3) 19366(2) 19280.1(17) 19114.5(16) 19131.6(14) 19167.1(19)

Z 4 4 4 4 4

Density (cal.) (mg/m3) 1.121 0.886 1.296 1.293 1.071

Abs. coefficient (mm-1) 0.222 0.199 0.739 3.198 1.400

F(000) 6818 5300 7190 7180 6150

Crystal size (mm3) 0.36 × 0.31 × 0.30 0.35 × 0.31 × 0.30 0.18 × 0.14 ×0.12 0.29 × 0.28 × 0.24 0.18 × 0.15 × 0.10

Theta range (°) 1.52 to 23.61 1.52 to 22.10 0.89 to 12.56 1.87 to 21.66 1.08 to 23.28

Reflections collected 68046 67807 127863 112072 57548

Unique reflections (Rint) 2684 (0.0380) 2231 (0.0798) 2174 (0.1386) 2087 (0.0586) 2559 (0.0531)

Data completeness (%) 99.9 99.9 100.0 99.8 100.0

Goodness-of-fit on F2 1.071 1.070 1.090 1.080 1.054

R1/wR2 [I > 2sigma(I)] 0.1027/0.2715 0.1478/0.3725 0.3095/0.6278 0.1518/0.3780 0.1242/0.3299

Largest diff. peak/hole (e/Å3) 0.525/-0.344 0.555/-0.623 1.331/-0.844 0.906/-0.796 0.773/-0.760

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 20

Section S9. Thermal gravimetric analysis

Figure S9.1. Thermogravimetric Analysis (TGA) spectrum of a crystal of compound 1 collected during variable

temperature heating ramps (bottom of plot). The total mass loss prior to 200 oC may be attributed to 12 DMF

molecules, 12 dimethyl ammonium chloride or nitrate, 2 formic acid (from NMR) and approximately 18 water

molecules (from this TGA) for each quasi-truncated octahedron.

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 21

Section S10. Powder X-ray diffraction Variable temperature powder X-ray diffraction measurements were performed at the European Synchrotron Radiation Facility (ESRF) in Grenoble on BeamLine D8, using a Debye-Scherrer type diffractometer. The radiation wavelength of the incident X-rays was 0.7277 Å, and the 2θ range was from 1° to 40°. The powder sample was loaded into a glass capillary with a 0.5 mm inner diameter and heated at 2K/min from ambient temperature to 475K.

Figure S10.1. Variable temperature in-situ synchrotron radiation X-ray powder diffraction of compound 1 acquired

upon heating from ambient to 473K at 2 K/min. The data reveal that the compound is stable up to 433K (160 oC).

Supramolecular Archimedean Cages Assembled with Seventy-two Hydrogen Bonds 22

Figure S10.2. Synchrotron radiation powder X-ray diffraction pattern collected at 433K. Experimental (crosses),

calculated with Le Bail refinement (red line) and difference (blue line) profiles.

References 33. N. Tugcu, S. K. Park, J. A. Moore, S. M. Cramer, Ind. Eng. Chem. Res. 41, 6482 (2002). 34. V. Z. Vassileva, Thermochim. Acta 399, 57 (2003). 35. S. Torquato, Y. Jiao, Nature 460, 876 (2009). 36. APEXII (version 2009.5). Program for Bruker CCD X-ray Diffractometer Control, Bruker AXS Inc., Madison,

WI, 2009. 37. SAINT+ (version 7.60A), Program for reduction of data collected on a Bruker CCD area detector diffractometer,

Bruker AXS Inc., Madison, WI, 2008. 38. G. M. Sheldrick, SADABS, Program for empirical absorption correction of area-detector data, Universität

Göttingen, Germany, 2008. 39. G. M. Sheldrick, SHELXS-97, Program for solution of crystal structures, Universität Göttingen, Germany,

1997. 40. G. M. Sheldrick, SHELXL-97. Program for refinement of crystal structures, Universität Göttingen, Germany,

1997. 41. A. L. Spek, J. App. Cryst. 36, 7 (2003).