Wei-Jie Zhang, Yi-Lin Pan, Wen-Hui Bi, Tanya K. Ronson, Laura Schneider, Guido H. Clever, Mladen Vinković, Quentin Duez, Cheng-Yong Su, Jonathan R. Nitschke, Kai Wu. “Guest-programmed adaptive reconfiguration in heteroleptic metal–organic cages.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007497/v1

Pentagonal prism 1 [Zn10LA2LC5](NTf2)20
¹H NMR (600 MHz, CD₃CN) δ 8.83 (br), 8.46 (br), 8.32 (br), 8.08 (br), 7.99 (br), 7.93 (br), 7.40 (br), 7.28 (br), 7.02 (br), 6.93 (br), 6.30 (br), 5.94 (br)
¹⁹F NMR (376 MHz, CD₃CN) δ −79.92 (s, CF3)
High-resolution ESI-MS (CH3CN) 624.4 [M−15NTf₂⁻]¹⁵⁺, 688.9 [M−14NTf₂⁻]¹⁴⁺, 763.5 [M−13NTf₂⁻]¹³⁺, 850.6 [M−12NTf₂⁻]¹²⁺, 953.4 [M−11NTf₂⁻]¹¹⁺, 1076.7 [M−10NTf₂⁻]¹⁰⁺, 1227.3 [M−9NTf₂⁻]⁹⁺, 1415.9 [M−8NTf₂⁻]⁸⁺, 1658.2 [M−7NTf₂⁻]⁷⁺
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.79 × 10⁻¹⁰ m² s⁻¹, r = 21.2 Å
Crystal structure All ten ZnII centres have the same Δ or Λ handedness; cage enantiomers are related by inversion; all LC ligands adopt a landscape orientation with no orientational disorder
Top-to-bottom pentatopic-ligand offset Approximately 22°
Dihedral angles between the five LC ligands Approximately 108°
Main, pp. 5–6; SI, pp. 5, 7
Pentagonal prism 2 [Zn10LA2LD5](NTf2)20
¹H NMR (400 MHz, CD₃CN) δ 8.78 (br), 8.54 (br), 8.29 (br), 7.92 (br), 7.46 (br), 6.38 (br), 3.99 (br, OMe)
¹⁹F NMR (376 MHz, CD₃CN) δ −80.03 (s, CF3)
High-resolution ESI-MS (CH3CN) 753.42 [M−14NTf₂⁻]¹⁴⁺, 832.91 [M−13NTf₂⁻]¹³⁺, 925.65 [M−12NTf₂⁻]¹²⁺, 1035.33 [M−11NTf₂⁻]¹¹⁺, 1166.86 [M−10NTf₂⁻]¹⁰⁺, 1327.28 [M−9NTf₂⁻]⁹⁺, 1528.56 [M−8NTf₂⁻]⁸⁺
¹H–¹H NOESY (700 MHz, 298 K, CD₃CN) Correlations between methoxy 8 and protons 9 or 7
¹H–¹³C HSQC (700 MHz, 298 K, CD₃CN) Correlations between imine C signals at ca. 163 ppm and imine proton 5 were used to assign imine proton signals
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.86 × 10⁻¹⁰ m² s⁻¹, r = 20.7 Å
Concentration-dependent ¹H NMR (400 MHz, 298 K, CD₃CN) Dilution did not change NMR spectra significantly
¹H NMR with excess TBAPF6 (400 MHz, 298 K, CD₃CN) No obvious change in the NMR spectra
TWIM-MS (m/z, charge state, CCS) 832.91, 13+, 1807.4 Ų; 925.65, 12+, 1782.7 Ų; 1035.33, 11+, 1769.2 Ų; 1166.86, 10+, 1734.0 Ų; 1327.28, 9+, 1712.6 Ų
cIMS arrival-time distributions Broadened or tailed for all charge states
Crystal structure All ten ZnII centres have the same Δ or Λ handedness; cage enantiomers are related by inversion; all LD ligands adopt a landscape orientation with no orientational disorder
Average neighbouring ZnII distance along the long LD axis 14.7 Å
Average neighbouring ZnII distance along the short axes 13.5 Å
Absorption maxima Correspond to those of A (308 nm) and B (385 nm)
Lifetime 3.0 ns
Main, pp. 4–6, 9; SI, pp. 8, 10–15, 93
Pentagonal prism 3 [Zn10LA2LE5](NTf2)20
¹H NMR (400 MHz, CD₃CN) δ 8.64 (br), 8.36 (br), 8.25 (br), 8.11 (br), 8.04 (br), 7.74 (br), 7.44 (br), 7.25 (br), 6.97 (br), 6.90 (br), 6.29 (br), 5.93 (br)
¹⁹F NMR (376 MHz, CD₃CN) δ −80.02 (s, CF3), −113.48 (br), −113.57 (br), −113.64 (br), −113.87 (br), −113.98 (br), −114.04 (br)
High-resolution ESI-MS (CH3CN) 895.60 [M−12NTf₂⁻]¹²⁺, 1002.37 [M−11NTf₂⁻]¹¹⁺, 1130.60 [M−10NTf₂⁻]¹⁰⁺, 1287.66 [M−12NTf₂⁻]⁹⁺, 1483.36 [M−8NTf₂⁻]⁸⁺, 1735.25 [M−7NTf₂⁻]⁷⁺
Variable-temperature ¹⁹F NMR (376 MHz, CD₃CN) Many more than three signals were observed
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.96 × 10⁻¹⁰ m² s⁻¹, r = 20.0 Å
Main, p. 5; SI, pp. 17–20
Pentagonal prism 6 [Zn10LA2LF5](NTf2)20
¹H NMR (600 MHz, CD₃CN) δ 9.56 (br), 9.24 (br), 8.78–8.75 (br), 8.62–8.60 (br), 8.31–8.29 (br), 8.21–8.18 (br), 8.02–7.99 (br), 7.90 (br), 7.81 (br), 7.58 (br), 7.30 (br)
¹⁹F NMR (376 MHz, CD₃CN) δ −79.92 (s, CF3)
High-resolution ESI-MS (CH3CN) 871.4 [M−17NTf₂⁻]¹⁷⁺, 943.4 [M−16NTf₂⁻]¹⁶⁺, 1025.0 [M−15NTf₂⁻]¹⁵⁺, 1118.2 [M−14NTf₂⁻]¹⁴⁺, 1225.8 [M−13NTf₂⁻]¹³⁺, 1351.2 [M−12NTf₂⁻]¹²⁺, 1499.5 [M−11NTf₂⁻]¹¹⁺, 1677.4 [M−10NTf₂⁻]¹⁰⁺, 1895.0 [M−9NTf₂⁻]⁹⁺
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.49 × 10⁻¹⁰ m² s⁻¹, r = 23.8 Å
Emission maximum in acetonitrile 540 nm
Photoluminescence quantum yield 5.5 %
Lifetime at 540 nm 4.4 ns
Main, pp. 8–9; SI, pp. 21, 23
(G3)2⊂4, direct assembly
¹H NMR (600 MHz, CD₃CN) δ 8.56 (br), 8.27 (br), 7.93 (br), 7.60 (br), 7.20 (br), 6.73 (br), 6.55 (br), 6.42 (br), 5.58 (br), −0.52 (br, G3), −0.92 (br, G3), −1.22 (br, G3), −1.69 (br, G3)
¹⁹F NMR (376 MHz, CD₃CN) δ −79.92 (s, CF3)
High-resolution ESI-MS (CH3CN) 499.8 [M−15NTf₂⁻]¹⁵⁺, 555.6 [M−14NTf₂⁻]¹⁴⁺, 620.0 [M−13NTf₂⁻]¹³⁺, 695.0 [M−12NTf₂⁻]¹²⁺, 783.6 [M−11NTf₂⁻]¹¹⁺, 890.0 [M−10NTf₂⁻]¹⁰⁺, 1019.9 [M−9NTf₂⁻]⁹⁺, 1182.5 [M−8NTf₂⁻]⁸⁺, 1391.4 [M−7NTf₂⁻]⁷⁺, 1670.0 [M−6NTf₂⁻]⁶⁺
¹H–¹H NOESY (600 MHz, 298 K, CD₃CN) Supports proximity between guest G3 and pseudo-cube 4, consistent with encapsulation
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 3.18 × 10⁻¹⁰ m² s⁻¹, r = 18.6 Å
SI, pp. 24, 27
(G1×G4)⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 721.5 [M−12NTf₂⁻]¹²⁺, 812.4 [M−11NTf₂⁻]¹¹⁺, 921.6 [M−10NTf₂⁻]¹⁰⁺, 1055.0 [M−9NTf₂⁻]⁹⁺, 1222.2 [M−8NTf₂⁻]⁸⁺, 1436.6 [M−7NTf₂⁻]⁷⁺, 1723.0 [M−6NTf₂⁻]⁶⁺
¹H–¹H NOESY (600 MHz, 298 K, CD₃CN) Provides supporting evidence for proximity between guest G4 and pseudo-cube 4, consistent with co-encapsulation of the two guests
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.96 × 10⁻¹⁰ m² s⁻¹, r = 20.0 Å
Other host–guest complexes No G1⊂4 or G4⊂4 signals were observed by HR-ESI-MS
Main, p. 9; SI, pp. 28, 30–31
(G1×G5)⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 578.1 [M−14NTf₂⁻]¹⁴⁺, 644.1 [M−13NTf₂⁻]¹³⁺, 721.1 [M−12NTf₂⁻]¹²⁺, 812.2 [M−11NTf₂⁻]¹¹⁺, 921.4 [M−10NTf₂⁻]¹⁰⁺, 1054.9 [M−9NTf₂⁻]⁹⁺, 1221.9 [M−8NTf₂⁻]⁸⁺, 1437.6 [M−7NTf₂⁻]⁷⁺, 1722.5 [M−6NTf₂⁻]⁶⁺
¹H–¹H NOESY (600 MHz, 298 K, CD₃CN) Provides supporting evidence for proximity between guest G5 and pseudo-cube 4, consistent with co-encapsulation of the two guests
SI, pp. 32, 34
(G1×G6)⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 577.8 [M−14NTf₂⁻]¹⁴⁺, 643.9 [M−13NTf₂⁻]¹³⁺, 720.8 [M−12NTf₂⁻]¹²⁺, 811.8 [M−11NTf₂⁻]¹¹⁺, 921.0 [M−10NTf₂⁻]¹⁰⁺, 1054.5 [M−9NTf₂⁻]⁹⁺, 1221.3 [M−8NTf₂⁻]⁸⁺, 1435.7 [M−7NTf₂⁻]⁷⁺, 1722.0 [M−6NTf₂⁻]⁶⁺
SI, p. 35
G7⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 682.4 [M−12NTf₂⁻]¹²⁺, 769.9 [M−11NTf₂⁻]¹¹⁺, 875.0 [M−10NTf₂⁻]¹⁰⁺, 1003.3 [M−9NTf₂⁻]⁹⁺, 1163.6 [M−8NTf₂⁻]⁸⁺, 1370.1 [M−7NTf₂⁻]⁷⁺, 1645.1 [M−6NTf₂⁻]⁶⁺
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.96 × 10⁻¹⁰ m² s⁻¹, r = 20.0 Å
SI, pp. 36–37
(G1×G4)⊂5, direct assembly
High-resolution ESI-MS (CH3CN) 793.5 [M−15NTf₂⁻]¹⁵⁺, 870.1 [M−14NTf₂⁻]¹⁴⁺, 958.7 [M−13NTf₂⁻]¹³⁺, 1061.8 [M−12NTf₂⁻]¹²⁺, 1183.8 [M−11NTf₂⁻]¹¹⁺, 1130.2 [M−10NTf₂⁻]¹⁰⁺, 1509.1 [M−9NTf₂⁻]⁹⁺, 1732.8 [M−8NTf₂⁻]⁸⁺
Average Cl···π interaction distance 3.08 Å
Labelled Cl···π interaction distances 3.11(8) and 3.04(8) Å
Labelled π···π interaction distance 4.31(4) Å
High-resolution ESI-MS (CH3CN), other host–guest complexes No (G1)2⊂5 or (G4)2⊂5 peaks were observed
Main, pp. 6, 9; SI, p. 38
G1⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 507.1 [M−15NTf₂⁻]¹⁵⁺, 563.3 [M−14NTf₂⁻]¹⁴⁺, 628.2 [M−13NTf₂⁻]¹³⁺, 703.8 [M−12NTf₂⁻]¹²⁺, 793.2 [M−11NTf₂⁻]¹¹⁺, 900.5 [M−10NTf₂⁻]¹⁰⁺, 1031.6 [M−9NTf₂⁻]⁹⁺, 1195.5 [M−8NTf₂⁻]⁸⁺, 1406.5 [M−7NTf₂⁻]⁷⁺, 1687.5 [M−7NTf₂⁻]⁶⁺
SI, p. 39
(G4)2⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 693.1 [M−12NTf₂⁻]¹²⁺, 781.5 [M−11NTf₂⁻]¹¹⁺, 887.7 [M−10NTf₂⁻]¹⁰⁺, 1017.5 [M−9NTf₂⁻]⁹⁺, 1179.6 [M−8NTf₂⁻]⁸⁺, 1388.1 [M−7NTf₂⁻]⁷⁺
SI, p. 40
(G5)2⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 617.9 [M−13NTf₂⁻]¹³⁺, 692.7 [M−12NTf₂⁻]¹²⁺, 781.1 [M−11NTf₂⁻]¹¹⁺, 887.1 [M−10NTf₂⁻]¹⁰⁺, 1016.9 [M−9NTf₂⁻]⁹⁺, 1178.9 [M−8NTf₂⁻]⁸⁺, 1387.4 [M−7NTf₂⁻]⁷⁺
SI, p. 40
(G6)3⊂4, direct assembly
High-resolution ESI-MS (CH3CN) 798.9 [M−11NTf₂⁻]¹¹⁺, 906.7 [M−10NTf₂⁻]¹⁰⁺, 1038.6 [M−9NTf₂⁻]⁹⁺, 1203.3 [M−8NTf₂⁻]⁸⁺, 1415.1 [M−7NTf₂⁻]⁷⁺
SI, p. 41
G1⊂1
High-resolution ESI-MS (CH3CN) 728.1 [M−14NTf₂⁻]¹⁴⁺, 805.6 [M−13NTf₂⁻]¹³⁺, 895.9 [M−12NTf₂⁻]¹²⁺, 1002.9 [M−11NTf₂⁻]¹¹⁺, 1131.3 [M−10NTf₂⁻]¹⁰⁺, 1288.2 [M−9NTf₂⁻]⁹⁺, 1484.3 [M−8NTf₂⁻]⁸⁺, 1736.2 [M−7NTf₂⁻]⁷⁺
Cl···π interaction distance 3.17(3) Å
Phenyl-ring torsion angle near the binding site 8°, compared with 28° for empty 1
Main, pp. 6, 10; SI, p. 42
G2⊂1
High-resolution ESI-MS (CH3CN) 725.4 [M−14NTf₂⁻]¹⁴⁺, 802.7 [M−13NTf₂⁻]¹³⁺, 893.0 [M−12NTf₂⁻]¹²⁺, 999.6 [M−11NTf₂⁻]¹¹⁺, 1127.6 [M−10NTf₂⁻]¹⁰⁺, 1284.1 [M−9NTf₂⁻]⁹⁺, 1479.5 [M−8NTf₂⁻]⁸⁺, 1731.0 [M−7NTf₂⁻]⁷⁺
Cl···π interaction distance 3.16(3) Å
Main, p. 6; SI, p. 43
BPh4−·2
High-resolution ESI-MS (CH3CN) 697.5 [M−15BPh₄⁻]¹⁵⁺, 770.2 [M−14BPh₄⁻]¹⁴⁺, 854.0 [M−13BPh₄⁻]¹³⁺, 951.7 [M−12BPh₄⁻]¹²⁺, 1067.4 [M−11BPh₄⁻]¹¹⁺, 1205.9 [M−10BPh₄⁻]¹⁰⁺, 1375.5 [M−9BPh₄⁻]⁹⁺, 1587.1 [M−8BPh₄⁻]⁸⁺, 1859.7 [M−7BPh₄⁻]⁷⁺
SI, p. 44
G1⊂2
High-resolution ESI-MS (CH3CN) 874.96 [M−13NTf₂⁻]¹³⁺, 970.95 [M−12NTf₂⁻]¹²⁺, 1084.76 [M−11NTf₂⁻]¹¹⁺, 1221.32 [M−10NTf₂⁻]¹⁰⁺, 1388.24 [M−9NTf₂⁻]⁹⁺, 1597.01 [M−8NTf₂⁻]⁸⁺
TWIM-MS (m/z, charge state, CCS) 874.96, 13+, 1808.9 Ų; 970.95, 12+, 1785.4 Ų; 1084.76, 11+, 1768.4 Ų; 1221.42, 10+, 1733.0 Ų; 1388.24, 9+, 1710.0 Ų
cIMS arrival-time distributions Broadened or tailed for all charge states
Lifetime 3.9 ns
Main, pp. 4, 7, 9; SI, pp. 44–45, 94
G2⊂2
High-resolution ESI-MS (CH3CN) 789.7 [M−14NTf₂⁻]¹⁴⁺, 872.0 [M−13NTf₂⁻]¹³⁺, 968.1 [M−12NTf₂⁻]¹²⁺, 1081.5 [M−11NTf₂⁻]¹¹⁺, 1217.6 [M−10NTf₂⁻]¹⁰⁺, 1384.1 [M−9NTf₂⁻]⁹⁺, 1592.1 [M−8NTf₂⁻]⁸⁺, 1859.6 [M−7NTf₂⁻]⁷⁺
Main, p. 7; SI, p. 46
G1⊂3
High-resolution ESI-MS (CH3CN) 1052.16 [M−11NTf₂⁻]¹¹⁺, 1185.26 [M−10NTf₂⁻]¹⁰⁺, 1348.17 [M−9NTf₂⁻]⁹⁺, 1551.69 [M−8NTf₂⁻]⁸⁺, 1813.35 [M−7NTf₂⁻]⁷⁺
SI, pp. 49–50
G1⊂6
Low-resolution ESI-MS (CH3CN) 977.9 [M−16NTf₂⁻]¹⁶⁺, 1061.7 [M−15NTf₂⁻]¹⁵⁺, 1157.6 [M−14NTf₂⁻]¹⁴⁺, 1268.3 [M−13NTf₂⁻]¹³⁺, 1397.2 [M−12NTf₂⁻]¹²⁺, 1549.7 [M−11NTf₂⁻]¹¹⁺, 1732.8 [M−10NTf₂⁻]¹⁰⁺, 1956.3 [M−9NTf₂⁻]⁹⁺
Photoluminescence quantum yield 7.3 %
Lifetime at 540 nm 4.4 ns
Main, pp. 8–9; SI, pp. 50–51
Pentagonal prism 2 and G1⊂2
Fluorescence intensity Enhanced upon guest binding
Emission shift upon guest binding Blue shift of 5 nm
Lifetime Increased from 3.0 to 3.9 ns
Main, p. 9
Pentagonal prism 6 and G1⊂6
UV–Vis absorption maxima 240, 276, 343 nm
Fluorescence enhancement upon guest binding 146 %
Lifetime Unchanged at 4.4 ns
Main, pp. 8–9
Pentagonal prisms 2 and 6
Photoluminescence quantum yield under 360 nm excitation Pentagonal prism 6 exhibits a 9-fold enhancement compared with pentagonal prism 2
Main, p. 9
Pentagonal prism 2 with G3
High-resolution ESI-MS (CH3CN), (G3)2⊂4 889.97 [M−10NTf₂⁻]¹⁰⁺, 1019.96 [M−9NTf₂⁻]⁹⁺, 1182.57 [M−8NTf₂⁻]⁸⁺, 1391.49 [M−7NTf₂⁻]⁷⁺, 1670.06 [M−6NTf₂⁻]⁶⁺
Host–guest complex between G3 and 2 No evidence was observed by HR-ESI-MS
Main, p. 8; SI, pp. 46–47
Pentagonal prism 2 with G4
High-resolution ESI-MS (CH3CN), (G4)2⊂4 781.9 [M−11NTf₂⁻]¹¹⁺, 887.9 [M−10NTf₂⁻]¹⁰⁺, 1017.7 [M−9NTf₂⁻]⁹⁺
Ion sets Principal ions correspond to empty prism 2; a minor set corresponds to (G4)2⊂4
SI, pp. 47–48
Pentagonal prism 2 with G5
High-resolution ESI-MS (CH3CN), (G5)2⊂4 692.9 [M−12NTf₂⁻]¹²⁺, 781.4 [M−11NTf₂⁻]¹¹⁺, 887.5 [M−10NTf₂⁻]¹⁰⁺, 1017.3 [M−9NTf₂⁻]⁹⁺
Ion sets Principal ions correspond to empty prism 2; a minor set corresponds to (G5)2⊂4
SI, p. 48
Pentagonal prism 2 with G6
High-resolution ESI-MS (CH3CN), (G6)3⊂4 799.0 [M−11NTf₂⁻]¹¹⁺, 907.1 [M−10NTf₂⁻]¹⁰⁺, 1038.8 [M−9NTf₂⁻]⁹⁺
Ion sets Principal ions correspond to empty prism 2; a minor set corresponds to (G6)3⊂4
SI, pp. 48–49
(G3)2⊂4, guest-triggered transformation
High-resolution ESI-MS (CH3CN) 694.82 [M−12NTf₂⁻]¹²⁺, 783.62 [M−11NTf₂⁻]¹¹⁺, 889.97 [M−10NTf₂⁻]¹⁰⁺, 1020.07 [M−9NTf₂⁻]⁹⁺, 1182.57 [M−8NTf₂⁻]⁸⁺, 1391.35 [M−7NTf₂⁻]⁷⁺, 1669.90 [M−6NTf₂⁻]⁶⁺
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 3.16 × 10⁻¹⁰ m² s⁻¹, r = 18.7 Å
SI, pp. 52–53
(G1×G4)⊂4, guest-triggered transformation
High-resolution ESI-MS (CH3CN) 921.60 [M−10NTf₂⁻]¹⁰⁺, 1055.22 [M−9NTf₂⁻]⁹⁺, 1222.11 [M−8NTf₂⁻]⁸⁺, 1436.68 [M−7NTf₂⁻]⁷⁺, 1722.78 [M−6NTf₂⁻]⁶⁺, 2123.51 [M−5NTf₂⁻]⁵⁺
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.96 × 10⁻¹⁰ m² s⁻¹, r = 20.0 Å
Time-dependent high-resolution ESI-MS G1⊂2 signals decreased and (G1×G4)⊂4 signals increased over 24 h under the same measurement conditions
Time-dependent high-resolution ESI-MS, residual G1⊂2 Only very weak peaks were observed
Main, p. 8; SI, pp. 54–56
(G1×G5)⊂4, guest-triggered transformation
High-resolution ESI-MS (CH3CN) 921.41 [M−10NTf₂⁻]¹⁰⁺, 1054.44 [M−9NTf₂⁻]⁹⁺, 1221.86 [M−9NTf₂⁻]⁸⁺, 1436.41 [M−7NTf₂⁻]⁷⁺, 1722.79 [M−6NTf₂⁻]⁶⁺
Main, p. 8; SI, p. 57
(G1×G6)⊂4, guest-triggered transformation
High-resolution ESI-MS (CH3CN) 1054.44 [M−9NTf₂⁻]⁹⁺, 1221.23 [M−8NTf₂⁻]⁸⁺, 1435.83 [M−7NTf₂⁻]⁷⁺, 1721.61 [M−6NTf₂⁻]⁶⁺
Main, p. 8; SI, p. 58
G7⊂4, guest-triggered transformation
High-resolution ESI-MS (CH3CN) 769.87 [M−11NTf₂⁻]¹¹⁺, 874.95 [M−10NTf₂⁻]¹⁰⁺, 1003.27 [M−9NTf₂⁻]⁹⁺, 1163.67 [M−6NTf₂⁻]⁸⁺, 1369.90 [M−7NTf₂⁻]⁷⁺, 1645.03 [M−6NTf₂⁻]⁶⁺
¹H DOSY (400 MHz, 298 K, CD₃CN) D = 2.84 × 10⁻¹⁰ m² s⁻¹, r = 20.8 Å
SI, pp. 59, 61
Cube 4-Co
Wide-sweep ¹H NMR (400 MHz, 298 K, CD₃CN) The NMR peaks are distributed over a larger region due to the paramagnetic nature of the CoII centres
SI, p. 64
(G1×G4)⊂4-Co
Wide-sweep ¹H NMR (400 MHz, 298 K, CD₃CN) The guest-triggered transformed and one-pot synthesized samples have identical spectral features
Encapsulated G4 proton c Split into four sets of signals, indicating that all four protons of c have different chemical environments
SI, pp. 65–66
1-BF4 single crystal
Identification code wjz01m_sq
Empirical formula C₅₄₂H₄₂₀B₄F₅₂N₇₀O₄₂S₁₂Zn₁₀
Formula weight 10655.12
Temperature 100(2) K
Crystal system Monoclinic
Space group C2/c (15)
a 46.7053(5) Å
b 34.2928(7) Å
c 47.8087(5) Å
α 90°
β 91.4610(10)°
γ 90°
Volume 76548.2(19) ų
Z 4
ρcalc 0.925 g cm⁻³
μ 1.163 mm⁻¹
F(000) 21912
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 4.85 to 133.20° (0.84 Å)
Index ranges −55 ≤ h ≤ 55, −40 ≤ k ≤ 40, −51 ≤ l ≤ 56
Reflections collected 405430
Independent reflections 67613, Rint = 0.0920, Rsigma = 0.0367
Completeness to θ = 67.679° 99.9 %
Data / restraints / parameters 67613 / 990 / 3342
Goodness-of-fit on F2 1.162
Final R indexes [I≥2σ(I)] R1 = 0.1296, wR2 = 0.4102
Final R indexes [all data] R1 = 0.1454, wR2 = 0.4429
Largest peak/hole 1.17/−1.55 eÅ⁻³
SI, p. 74
2-PF6 single crystal
Identification code wjz02f_sq
Empirical formula C₆₂₆H₅₇₀F₈₄N₆₆O₅₀P₁₄Zn₁₀
Formula weight 12500.73
Temperature 100(2) K
Crystal system Monoclinic
Space group I2/a (15)
a 51.1963(8) Å
b 35.8366(5) Å
c 52.9973(7) Å
α 90°
β 101.947(2)°
γ 90°
Volume 95128(2) ų
Z 4
ρcalc 0.873 g cm⁻³
μ 1.019 mm⁻¹
F(000) 25816
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 4.28 to 117.87° (0.90 Å)
Index ranges −56 ≤ h ≤ 56, −39 ≤ k ≤ 38, −45 ≤ l ≤ 58
Reflections collected 244368
Independent reflections 68097, Rint = 0.0565, Rsigma = 0.0399
Completeness to θ = 67.679° 99.7 %
Data / restraints / parameters 68097 / 3593 / 3830
Goodness-of-fit on F2 1.015
Final R indexes [I≥2σ(I)] R1 = 0.1152, wR2 = 0.3444
Final R indexes [all data] R1 = 0.1421, wR2 = 0.4115
Largest peak/hole 1.24/−0.58 eÅ⁻³
SI, p. 74
2-AsF6 single crystal
Identification code wjz03e_sq
Empirical formula C₆₀₃.₂H₅₁₃.₄As₁₃F₇₈N₇₇O₄₇.₆Zn₁₀
Formula weight 12711.94
Temperature 100(2) K
Crystal system Monoclinic
Space group I2/a (15)
a 53.0759(4) Å
b 36.1585(4) Å
c 50.9183(5) Å
α 90°
β 103.1990(10)°
γ 90°
Volume 95138.1(16) ų
Z 4
ρcalc 0.887 g cm⁻³
μ 1.282 mm⁻¹
F(000) 25930
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 4.25 to 133.20° (0.84 Å)
Index ranges −63 ≤ h ≤ 63, −39 ≤ k ≤ 43, −50 ≤ l ≤ 60
Reflections collected 287540
Independent reflections 83574, Rint = 0.0567, Rsigma = 0.0421
Completeness to θ = 67.679° 99.5 %
Data / restraints / parameters 83574 / 4662 / 3921
Goodness-of-fit on F2 1.137
Final R indexes [I≥2σ(I)] R1 = 0.1264, wR2 = 0.3802
Final R indexes [all data] R1 = 0.1460, wR2 = 0.4369
Largest peak/hole 1.84/−1.80 eÅ⁻³
SI, p. 74
BPh4·2 single crystal
Identification code wjz04b_sq
Empirical formula C₈₂₆H₆₄₀B₁₂N₆₂O₃₀Zn₁₀
Formula weight 12697.38
Temperature 100(2) K
Crystal system Monoclinic
Space group P21/n (14)
a 40.5903(4) Å
b 54.6292(5) Å
c 56.7313(4) Å
α 90°
β 90.3440(10)°
γ 90°
Volume 125794.6(19) ų
Z 4
ρcalc 0.670 g cm⁻³
μ 0.502 mm⁻¹
F(000) 26520
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 4.12 to 72.74° (1.30 Å)
Index ranges −31 ≤ h ≤ 30, −23 ≤ k ≤ 42, −43 ≤ l ≤ 43
Reflections collected 208298
Independent reflections 59722, Rint = 0.0402, Rsigma = 0.0324
Completeness to θ = 67.679° 99.6 %
Data / restraints / parameters 59722 / 19536 / 8461
Goodness-of-fit on F2 1.165
Final R indexes [I≥2σ(I)] R1 = 0.1275, wR2 = 0.4078
Final R indexes [all data] R1 = 0.1486, wR2 = 0.4583
Largest peak/hole 0.59/−0.35 eÅ⁻³
SI, p. 74
G1⊂1 single crystal
Identification code wjz05m_sq
Empirical formula C₅₆₃.₈H₅₁₅.₂B₁₁.₈Cl₁₂F₅₃.₂N₆₃O₄₇.₈S₂Zn₁₀
Formula weight 11219.54
Temperature 100(2) K
Crystal system Triclinic
Space group P1̅ (2)
a 29.9313(4) Å
b 33.1124(5) Å
c 38.8997(5) Å
α 99.3860(10)°
β 91.5540(10)°
γ 104.5920(10)°
Volume 36716.2(9) ų
Z 2
ρcalc 1.015 g cm⁻³
μ 1.368 mm⁻¹
F(000) 11590
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 4.10 to 100.87° (1.00 Å)
Index ranges −29 ≤ h ≤ 29, −33 ≤ k ≤ 33, −38 ≤ l ≤ 38
Reflections collected 217121
Independent reflections 76052, Rint = 0.0822, Rsigma = 0.0468
Completeness to θ = 67.679° 98.9 %
Data / restraints / parameters 76052 / 14366 / 6995
Goodness-of-fit on F2 1.325
Final R indexes [I≥2σ(I)] R1 = 0.1869, wR2 = 0.4960
Final R indexes [all data] R1 = 0.2144, wR2 = 0.5457
Largest peak/hole 2.54/−0.98 eÅ⁻³
SI, p. 80
G2⊂1 single crystal
Identification code wjz06m_sq
Empirical formula C₅₂₃H₃₆₂B₉Cl₁₀F₃₆N₆₂O₇Zn₁₀
Formula weight 9416.21
Temperature 100(2) K
Crystal system Triclinic
Space group P1̅ (2)
a 30.1478(4) Å
b 33.1143(6) Å
c 38.7591(6) Å
α 100.5180(10)°
β 91.0560(10)°
γ 105.5110(10)°
Volume 36565.9(10) ų
Z 2
ρcalc 0.855 g cm⁻³
μ 1.114 mm⁻¹
F(000) 9658
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 3.96 to 100.87° (1.00 Å)
Index ranges −29 ≤ h ≤ 30, −33 ≤ k ≤ 33, −38 ≤ l ≤ 38
Reflections collected 220954
Independent reflections 75949, Rint = 0.0603, Rsigma = 0.0437
Completeness to θ = 67.679° 99.2 %
Data / restraints / parameters 75949 / 12898 / 5918
Goodness-of-fit on F2 1.320
Final R indexes [I≥2σ(I)] R1 = 0.1768, wR2 = 0.5150
Final R indexes [all data] R1 = 0.2124, wR2 = 0.5679
Largest peak/hole 1.52/−0.74 eÅ⁻³
SI, p. 80
(G1×G4)⊂5 single crystal
Identification code wjz07b_sq
Empirical formula C₇₉₄H₄₆₀Cl₁₂N₄₈Zn₈
Formula weight 11620.43
Temperature 100(2) K
Crystal system Monoclinic
Space group Pn (7)
a 29.8557(7) Å
b 29.8569(10) Å
c 56.8853(11) Å
α 90°
β 89.949(2)°
γ 90°
Volume 50707(2) ų
Z 2
ρcalc 0.761 g cm⁻³
μ 0.809 mm⁻¹
F(000) 12008
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Yellow
Crystal shape Block
Radiation CuKα (λ = 1.54184 Å)
2θ range 4.19 to 53.93° (1.70 Å)
Index ranges −17 ≤ h ≤ 17, −17 ≤ k ≤ 17, −33 ≤ l ≤ 31
Reflections collected 29268
Independent reflections 16309, Rint = 0.0297, Rsigma = 0.0393
Completeness to θ = 67.679° 95.6 %
Data / restraints / parameters 16309 / 17392 / 7760
Goodness-of-fit on F2 1.325
Final R indexes [I≥2σ(I)] R1 = 0.2126, wR2 = 0.4694
Final R indexes [all data] R1 = 0.2286, wR2 = 0.5457
Largest peak/hole 1.86/−0.58 eÅ⁻³
Data-set completeness qualification 95.6 % due to X-ray damage preventing further data collection; diffraction intensity dropped significantly after around 1.7 Å resolution
SI, pp. 80, 83
G1×G4 single crystal
Identification code wjz08
Empirical formula C₂₆H₁₆Cl₁₂
Formula weight 753.79
Temperature 100.00(10) K
Crystal system Monoclinic
Space group C2/c (15)
a 20.5292(10) Å
b 12.7118(7) Å
c 10.7936(5) Å
α 90°
β 93.041(4)°
γ 90°
Volume 2812.8(2) ų
Z 4
ρcalc 1.780 g cm⁻³
μ 10.982 mm⁻¹
F(000) 1504
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Colourless
Crystal shape Block
Radiation Cu Kα (λ = 1.54184 Å)
2θ range 8.18 to 133.06° (0.84 Å)
Index ranges −24 ≤ h ≤ 17, −15 ≤ k ≤ 14, −12 ≤ l ≤ 12
Reflections collected 14370
Independent reflections 2454, Rint = 0.0674, Rsigma = 0.0302
Completeness to θ = 67.679° 98.9 %
Data / restraints / parameters 2454 / 127 / 172
Goodness-of-fit on F2 1.082
Final R indexes [I≥2σ(I)] R1 = 0.0942, wR2 = 0.2305
Final R indexes [all data] R1 = 0.0992, wR2 = 0.2346
Largest peak/hole 1.82/−0.99 eÅ⁻³
Average Cl···π interaction distance 3.25 Å
Main, p. 9; SI, p. 85
G1×G5 single crystal
Identification code wjz09
Empirical formula C₂₆H₁₄Cl₁₂
Formula weight 751.77
Temperature 100.00(10) K
Crystal system Triclinic
Space group P1̅ (2)
a 12.0624(3) Å
b 16.6273(5) Å
c 16.6773(4) Å
α 63.587(3)°
β 87.482(2)°
γ 70.141(2)°
Volume 2794.66(15) ų
Z 4
ρcalc 1.787 g cm⁻³
μ 11.053 mm⁻¹
F(000) 1496
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Colourless
Crystal shape Block
Radiation Cu Kα (λ = 1.54184 Å)
2θ range 5.97 to 133.20° (0.84 Å)
Index ranges −14 ≤ h ≤ 14, −19 ≤ k ≤ 19, −19 ≤ l ≤ 19
Reflections collected 32481
Independent reflections 9863, Rint = 0.0385, Rsigma = 0.0289
Completeness to θ = 67.679° 99.9 %
Data / restraints / parameters 9863 / 0 / 685
Goodness-of-fit on F2 1.035
Final R indexes [I≥2σ(I)] R1 = 0.0486, wR2 = 0.1372
Final R indexes [all data] R1 = 0.0506, wR2 = 0.1385
Largest peak/hole 1.25/−1.24 eÅ⁻³
SI, p. 85
G1×G6 single crystal
Identification code wjz10
Empirical formula C₂₆H₁₀Cl₁₂
Formula weight 747.74
Temperature 100.00(10) K
Crystal system Triclinic
Space group P1̅ (2)
a 7.9683(3) Å
b 8.3695(3) Å
c 11.3901(4) Å
α 101.759(3)°
β 107.813(3)°
γ 102.600(3)°
Volume 675.20(4) ų
Z 1
ρcalc 1.839 g cm⁻³
μ 11.437 mm⁻¹
F(000) 370
Crystal size 0.2 × 0.2 × 0.2 mm³
Crystal colour Colourless
Crystal shape Block
Radiation Cu Kα (λ = 1.54184 Å)
2θ range 11.32 to 133.16° (0.84 Å)
Index ranges −9 ≤ h ≤ 9, −9 ≤ k ≤ 9, −9 ≤ l ≤ 13
Reflections collected 5615
Independent reflections 2379, Rint = 0.0416, Rsigma = 0.0290
Completeness to θ = 67.679° 99.9 %
Data / restraints / parameters 2379 / 114 / 172
Goodness-of-fit on F2 1.070
Final R indexes [I≥2σ(I)] R1 = 0.0594, wR2 = 0.1567
Final R indexes [all data] R1 = 0.0599, wR2 = 0.1574
Largest peak/hole 1.11/−0.84 eÅ⁻³