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Interaction between cucurbit[6]uril and bispyridinecarboxamide

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Abstract

The interaction between cucurbit[6]uril and N,N′-(m-bispyridinecarboxamide)-1,n-alkane (m = 2, 3, 4; n = 4, 6, 8) has been investigated by 1H-NMR, ESI-MS and single crystal X-ray diffraction method. The results show that cucurbit[6]uril can form pseudorotaxanes with N,N′-(m-bispyridinecarboxamide)-1,6-hexane (m = 2, 3, 4) easily. When the alkyl chain length increases (n = 8), the binding mode is identical, but the binding ability of the host towards guest decreases. In both two cases cucurbit[6]uril shows no selectivity towards positional isomers. However, in the case of n = 4, the binding mode is different, having relations with positional substitution of the guest. Only N,N′-(m-bispyridinecarboxamide)-1,4-butane (m = 2) can form pseudorotaxane with cucurbit[6]uril, while the other two (m = 3, m = 4) form external complex with cucurbit[6]uril. The possible reason for the difference has been discussed.

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  1. CB[6]: 1H-NMR (20%DCl/D2O): 4.495 (Hx, d, 12H, J=15.6Hz), 5.645 (Hy, s, 12H), 5.706 (Hz, s, 12H). FAB-MS: m/z 997 [M+H]+. Anal. calcd. for C36H36N24O12·4H2O: C, 40.45; H, 4.12; N, 31.46. Found: C, 40.61; H, 4.29; N, 31.61. 2-H2BPBu: 1H-NMR (20% DCl/D2O): 1.817 (H2, s, 4H), 3.570 (H1, s, 4H), 8.342 (Hb, t, 2H), 8.724 (Hc, d, 2H), 8.849 (Hd, t, 2H), 9.019 (Ha, d, 2H). FAB-MS: m/z 299 [M+H]+. Anal. calcd. for C16H18N4O2: C, 64.43; H, 6.04; N, 18.79. Found: C, 64.46 ; H, 6.54 ; N, 18.85. 2-H2BPH: 1H-NMR (20% DCl/D2O): 1.456 (H3, s, 4H), 1.714 (H2, s, 4H), 3.510 (H1, t, 4H), 8.344 (Hb, t, 2H), 8.715 (Hc, d, 2H), 8.849 (Hd, t, 2H), 9.019 (Ha, d, 2H). FAB-MS: m/z 327 [M +H]+. Anal. calcd. for C18H22N4O2: C, 66.26; H, 6.74; N, 17.18. Found: C, 66.24; H, 6.79; N, 17.17. 2-H2BPO: 1H-NMR (20% DCl/D2O): 1.361 (H3, H4, s, 8H), 1.682 (H2, s, 4H), 3.488 (H1, t, 4H), 8.342 (Hb, t, 2H), 8.711 (Hc, d, 2H), 8.848 (Hd, t, 2H), 9.019 (Ha, d, 2H). FAB-MS: m/z 355 [M+H]+. Anal. calcd. for C20H26N4O2: C, 67.42; H, 7.30; N, 15.73. Found: C, 67.26; H, 7.43; N, 15.63. 3-H2BPBu 1H-NMR (20% DCl/D2O): 1.795 (H2, s, 4H), 3.523 (H1, s, 4H), 8.279 (Hc, t, 2H), 9.035 (Hb, Hd, t, 4H), 9.276 (Ha, s, 2H). FAB-MS: m/z 299 [M+H]+. Anal. calcd. for C16H18N4O2: C, 64.43, H, 6.04, N, 18.79. Found: C, 64.73; H, 5.99; N, 18.66. 3-H2PBH: 1H-NMR (20% DCl/D2O): 1.448 (H3, s, 4H), 1.689 (H2, s, 4H), 3.450 (H1, t, 4H), 8.249 (Hc, t, 2H), 9.006 (Hb, Hd, t, 4H), 9.225 (Ha, s, 2H). FAB-MS: m/z 327 [M+H]+. Anal. calcd. for C18H22N4O2: C, 66.26; H, 6.74; N, 17.18. Found: C, 66.24; H, 6.79; N, 17.17. 3-H2BPO: 1H-NMR (20% DCl/D2O): 1.359 (H3, H4, s, 8H), 1.659 (H2, s, 4H), 3.430 (H1, s, 4H), 8.249 (Hc, t, 2H), 9.002 (Hb, Hd, d, 4H), 9.219 (Ha, s, 2H). MS: m/z 355 [M+H]+. Anal. calcd. for C20H26N4O2: C, 67.42; H, 7.30; N, 15.73. Found: C, 67.78; H, 7.25; N, 15.67. 4-H2BPBu 1H-NMR (20% DCl/D2O): 1.796 (H2, s, 4H), 3.531 (H1, s, 4H), 8.452 (Ha, d, 4H), 9.047 (Hb, d, 4H). FAB-MS: m/z 299 [M+H]+. Anal. calcd. for C16H18N4O2 : C, 64.43 ; H, 6.04; N, 18.79. Found: C, 64.25; H, 6.212; N, 18.83. 4-H2BPH. 1H-NMR (20% DCl/D2O): 1.453 (H3, s, 4H), 1.698 (H2, s, 4H), 3.468 (H1, t, 4H), 8.435 (Ha, s, 4H), 9.044 (Hb, s, 4H). FAB-MS: m/z 327 [M+H]+. Anal. calcd. for C18H22N4O2: C, 66.26; H, 6.74; N, 17.18. Found: C, 66.24; H, 6.79; N, 17.17. 4-H2BPO 1H-NMR (20% DCl/D2O): 1.360 (H3, H4, s, 8H), 1.662 (H2, s, 4H), 3.434 (H1, t, 4H), 8.394 (Ha, d, 4H), 9.006 (Hb, d, 4H). FAB-MS: m/z 355 [M+H]+. Anal. calcd. for C20H26N4O2: C, 67.42; H, 7.30; N, 15.73. Found: C, 67.69; H, 7.288; N, 15.68.

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  1. College of Chemistry and Molecular Science, Wuhan University, Wuhan, 430072, P.R. China

    Huijuan Lu, Lei Mei, Gaoyong Zhang & Xiaohai Zhou

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Lu, H., Mei, L., Zhang, G. et al. Interaction between cucurbit[6]uril and bispyridinecarboxamide. J Incl Phenom Macrocycl Chem 59, 81–90 (2007). https://doi.org/10.1007/s10847-007-9296-1

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