Supplementary data
One-pot synthesis-assembly-separation of cucurbit[6]uril via
SO3H-functionalized ionic liquids
Xiao Jiang1, Peipei Li2, Xiumei Liu2, Xinwen Guo1 and Li Liu1*
1
2
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China;
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
E-mail: lliu@dlut.edu.cn
[C3SO3Hmim]HSO4: 1H NMR (400 MHz, D2O) δ 2.17-2.25 (2H, m), 2.82 (2H, t, J = 7.6 Hz), 3.79
(3H, s), 4.26 (2H, t, J = 7.2 Hz), 7.34 (1H, s), 7.41 (1H, s), 8.64 (1H, s). 13C NMR (100 MHz, D2O) δ
24.6, 35.2, 46.7, 47.2, 121.6, 123.2, 135.7.
[C4SO3Hmim]HSO4: 1H NMR (400 MHz, D2O) δ 1.60-1.66 (2H, m), 1.87-1.94 (2H, m), 2.83 (2H, t,
J = 7.6 Hz), 3.77 (3H, s), 4.13 (2H, t, J = 7.2 Hz), 7.32 (1H, s), 7.38 (1H, s), 8.62 (1H, s). 13C NMR
(100 MHz, D2O) δ 20.3, 27.5, 35.1, 48.3, 49.5, 121.6, 123.1, 135.4.
[C3SO3HPy]HSO4: 1H NMR (400 MHz, D2O) δ 1.79-1.87 (2H, m), 2.36 (2H, t, J = 7.4 Hz), 4.14
(2H, t, J = 7.4 Hz), 7.47 (2H, t, J = 7.2 Hz), 7.94 (1H, t, J = 8.0 Hz), 8.24 (2H, d, J = 6.4 Hz). 13C
NMR (100 MHz, D2O) δ 25.6, 46.5, 59.4, 127.9, 143.9, 145.4.
[C3SO3HN111]HSO4: 1H NMR (400 MHz, D2O) δ 1.65-1.69 (2H, m), 2.43 (2H, t, J = 7.2 Hz), 2.59
(9H, s), 2.92 (2H, t, J = 8.6 Hz). 13C NMR (100 MHz, D2O) δ 17.7, 46.5, 52.1, 63.8.
[C3SO3Hmim]pTSA: 1H NMR (400 MHz, D2O) δ 2.19-2.26 (2H, m), 2.30 (3H, s), 2.83 (2H, t, J =
7.4 Hz), 3.79 (3H, s), 4.25 (2H, t, J = 7.2 Hz), 7.27 (2H, d, J = 8.0 Hz), 7.34 (1H, s), 7.41 (1H, s),
7.60 (2H, d, J = 8.0 Hz), 8.63 (1H, s). 13C NMR (100 MHz, D2O) δ 20.0, 24.6, 35.2, 46.7, 47.3, 121.7,
123.3, 124.9, 129.0, 135.7, 139.0, 142.0.
[C3SO3Hmim]BF4: 1H NMR (400 MHz, D2O) δ 2.22-2.29 (2H, m), 2.87 (2H, t, J = 7.4 Hz), 3.83
(3H, s), 4.30 (2H, t, J = 7.0 Hz), 7.38 (1H, s), 7.45 (1H, s), 8.67 (1H, s). 13C NMR (100 MHz, D2O) δ
24.5, 35.0, 46.7, 47.1, 121.5, 123.1, 135.5.
Determination of product distribution by 13C NMR. The 13C NMR resonances for each CB
homologue were more distinguishable than the 1H NMR signals which overlapped substantially.
Hence, the integrals of 13C NMR resonances were compared to determine the product distribution of
CB[n], using correction factors to compensate the integrals of methine peaks attributing to different
CB homologues. After the MW-assisted synthesis in [C3SO3Hmim]HSO4, CB[6] crystallized from
the reaction mixture as a water soluble complex (CB[6]·10H2O·2H2SO4, CCDC 755253).1 The CB[6]
complex (72.6% of CB[6]) was used as standard sample in the 13C NMR quantitative experiments,
together with the standard samples of CB[5] and CB[7]. The method herein enabled the in-situ
determination of CB[n] product distribution by using D2O as co-solvent with ionic liquids. The
accuracy of the correction factors has been verified by ideal applications to mixtures containing
known amounts of CB[5], CB[6] and CB[7]. The correction factors relative to CB[5] are listed in
Table S1, which were calculated based on the integration of methine groups belonging to each CB
homologue in the 13C NMR spectra.
Table S1 13C NMR correction factors for CB[5]–CB[7] in D2O.
CB[n]
CB[5]
CB[6]
Methine (ppm)
68.5
69.8
Correction factor
1.00
0.53
CB[7]
70.8
0.64
Reference
[1] L. Liu, X. Jiang and J. Zhang, CrystEngComm, 2010, 12, 3445.