1
3
CH
(
1
2
). C NMR (75 MHz, CD
3
CN, 288 K) d (ppm) = 149.72
receptor must be rapid on the NMR timescale. Therefore the
signal is a weighted average of the signals of the two species.
NCHN), 132.00, 131.90 (ArC), 127.73, 127.84 (ArCH), 114.02,
13.80 (ArCH), 47.15 (N–CH
1
2
–), 44.70 (N–CH –), 28.63, 26.07
2
The procedure for H NMR titrations was as follows: 1.5 ×
−
+
−6
(–CH
2
–); MS (ESI positive ion, MeCN): m/z 1099 [M − PF
Anal. calcd for C42 24: C, 40.91; H, 3.97; N, 9.18. Found:
C, 40.53; H, 3.89; N, 9.00.
Tetra(bromomethyl)resorcinarene cavitand 12. Tetramethyl-
resorcinarene cavitand (7.00 g, 8.02 mmol) and a catalytic
amount of AIBN were dissolved in 1,2-dichloroethane (150 mL).
6
] .
10 moles of host was dissolved in 500 lL of 9 : 1 CD
H
3
CN–
−
5
H
48
N
8
P
4
F
2
O (so as to avoid deuterium exchange). 3 × 10 moles of
TBA anion salt was dissolved in 400 lL of the same solvent
corresponding to one equivalent having a volume of 20 lL. A
proton NMR of the hostwas recorded andsubsequently aliquots
of the anion solution were added to the host (11 × 0.2 eq., 2 ×
11
0
.4 eq., 2 × 1 eq., 1 × 2 eq. and 1 × 3 eq.). After each addition
NBS (7.00 g, 38.99 mmol) was added portionwise to the solution
which was then stirred at 80 C under N
1
◦
of anion, another H NMR was recorded.
2
for 3 h. Additional
NBS (1.00 g) and AIBN (catalytic amount) were added at this
stage. The orange solution was then stirred at room temperature
for a further 18 h, after which time the solvent was removed
under reduced pressure. The resulting solid was stirred in EtOH
Acknowledgements
We gratefully acknowledge the EPSRC for studentships
(
W.W.H.W and M.S.V.).
(
150 mL) for 2 h and the resulting precipitate filtered off. This
solid was dissolved in CH Cl (20 mL) and layered with EtOH
50 mL) in order to induce crystallisation. The resulting cream
crystals were collected and dried in vacuo (8.05 g, 84%).
2
2
References
(
1 (a) R. Mart
ınez-M a´ nˇ ez and F. Sancen o´ n, Chem. Rev., 2003, 103,
´
1
4419; P. D. Beer and P. A. Gale, Angew. Chem., Int. Ed., 2001,
H NMR (300 MHz, CDCl
.01 (d, J = 6.6 Hz, 4H, OCH
H, ArCH), 4.53 (d, J = 6.9 Hz, 4H, OCH
Br), 2.17 (m, 8H, ArCHCH ), 1.33 (m, 24H, CH
J = 6.9 Hz, 12H, CH ). Anal. calcd for C56
6.16; H, 5.81; Found: C, 56.06; H, 5.68.
Tetra(imidazolylmethyl)resorcinarene cavitand 13. Tetra-
bromomethyl)resorcinarene cavitand 12 (0.10 g, 0.10 mmol) in
THF (10 mL) was added dropwise to a suspension of imidazole
25 mg, 0.40 mmol) and NaOH (0.05 g) in THF (50 mL). The
3
) d (ppm) = 7.11 (s, 4H, ArH),
[Houter]), 4.75 (t, J = 7.8 Hz,
[Hinner]), 4.40 (s, 8H,
), 0.89 (t,
4
0(3), 486; P. A. Gale, Coord. Chem. Rev., 2003, 240, 191; F. P.
6
4
2
Schmidtchen and M. Berger, Chem. Rev., 1997, 97, 1609; P. D.
Beer and D. K. Smith, Prog. Inorg. Chem., 1997, 46, 1; J. L.
Atwood, K. T. Holman and J. W. Steed, Chem. Commun., 1996, 1401;
Supramolecular Chemistry of Anions, ed. A. Bianchi, K. Bowman-
James and E. Garc ´ı a-Esp a˜ na, New York, Chichester, Wiley-VCH,
2
CH
2
2
2
1
3
H
68Br
4
O
8
. H O: C,
2
2
5
1
997; (b) P. D. Beer, Acc. Chem. Res., 1998, 31, 71; A. P. de Silva,
H. Q. N. Guarantee, T. Gunnlaugsson, A. J. Huxley, C. P. McCoy,
J. T. Rademacher and T. R. Rice, Chem. Rev., 1997, 97, 1515.
(
2 (a) C. R. Bondy, P. A. Gale and S. J. Loeb, J. Am. Chem. Soc., 2004,
126, 5030; (b) K. Choi and A. D. Hamilton, Coord. Chem. Rev., 2003,
(
2
40, 101; (c) J. L. Sessler, S. Camiolo and P. A. Gale, Coord. Chem.
mixture was heated under reflux overnight, then the solvent
was removed in vacuo. The resulting residue was redissolved in
Rev., 2003, 240, 17; (d) F. P. Schmidtchen, Org. Lett., 2002, 4, 431.
(a) K. Kavallieratos, C. M. Bertao and R. H. Crabtree, J. Org. Chem.,
3
CH
layer was dried over anhydrous MgSO
powder (0.10 g, yield 96%) was obtained after solvent removal.
2
Cl
2
(50 mL) and washed with water (2× 50 mL). The organic
1
1
999, 64, 1675; (b) T. R. Kelly and M. H. Kim, J. Am. Chem. Soc.,
994, 116, 7072; (c) P. A. Gale, J. L. Sessler, V. Kral and V. Lynch,
4
, filtered and a pale yellow
J. Am. Chem. Soc., 1996, 118, 5140.
1
H NMR (300 MHz, CDCl
3
, 288 K) d (ppm) = 7.38 (s, 4H,
4 (a) S. Ramos, E. Alcalde, G. Doddi, P. Mencarelli and L. Perez-
Garcia, J. Org. Chem., 2002, 67, 8463; (b) M. S. Vickers, K.
Martindale and P. D. Beer, J. Mater. Chem., 2005, 15, 2784.
NCHN), 7.16 (s, 4H, ArH), 6.99 (s, 4H, NCHCHN), 6.87 (s,
4
H, NCHCHN), 5.90 (d, J = 6.6 Hz, 4H, OCH
2
[Houter]), 4.85
5
6
7
(a) S. K. Kim, N. J. Singh, S. J. Kim, H. G. Kim, J. K. Kim, J. W.
Lee, K. S. Kim and J. Yoon, Org. Lett., 2003, 12, 2083; (b) J. Yoon,
S. K. Kim, N. J. Singh, J. W. Lee, Y. J. Yang, K. Chellappan and K. S.
Kim, J. Org. Chem., 2004, 69, 581; (c) J. Y. Kwon, N. J. Singh, H. N.
Kim, S. K. Kim, K. S. Kim and J. Yoon, J. Am. Chem. Soc., 2004,
(
6
2
s, 8H, N–CH ), 4.70 (t, J = 7.8 Hz, 4H, ArCH), 4.08 (d, J =
.9 Hz, 4H, OCH [Hinner]), 2.16 (m, 8H, ArCHCH ), 1.34 (m,
). MS (ESI positive
2
2
2
4H, CH
2
), 0.88 (t, J = 6.9 Hz, 12H, CH
3
+
ion, MeCN): m/z 1137 [M + H ].
1
26, 8892.
Tetrakisimidazolium resorcinarene cavitand 14. Tetra(imida-
zolylmethyl)resorcinarene cavitand 13 (0.10 g, 0.10 mmol) and
(a) S. Yun, H. Ihm, H. G. Kim, C. W. Lee, B. Indrajit, K. S. Oh, Y. J.
Gong, J. W. Lee, J. Yoon, H. C. Lee and K. S. Kim, J. Org. Chem.,
1
-bromohexane (5 mL, excess) in toluene (10 mL) were heated
2
003, 68, 2467; (b) H. Ihm, S. Yun, H. G. Kim, J. K. Kim and K. S.
under reflux for 3 d. The solvent was removed under vacuum
and the residue redissolved in MeOH (10 mL). Saturated
Kim, Org. Lett., 2002, 4, 2897; (c) K. Sato, S. Arai and T. Yamagishi,
Tetrahedron Lett., 1999, 40, 5219; (d) W. W. H. Wong, D. E. Phipps
and P. D. Beer, Polyhedron, 2004, 23, 2821.
NH
precipitate was collected by filtration. A pale yellow powder
0.51 g, yield 37%) was obtained on drying in vacuo.
4
PF
6
(aq., 5 mL) was added to the solution and the resulting
Two examples of tetrakis(imidazolium) macrocycles can be found in
the literature: (a) K. Chellappan, N. J. Singh, I.-C. Hwang, J. W. Lee
and K. S. Kim, Angew. Chem., Int. Ed., 2005, 44, 2899; (b) K. Sato,
T. Onitake, S. Arai and T. Yamagishi, Heterocycles, 2003, 60(4), 779.
(
1
H NMR (300 MHz, CD
NCHN), 7.54 (s, 4H, ArH), 7.38 (s, 8H, NCHCHN), 6.23 (d, J
6.6 Hz, 4H, OCH [Houter]), 5.13 (s, 8H, N–CH
.8 Hz, 4H, ArCH), 4.55 (d, J = 6.9 Hz, 4H, OCH
), 2.16 (m, 8H, ArCHCH
), 1.38 (m, 24H, CH ), 3.15 (m, 24H,
). C NMR (75 MHz, CD CN,
3
CN, 288 K) d(ppm) = 8.53 (s, 4H,
8 P. A. Gale, P. Anzenbacher Jr. and J. L. Sessler, Coord. Chem. Rev.,
2001, 222, 57–102.
9 A. A. Gridnev and I. M. Mihaltseva, Synth. Commun., 1994, 24,
=
2
2
), 4.68 (t, J =
7
4
1
2
[Hinner]),
1
547.
.13 (t, J = 6.9 Hz, 8H, hexyl CH
2
2
),
1
1
0 E. Alcalde, S. Ramos and L. Perez-Garcia, Org. Lett., 1999, 1, 1035;
.82 (m, 8H, hexyl CH
2
2
R. Vilar, Angew. Chem., Int. Ed., 2003, 42, 1460.
1
3
hexyl CH
2
), 0.89 (m, 24H, CH
3
3
1 H. Boerrigter, W. Verboom and D. N. Reinhoudt, J. Org. Chem.,
2
9
88 K) d (ppm) = 153.2, 139.0, 135.5, 123.5, 122.6, 122.4, 121.0,
1
997, 62, 7148.
9.7, 49.7, 42.9, 37.5, 31.8, 30.7, 29.4, 27.2, 25.3, 22.3, 22.1, 13.4
12 C. D. Gutsche, Calixarenes, 1989; T. Harada, J. M. Rudzinski, E.
Osawa and S. Shinkai, J. Chem. Soc., Perkin Trans. 2, 1992, 2109.
13 M. J. Hynes, J. Chem. Soc., Dalton Trans., 1993, 311.
and 13.2 ppm. MS (ESI positive ion, MeCN): m/z 883 [M −
−
2+
−
+
2
PF
6
] , 1912 [M − PF
6
] .
1
4 Wavefunction Inc., 2004, SPARTAN 04 program for PC.
1
15 Z. Otwinowski, W. Minor, Processing of X-Ray Diffraction Data
Collected in Oscillation Mode (Methods Enzymol.), ed C. W. Carter
and R. M. Sweet, Academic Press, 1997, p. 276.
4
.3 H NMR titration protocol
1
H NMR spectroscopic titration experiments were carried out
1
6 A. Altomare, G. Cascarano, G. Giacovazzo, A. Guagliardi, M. C.
at ca. 293 K on a 500 MHz Varian Utility Spectrometer. Data
Burla, G. Ploidori and M. Camalli, J. Appl. Crystallogr., 1994, 27,
were analysed using the computer fitting program EQNMRꢀC
.
4
35.
For further details on the workings of the EQNMR computer
1
7 D. J. Watkin, C. K. Prout, J. R. Carruthers, P. W. Betteridge,
R. I. Cooper, CRYSTALS issue 11, Chemical Crystallography
Laboratory, Oxford, UK, 2001.
13
program please refer to Professor M. J. Hynes. To calculate
stability constants the binding stoichiometry must be known
and the rate of exchange between the complexed and the free
18 T. A. Halgren, J. Comput. Chem., 1996, 17, 616.
4
2 0 8
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 4 2 0 1 – 4 2 0 8