19. A mixture of 2,6-diisopropylphenol (178 mg, 1 mmol),
propargyl bromide (130 mg, 1.1 mmol) and potassium carbonate
(1.39 g, 10 mmol) was suspended in anhydrous DMF (25.0 mL).
The mixture was stirred at 80 ◦C for 16 h. After cooling, the
solution was poured into H2O (200 mL). The resulting mixture
was extracted with EtOAc (3 ¥ 20 mL) and the combined organic
phases were washed three times with saturated aqueous NaCl
solution (3 ¥ 100 mL). After drying (MgSO4), the solvent was
removed in vacuo to afford the desired product 19 (210 mg, 99%)
as a colorless oil, which was used immediately in the next step
without further purification.
Collin, C. Dietrich-Buchecker, P. Gavin˜a, M. C. Jimenez-Molero and
J.-P. Sauvage, Acc. Chem. Res., 2001, 34, 477–487; (f) B. L. Feringa,
Acc. Chem. Res., 2001, 34, 504–513; (g) T. R. Kelly, Acc. Chem. Res.,
2001, 34, 514–522; (h) V. Balzani, A. Credi and M. Venturi, Proc. Natl.
Acad. Sci. U. S. A., 2002, 99, 4814–4817; (i) Y. Shirai, J.-F. Morin,
T. Sasaki, J. M. Guerrero and J. M. Tour, Chem. Soc. Rev., 2006, 35,
1043–1055; (j) V. Balzani, A. Credi, S. Silvi and M. Venturi, Chem.
Soc. Rev., 2006, 35, 1135–1149; (k) W. R. Browne and B. L. Feringa,
Nat. Nanotechnol., 2006, 1, 25–35; (l) E. R. Kay, D. A. Leigh and F.
Zerbetto, Angew. Chem., Int. Ed., 2007, 46, 72–191; (m) S. Saha, K.
C.-F. Leung, T. D. Nguyen, J. F. Stoddart and J. I. Zink, Adv. Funct.
Mater., 2007, 17, 685–693; (n) K. Patel, S. Angelos, W. R. Dichtel, A.
Coskun, Y.-W. Yang, J. I. Zink and J. F. Stoddart, J. Am. Chem. Soc.,
2008, 130, 2382–2383; (o) J. F. Stoddart, Chem. Soc. Rev., 2009, 38,
1802–1820; (p) J. F. Stoddart, Nat. Chem., 2009, 1, 14–15; (q) K. K.
Cot´ı, M. E. Belowich, M. Liong, M. W. Ambrogio, Y. A. Lau, H. A.
Khatib, J. I. Zink, N. M. Khashab and J. F. Stoddart, Nanoscale, 2009,
1, 16–39; (r) M. Liong, S. Angelos, E. Choi, K. Patel, J. F. Stoddart and
J. I. Zink, J. Mater. Chem., 2009, 19, 6251–6257.
2 (a) T. Hugel, N. B. Holland, A. Cattani, L. Moroder, M. Seitz and
H. E. Gaub, Science, 2002, 296, 1103–1106; (b) D. A. Leigh, J. K. Y.
Wong, F. Dehez and F. Zerbetto, Nature, 2003, 424, 174–179; (c) S. P.
Fletcher, F. Dumur, M. M. Pollard and B. L. Feringa, Science, 2005,
310, 80–82; (d) J. Berna´, D. A. Leigh, M. Lubomska, S. M. Mendoza,
E. M. Pe´rez, P. Rudolf, G. Teobaldi and F. Zerbetto, Nat. Mater., 2005,
4, 704–710; (e) M. N. Chatterjee, E. R. Kay and D. A. Leigh, J. Am.
Chem. Soc., 2006, 128, 4058–4073; (f) V. Serreli, C.-F. Lee, E. R. Kay
and D. A. Leigh, Nature, 2007, 445, 523–527; (g) F. Chiaravalloti, L.
Gross, K.-H. Rieder, S. M. Stojkovic, A. Gourdon, C. Joachim and F.
Moresco, Nat. Mater., 2007, 6, 30–33; (h) L. Grill, K.-H. Rieder, F.
Moresco, G. Rapenne, S. M. Stojkovic, X. Bouju and C. Joachim, Nat.
Nanotechnol., 2007, 2, 95–98; (i) G. Fioravanti, N. Haraszkiewicz, E.
R. Kay, S. M. Mendoza, C. Bruno, M. Marcaccio, P. G. Wiering, F.
Paolucci, P. Rudolf, A. M. Brouwer and D. A. Leigh, J. Am. Chem.
Soc., 2008, 130, 2593–2601; (j) M. von Delius, E. M. Geertsema and D.
A. Leigh, Nat. Chem., 2010, 2, 96–101.
3 (a) C. P. Collier, G. Mattersteig, E. W. Wong, Y. Luo, K. Beverly, J.
Sampaio, F. M. Raymo, J. F. Stoddart and J. R. Heath, Science, 2000,
289, 1172–1175; (b) D. W. Steuerman, H.-R. Tseng, A. J. Peters, A. H.
Flood, J. O. Jeppesen, K. A. Nielsen, J. F. Stoddart and J. R. Heath,
Angew. Chem., Int. Ed., 2004, 43, 6486–6491; (c) J. D. Badjic´, V. Balzani,
A. Credi, S. Silvi and J. F. Stoddart, Science, 2004, 303, 1845–1849;
(d) V. Balzani, M. Clemente-Leo´n, A. Credi, B. Ferrer, M. Venturi, A.
H. Flood and J. F. Stoddart, Proc. Natl. Acad. Sci. U. S. A., 2006, 103,
1178–1183; (e) J. E. Green, J. W. Choi, A. Boukai, Y. Bunimovich, E.
Johnston-Halperin, E. Delonno, Y. Luo, B. A. Sheriff, K. Xu, Y. S.
Shin, H.-R. Tseng, J. F. Stoddart and J. R. Heath, Nature, 2007, 445,
414–417; (f) J. R. Heath, Annu. Rev. Mater. Res., 2009, 39, 1–23; (g) S.
J. Van Der Molen and P. Liljeroth, J. Phys.: Condens. Mater., 2010, 22,
1–30; (h) W. Zhang, E. DeIonno, W. R. Dichtel, L. Fang, A. Trabolsi,
J.-C. Olsen, D. Ben´ıtez, J. R. Heath and J. F. Stoddart, J. Mater. Chem.,
2011, 21, 1487–1495.
4 (a) J. O. Jeppesen, J. Perkins, J. Becher and J. F. Stoddart, Angew.
Chem., Int. Ed., 2001, 40, 1216–1221; (b) J. O. Jeppesen, K. A. Nielsen,
J. Perkins, S. A. Vignon, A. di Fabio, R. Ballardini, M. T. Gandolfi,
M. Venturi, V. Balzani, J. Becher and J. F. Stoddart, Chem.–Eur. J.,
2003, 9, 2982–3007; (c) S. Kang, S. A. Vignon, H.-R. Tseng and J. F.
Stoddart, Chem.–Eur. J., 2004, 10, 2555–2564; (d) I. Aprahamian, T.
Yasuda, T. Ikeda, S. Saha, W. R. Dichtel, K. Isoda, T. Kato and J. F.
Stoddart, Angew. Chem., Int. Ed., 2007, 46, 4675–4679; (e) Y.-L. Zhao,
I. Aprahamian, A. Trabolsi, N. Erina and J. F. Stoddart, J. Am. Chem.
Soc., 2008, 130, 6348–6350.
3·6PF6. A solution of 18·2PF6 (32 mg, 0.026 mmol), 19
(80 mg, 0.37 mmol), CBPQT·4PF6 (30 mg, 0.027 mmol), TBTA
(9 mg,0.017 mmol), and tetrakis(acetonitrile)copper(I) hexafluo-
rophosphate (6 mg, 0.017 mmol) in anhydrous Me2CO (5 mL)
were stirred for 24 h at room temperature. The solvent was then
evaporated and the resulting purple solid was purified by column
chromatography [SiO2: 2 M NH4Cl/MeOH/MeNO2 (12 : 7 : 1)],
then MeOH, Me2CO and 2% NH4PF6/Me2CO, respectively]. The
purple fraction in Me2CO were collected, and concentrated to a
minimum volume before the crude product was precipitated by
the addition of H2O. The resulting solid was collected by filtration
1
to afford 3·6PF6 (20 mg, 27%) as a purple powder. H NMR
(500 MHz, CD3CN): d = 1.17 (d, 12H, J = 5.5 Hz), 1.18 (d, 12H,
J = 5.5 Hz), 2.55 (d, 1H, J = 6.0 Hz), 2.59 (d, 1H, J = 6.0 Hz),
3.35–3.40 (m, 4H), 3.90 (t, 2H, J = 3.5 Hz), 3.98 (t, 2H, J = 3.5
Hz), 4.03 (t, 2H, J = 4.5 Hz), 4.14 (t, 2H, J = 4.0 Hz), 4.20–4.23 (m,
4H), 4.27 (t, 2H, J = 3.0 Hz), 4.30 (t, 2H, J = 4.0 Hz), 4.36–4.41
(m, 6H), 4.49 (t, 2H, J = 4.3 Hz), 4.58 (t, 2H, J = 5.0 Hz), 4.73
(t, 2H, J = 4.0 Hz), 4.81 (s, 2H), 4.87 (t, 2H, J = 4.5 Hz), 4.88 (s,
2H), 5.05 (t, 2H, J = 4.3 Hz), 5.78 (d, 4H, J = 11.5 Hz), 5.86 (d,
4H, J = 11.5 Hz), 6.01 (t, 1H, J = 7.0 Hz), 6.05 (t, 1H, J = 7.0 Hz),
6.31 (d, 1H, J = 6.5 Hz), 6.38 (d, 1H, J = 6.5 Hz), 6.86 (t, 2H, J =
6.5 Hz), 7.09–7.15 (m, 6H), 7.31 (t, 2H, J = 7.0 Hz), 7.37 (d, 8H,
J = 5.0 Hz), 7.64 (d, 1H, J = 6.5 Hz), 7.70 (d, 1H, J = 7.0 Hz),
7.84 (d, 2H, J = 7.5 Hz), 7.87 (s, 2H), 7.99 (s, 8H), 8.01 (d, 1H,
J = 6.5 Hz), 8.11 (d, 2H, J = 6.5 Hz), 8.12 (s, 1H), 8.49 (d, 2H,
J = 6.0 Hz), 8.68 (d, 2H, J = 5.5 Hz), 8.74 (b, 8H), 8.99 (d, 2H,
J = 6.0 Hz). 13C NMR (125 MHz, CD3CN): d = 23.3, 23.3, 26.5,
26.5, 28.7, 29.9, 50.1, 54.2, 61.0, 67.2, 67.5, 67.7, 67.9, 69.0, 69.3,
69.3, 69.4, 69.5, 69.8, 70.0, 104.5, 105.6, 105.9, 114.1, 124.1, 124.2,
124.3, 124.4, 124.7, 125.0, 125.2, 125.4, 125.6, 126.5, 129.1, 129.1,
131.3, 136.6, 141.6, 141.9, 143.7, 144.6, 145.0, 145.3, 150.9, 152.7,
152.8, 154.0. HRMS: calcd for C118H128F24N12O10P4 [M - 2PF6]2+
m/z = 1226.9238, found m/z = 1226.9281.
Acknowledgements
The research was supported by the US National Science Foun-
dation (NSF) under grant number CHE-0924620. We thank the
NSF for the award of a graduate research fellowship to A. C. F.
5 (a) H.-R. Tseng, S. A. Vignon and J. F. Stoddart, Angew. Chem., Int.
Ed., 2003, 42, 1491–1495; (b) H.-R. Tseng, S. A. Vignon, P. C. Celestre,
J. Perkins, J. O. Jeppesen, A. di Fabio, R. Ballardini, M. T. Gandolfi,
M. Venturi, V. Balzani and J. F. Stoddart, Chem.–Eur. J., 2004, 10,
155–172.
6 (a) Y. Liu, A. H. Flood, P. A. Bonvallet, S. A. Vignon, B. H. Northrop,
H.-R. Tseng, J. O. Jeppesen, T. J. Huang, B. Brough, M. Baller, S.
Magonov, S. D. Solares, W. A. Goddard III, C.-M. Ho and J. F.
Stoddart, J. Am. Chem. Soc., 2005, 127, 9745–9759; (b) S. Nygaard,
K. C.-F. Leung, I. Aprahamian, T. Ikeda, S. Saha, B. W. Laursen, S.-Y.
Kim, S. W. Hansen, P. C. Stein, A. H. Flood, J. F. Stoddart and J. O.
References
1 (a) V. Balzani, A. Credi, F. M. Raymo and J. F. Stoddart, Angew.
Chem., Int. Ed., 2000, 39, 3348–3391; (b) A. R. Pease, J. O. Jeppesen, J.
F. Stoddart, Y. Luo, C. P. Collier and J. R. Heath, Acc. Chem. Res., 2001,
34, 433–444; (c) R. Ballardini, V. Balzani, A. Credi, M. T. Gandolfi and
M. Venturi, Acc. Chem. Res., 2001, 34, 445–455; (d) C. A. Schalley,
K. Beizai and F. Vo¨gtle, Acc. Chem. Res., 2001, 34, 465–476; (e) J.-R.
ˇ
Jeppesen, J. Am. Chem. Soc., 2007, 129, 960–970; (c) I. Yoon, O. S.
Miljanic´, D. Ben´ıtez, S. I. Khan and J. F. Stoddart, Chem. Commun.,
This journal is
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