The Journal of Organic Chemistry
ARTICLE
evaporated, and the residue was purified by column chromatography
of a two-spin system undergoing mutual exchange. Using the Eyring
plot, activation of enthalpy (ΔH ) and activation of entropy (ΔS ) were
q
q
(
SiO , DCM/MeOH = 99.5:0.5, R = 0.4). The compound was further
2
f
purified by recrystallization from toluene/chloroform (3:1) mixture: yield
determined from the slope and the intercept of the plot, respectively.
1
q
5
9%; mp >300 °C; H NMR (400 MHz, CDCl
3
/TFA = 99.5:0.5) δ =
Activation barrier (ΔG ) for the tumbling process at 298 K was
3
q
q
q
1.93 (s, 12 H, e-H), 2.68 (s, 6 H, g-H), 7.42 (s, 4 H, f-H), 8.17 (d, J = 6.6
determined using ΔG = ΔH ꢀ TΔS .
3
3
Hz, 4 H, c-H), 8.26 (d, J = 8.2 Hz, 4 H, a-H), 8.61 (d, J = 8.2 Hz, 4 H,
b-H), 8.72 (d, J = 8.8 Hz, 4 H, β1-H), 8.73 (d, J = 8.8 Hz, 4 H, β2-H),
3
3
’
ASSOCIATED CONTENT
Supporting Information. H NMR, C NMR, ESI-MS,
3
13
9
9
1
1
1
1
3
.03 (d, J = 6.6 Hz, 4 H, d-H); C NMR (100 MHz, CDCl /TFA =
9.5:0.5) δ = 21.1, 21.5, 87.3, 104.1, 110.0, 112.9, 115.7, 118.5, 121.1,
21.8, 122.1, 128.8, 129.1, 129.5, 132.6, 138.1, 140.0, 141.1, 141.6, 145.0,
45.8; IR (KBr) ν = 2944 (w), 2918 (s), 2850 (w), 2360 (w), 2343 (w),
612 (w), 1577 (s), 1490 (s), 1428 (w), 1377 (w), 1336 (w), 1204 (s),
1
13
S
b
UVꢀvis, and DOSY for all relevant compounds and aggregates.
This material is available free of charge via the Internet at http://
pubs.acs.org.
ꢀ
1
099 (w), 1064 (w), 998 (s), 884 (w), 851 (s), 798 (s) cm ; ESI-MS:
+
46 6
m/z (%) 964.8 (100) [M + H] . Anal. Calcd for C64H N Zn: C, 79.70;
’
AUTHOR INFORMATION
H, 4.81; N, 8.71. Found: C, 79.33; H, 4.80; N, 8.87.
Complex 1. Compound 2 (2.05 mg, 1.23 μmol) and Cu(CH3-
CN) PF (0.917 mg, 2.46 μmol) were poured in a round-bottomed flask
and dissolved in dry CHCl and dry DCM. Then 3 (1.19 mg, 1.23 μmol)
3
Corresponding Author
*E-mail: schmittel@chemie.uni-siegen.de.
4
6
and DABCO (0.138 mg, 1.23 μmol) were added to the solution. After
the solution was heated at 60 °C for 3 h, the solvent was removed,
’
ACKNOWLEDGMENT
1
furnishing the complex in quantitative yield: mp > 300 °C; H NMR
DABCO
Financial support by the Deutsche Forschungsgemeinschaft
(
(
400 MHz, CD
2
Cl
2
/CDCl
3
9:1) δ = ꢀ4.57 (s, 6 H, CH ), ꢀ4.54
2
DABCO
(Schm 647/15-1) and the University of Siegen is gratefully
acknowledged.
s, 6 H, CH
2
), 1.10 (s, 6 H, mes-CH ), 1.11 (s, 6 H, mes-CH ),
3 3
1
.72 (s, 6 H, mes-CH ), 1.77 (s, 6 H, mes-CH ), 2.03 (s, 12 H, duryl-
3
3
CH
3
), 2.15 (s, 12 H, duryl-CH
3
), 2.50 (s, 6 H, mes-CH
3
), 2.58 (s, 12 H,
3
mes-CH
3
), 2.63 (s, 12 H, mes-CH
3
), 6.49 (d, J = 5.6 Hz, 4 H, d-H), 7.08
’
REFERENCES
3
(
d, J = 5.6 Hz, 4 H, c-H), 7.13 (s, 4 H, 11-H), 7.32 (s, 4 H, f-H), 7.34 (s,
3
3
(1) (a) Von Delius, M.; Leigh, D. A. Chem. Soc. Rev. 2011,
4
H, k-H), 7.57 (d, J = 8.0 Hz, 4 H, [a or b]-H), 7.97 (d, J = 8.0 Hz, 4 H,
4
(
2
0, 3656–3676. (b) Ma, X.; Tian, H. Chem. Soc. Rev. 2010, 39, 70.
c) Balzani, V.; Credi, A.; Venturi, M. Molecular Devices and Machines,
nd ed.; Wiley-VCH: Weinheim, 2008. (d) Ballardini, R.; Balzani, V.;
Credi, A.; Gandolfi, M. T.; Venturi, M. Acc. Chem. Res. 2001, 34, 445.
3
3
[b or a]-H), 8.00 (d, J = 8.0 Hz, 4 H, [l or m]-H), 8.01 (d, J = 8.0 Hz, 2
3
H, [4 or 7]-H), 8.02 (d, J = 8.0 Hz, 2 H, [7 or 4]-H), 8.25 (s, 4 H, 5-,
3
3
6
-H), 8.29 (d, J = 8.0 Hz, 4 H, [m or l]-H), 8.37 (d, J = 4.6 Hz, 4 H,
0
3
0
3
0
β -H), 8.38 (d, J = 4.6 Hz, 4 H, β -H), 8.56 (d, J = 4.6 Hz, 4 H, β -H),
(e) Urry, D. W. Angew. Chem., Int. Ed. 1993, 32, 819.
3
0
3
8.57 (d, J = 4.6 Hz, 4 H, β -H), 8.78 (d, J = 8.0 Hz, 2 H, [3 or 8]-H),
(2) (a) Fang, L.; Wang, C.; Fahrenbach, A. C.; Trabolsi, A.; Botros,
3
13
8.80 (d, J = 8.0 Hz, 2 H, [8 or 3]-H); C NMR (100 MHz, CD
2
Cl
2
/
Y. Y.; Stoddart, J. F. Angew. Chem., Int. Ed. 2011, 50, 1805. (b) Barrell,
M. J.; Campana, A. G.; von Delius, M.; Geertsema, E. M.; Leigh, D. A.
Angew. Chem., Int. Ed. 2011, 50, 285.(c) Silvi, S.; Venturi, M.; Credi, A.
Chem. Commun. 2011, 47, 2483. (d) Carrol, G. T.; Pollard, M. M.;
Delden, R. V.; Feringa, B. L. Chem. Sci. 2010, 1, 97. (e) Haberhauer, G.
Angew. Chem., Int. Ed. 2010, 49, 9286. (f) Haberhauer, G.; Kallweit, C.
Angew. Chem., Int. Ed. 2010, 49, 2418. (g) Balzani, V.; Credi, A.; Venturi,
M. Chem. Soc. Rev. 2009, 38, 1542. (h) Kelly, R. T.; De Silva, H.; Silva,
R. A. Nature 1999, 401, 150.
CDCl 9:1) δ = 2.2 (CDABCO), 18.4, 18.8, 20.8, 21.3, 21.5, 21.6, 22.5,
3
2
1
1
1
1
1
2.6, 27.3, 31.7, 39.4, 39.5, 87.1, 88.2, 98.4, 98.9, 116.9, 117.0, 118.0,
18.8, 119.2, 119.5, 120.6, 122.8, 125.5, 126.8, 127.6, 127.7, 127.8, 128.1,
28.6, 128.6, 129.2, 129.4, 130.5, 130.6, 130.9, 132.0, 132.1, 132.6, 134.5,
34.6, 134.9, 136.4, 137.7, 137.9, 138.0, 138.2, 138.9, 139.2, 139.7, 139.8,
40.0, 140.1, 140.2, 140.6, 143.7, 144.0, 144.2, 145.0, 148.8, 149.4, 149.6,
2
49.7, 150.6, 161.3, 161.6; IR (KBr) ν = 3445 (br, H O), 2975 (s), 2847
(
(
(
s), 2306 (br), 2196 (br), 1604 (s), 1595 (s), 1422 (s), 1376 (w), 1340
w), 1258 (s), 1224 (w), 1203 (w), 1153 (s), 1062 (w), 1030 (s), 850
(3) (a) Barin, G.; Coskun, A.; Friedman, D. C.; Olson, M. A.; Colvin,
ꢀ1
2+
M. T.; Carmielli, R.; Dey, S. K.; Bozdemir, O. A.; Wasielewski, M. R.;
Stoddaart, J. F. Chem.—Eur. J. 2011, 17, 213. (b) Jiang, Y.; Guo, G.-B.;
Chen, C.-F. Org. Lett. 2010, 12, 4248. (c) Busseron, E.; Romuald, C.;
Coutrot, F. Chem.—Eur. J. 2010, 16, 10062. (d) Collin, J.-P.; Durola, F.;
Lux, J.; Sauvage, J.-P. Angew. Chem., Int. Ed. 2009, 48, 8532. (e) Periyasamy,
G.; Collin, J.-P.; Sauvage, J.-P.; Levine, R. D.; Remacle, F. Chem.—Eur. J.
2009, 15, 1310. (f) Coutrot, F.; Busseron, E. Chem.—Eur. J. 2009,
15, 5186. (g) Coutrot, F.; Romuald, C.; Busseron, E. Org. lett. 2008,
10, 3741. (h) Hirose, K.; Shiba, Y.; Ishibashi, K.; Doi, Y.; Tobe, Y. Chem.—
Eur. J. 2008, 14, 3427.
w), 797 (s) cm ; ESI-MS: m/z (%) 1435.0 (100) [M ꢀ 2PF
6
] . Anal.
Calcd for C186
4
H
154
Cu F N P Zn 2CH Cl CH CN: C, 67.68; H,
2
12 16
2
2
3
2
2
3
3
.81; N, 7.06. Found: C, 67.57; H, 4.93; N, 7.40.
X-ray Crystal Structure Analysis. X-ray single-crystal diffraction
data for compound 3 was collected on a SIEMENS SMART CCD
diffractometer with Mo Kα radiation. The structure was solved using
2
2
SHELXS-97 and refined by full-matrix least-squares analysis. The
hydrogen atoms were generated theoretically onto the specific atoms
and refined isotropically with fixed thermal factors. The non-hydrogen
atoms were refined with aniosotropic thermal parameters. There are
disordered solvent molecules in the crystal lattice of the compounds,
whose contribution to the structural data was removed by the
(4) (a) Ruangsupapichat, N.; Pollard, M. M.; Harutyunyan, S. R.;
Feringa, B. L. Nature Chem. 2011, 3, 53. (b) Ogi, S.; Ikeda, T.;
Wakabayashi, R.; Shinkai, S.; Takeuchi, M. Eur. J. Org. Chem.
2011, 1831. (c) Ogi, S.; Ikeda, T.; Wakabayashi, R.; Shinkai, S.;
Takeuchi, M. Chem.—Eur. J. 2010, 16, 8285. (d) Otsuki, J.; Komatsu,
Y.; Kobayashi, D.; Asakawa, M.; Miyake, K. J. Am. Chem. Soc. 2010,
23
SQUEEZE function. Further details are provided in the Supporting
Information.
Crystal data for 3: purple crystal; 0.70 ꢁ 0.32 ꢁ 0.22 mm; monoclinic;
1
(
32, 6870. (e) Moraoka, T.; Kinbara, K.; Aida, T. Nature 2006, 440, 512.
f) Koumura, N.; Zijlstra, R. W. J.; Van Delden, R. A.; Harada, N.;
Feringa, B. L. Nature 1999, 401, 152.
5) (a) Guenet, A.; Graf, E.; Kyritsakas, N.; Hosseini, M. W. Chem.—
3
P21/c;a= 27.263 Å, b= 19.990 Å, c= 16.688 Å, β= 103.50°, V= 8842.35 Å ;
ꢀ
3
ꢀ1
T = 164(2) K; Z = 4; Fcal = 1.416 g cm ; μ = 0.344 mm ; 70244 collected
reflections, 9483 independent (R(int) = 0.256), GoF = 0.90, R1 = 0.0843,
wR2 = 0.1712 for I > 2σ(I) and R1 = 0.1918, wR2 = 0.1956 for all data.
Line Shape Analysis and Determination of Activation
(
Eur. J. 2011, 17, 6443. (b) Lang, T.; Graf, E.; Kyritsakas, N.; Hosseini,
M. W. Dalton Trans. 2011, 40, 3517. (c) Lang, T.; Guenet, A.; Graf,
E.; Kyritsakas, N.; Hosseini, M. W. Chem. Commun. 2010, 46, 3508.
19
Barrier. The spectral simulations were performed using the model
7
472
dx.doi.org/10.1021/jo201252q |J. Org. Chem. 2011, 76, 7466–7473