T. Kraus, V. Heitz, J.-P. Sauvage et al.
(silica gel, 40 g, CH2Cl2/MeOH 99:1) to give 6 as an amorphous white
material (124 mg, 65% overall yield). 1H NMR (500.13 MHz, CDCl3):
d=8.04 (s, 1H), 8.01 (s, 1H), 7.74 (s, 2H), 7.655 (m, 2H), 7.48 (m, 2H),
AgACTHNGUTERNNUG
(OTf) (2.6 mg, 1.00ꢄ10ꢀ5 mol, 1 equiv) in CD3CN (0.4 mL) was intro-
duced with a syringe (total concentration of compound 9=10ꢀ2 m). The
fluorescence of the solution disappeared as the ligand dissolved. The
progress of the threading reaction was followed by TLC and there was
no remaining starting material after 2 h. Four NMR spectroscopy samples
were prepared with the following concentrations: 10ꢀ2, 5ꢄ10ꢀ3, 10ꢀ3, and
10ꢀ4 m. The mixture of [9+Ag]3·3OTf and [9+Ag]4·4OTf was obtained
quantitatively. For AgI complexes: 1H NMR (500.13 MHz, c=5.10ꢀ3 m in
CD3CN, the temperature of acquisition was 346 K, so the proportion of
trimer (t)/tetramer (T) was modified to t/T=51/49; the proportion was
determined by using the integration of the methoxy group signal).
1H NMR: d=9.25 (d, J=8.5 Hz, 1H; H-7’T), 9.19 (m, 1H; H-7’t), 9.11
(d, J=8.5 Hz, 1H; H-4’T), 9.06 (m, 1H; H-4’t), 8.94 (s, 1H; H-7t), 8.71
(s, 1H; H-7T), 8.64 (s, 1H; H-4T), 8.63 (m, 2H; H-m1T), 8.54 (d, J=
8.0 Hz, 2H; H-m1t), 8.47 (s, 1H; H-4t), 8.35 (m, 2H; H-3’,8’t), 8.30 (m,
2H; H-3’,8’T), 8.26 (s, 1H; H-5T), 8.25 (s, 1H; H-6T), 8.06 (s, 1H; H-5t),
8.05 (s, 1H; H-6t), 7.82 (d, J=8.0 Hz, 2H; H-o1T), 7.77 (m, 2H; H-o’T),
7.70 (m, 6H; H-o1,o’t), 7.61 (d, J=8.0 Hz, 2H; H-o2t), 7.50 (d, J=8.5 Hz,
2H; H-o2T), 7.17 (d, J=8.5 Hz, 2H; H-m2t), 7.13 (d, J=9.0 Hz, 2H; H-
m2T), 6.29 (m, 8H; H-m’T,m’t), 3.94 (s, 3H; H-OMet), 3.91 (s, 3H; H-
OMeT), 3.69–3.25 (m, 40H; H-a,b,g,d,e t and T), 2.60 (s, 3H; H-gt),
2.48 ppm (s, 3H; H-gT); d=2.44 ppm (s, 3H; H-hT); DOSY: diffusion
coefficients values were 390 mm2sꢀ1 for [9+Ag]3·3OTf and 330 mm2sꢀ1 for
[9+Ag]4·4OTf in CD3CN, at 298 K and C=5.10ꢀ3 m; MS (ESI): m/z:
7.40 (m, 2H), 7.04 (m, 2H), 5.505 (s, 1H), 3.90 (s, 3H), 3.83 (dt, J
ACHTUNGTRNE(NUNG gem)=
11.2 Hz, 2H), 3.72 (dm, J(gem)=11.2 Hz, 2H), 2.90 (s, 3H), 2.86 (s, 3H),
AHCTUNGTRENNUNG
1.35 (s, 3H), 0.84 ppm (s, 3H); 13C NMR (125.77 MHz, CDCl3): d=
159.3, ꢁ158.0, ꢁ157.6, ꢁ144.5, ꢁ144.0, ꢁ140.4, 138.0, ꢁ136.9, ꢁ136.8,
136.4, 133.4, 132.2, 130.4, 129.2, 127.2, 127.0, 126.4, 125.8, 125.7, 113.9,
101.5, 77.8, 55.3, 30.3, 23.0, 21.9, 25.2, 25.1 ppm; MS (FAB): m/z: 527
[M+Na]+; elemental analysis calcd (%) for C33H32N2O3: C 78.55, H 6.39,
N 5.55; found: C 78.42, H 6.27, N 5.43.
Compound 7: Compound 6 (102 mg, 0.202 mmol) was dissolved in diox-
ane (2 mL) under argon atmosphere and a 1m aqueous solution of HCl
(2 mL) was added. The solution was heated at 808C for 15 h and cooled
to room temperature. Then it was concentrated under reduced pressure
to about one half of the volume and the remaining suspension was neu-
tralized with NaHCO3. The precipitate was collected and dried in
vacuum to give
7 as a
brown powder (70 mg, 83%). 1H NMR
(500.13 MHz, CDCl3): d=10.13 (s, 1H), 8.09 (s, 1H), 8.06 (s, 1H), 8.04
(m, 2H), 7.78 (d, J=8.7 Hz, 1H), 7.76 (d, J=8.7 Hz, 1H), 7.66 (m, 2H),
7.41 (m, 2H), 7.05 (m, 2H), 3.90 (s, 3H, OCH3), 2.92 (s, 3H), 2.90 ppm
(s, 3H); 13C NMR (125.77 MHz, CDCl3): d=191.8, 159.3, 158.1, 156.8,
146.2, ꢁ144.5, ꢁ143.8, 137.2, 136.5, 135.7, 135.6, 131.9, 130.4, 130.0,
129.9, 127.4, 126.9, 126.2, 125.6, 114.0, 55.4, 25.1 ppm; MS (ESI): m/z: 441
[M+Na]+; elemental analysis calcd (%) for C28H22N2O2: C 80.36, H 5.30,
N 6.69; found: C 80.14, H 5.11, N 6.58.
calcd for [C186H159N15O24Ag3]3+
: 1103.96, found 1104.16; calcd for
[C248H212N20O32Ag4]4+ CF3SO3: 1521.71; found 1521.64.
Computational methods: The equilibrium constant defined by Equa-
tion (1) was expressed in terms of concentrations [Eq. (2)], in which [C4]
and [C3] represent equilibrium concentrations of the tetrameric and tri-
meric cyclic complexes, respectively.
Compound 9: Compounds 7 (15.0 mg, 0.0358 mmol) and 8 (21.4 mg,
0.0359 mmol) were dissolved in anhydrous ethanol (2.5 mL) in a pres-
sure-resistant tube and ammonium acetate (27.6 mg, 0.358 mmol, freshly
purified by sublimation) was added. The reaction mixture was briefly
bubbled with argon, the pressure tube was closed, and heated with stir-
ring at 1008C for 24 h. Then it was evaporated, the residue was dissolved
in chloroform, and charged onto a column (silica, 12ꢄ1 cm, prepared in
chloroform). Gradient elution from chloroform to chloroform/methanol
3
4
ð2Þ
K ¼ ½C4ꢃ =½C3ꢃ
Combining Equation (2) and the mass balance equation [Eq. (3)] allows
the dependence of the concentration of the trimeric species [C3] on [L]
and the equilibrium constant, K, to be expressed [Eq. (4); [L] stands for
the total concentration of ligand 9].
97:3 afforded
9 as a
yellowish solid (21 mg, 59%). 1H NMR
(500.13 MHz, CDCl3): d=8.98 (d, J=8.3, 1H; H-7’), 8.72 (d, J=8.3 Hz,
1H; H-4’), 8.52 (m, 2H; H-m1), 8.46 (d, J=8.9 Hz, 4H; H-o’), 8.21 (m,
3H; H-3’,8’,7), 8.08 (s, 1H; H-4), 7.80 (s, 1H; H-5,6), 7.71 (d, J=8.3 Hz,
2H; H-o1), 7.42 (d, J=8.3 Hz, 2H; H-o2), 7.21 (d, J=8.9 Hz, 4H; H-m’),
7.06 (d, J=8.6 Hz, 2H; H-m2), 4.36 (t, J=5.4 Hz, 4H; H-a), 3.91 (s, 3H;
H-OMe), 3.88 (t, J=5.4 Hz, 4H; H-b), 3.74 (m, 12H; H-g,d,e), 2.99 (s,
3H; H-g), 2.94 ppm (s, 3H; H-h); 13C NMR (125.77 MHz, CDCl3): d=
163.0, 160.4, 160.2, 159.4, 158.0, 157.1, 155.9, 155.8, 144.7, 144.6, 144.0,
143.7, 142.9, 137.0, 136.5, 136.4, 136.0, 134.7, 132.7, 132.4, 132.1, 131.5,
130.4, 130.0, 129.4, 129.0, 128.9, 127.4, 127.4, 127.0, 126.6, 126.1, 125.6,
121.4, 119.6, 119.4, 116.3, 115.68, 115.65, 114.0, 71.3, 70.8, 70.6, 69.6, 67.9,
55.4, 25.3, 25.3 ppm; MS (ESI): m/z: 1020 [M+Na]+; elemental analysis
calcd (%) for C62H53N5O8: C 74.76, H 5.36, N 7.03; found: C 74.48, H
5.18, N 6.87.
4½C4ꢃþ3½C3ꢃ ¼ ½Lꢃ
ð3Þ
ð4Þ
ð5Þ
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ꢀ
ꢁ
u
3
½Lꢃꢀ3½C3
ꢃ
u
4
t
4
½C3ꢃ ¼
K
y ¼ 300½C3ꢃ=½Lꢃ
A unique algebraic solution of Equation (4) for [C3] was found by using
the Derive 6 program (Texas Instruments) under the constraints K2(0,
1); [C3]2[0, 1]; [L]2[0, 1], and implemented in the Origin 7 program
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
Copper(I) complexes: Compound 9 (10 mg, 0.01 mmol, 1 equiv) was in-
troduced in a degassed round-bottomed flask and degassed CD3CN
(0.6 mL) was added by using a syringe. Then a degassed solution of [Cu-
(OriginLab) in the form of Equation (5) (to fit the percentage yields of
the trimeric species with K as a fitting parameter) as a user-defined func-
tion. The fitting function was then tested by using exact-fit data generat-
ed with Equation (4) and the Derive 6 program for arbitrarily chosen
values of K, [L]. Subsequently it was used for fitting the percentage
yields of the trimeric species (Figure 6) experimentally determined in
mixtures of CuI and AgI complexes.
ACHTUNGTRENNUNG(CH3CN)4]ACHTUNGTRENNUNG
[PF6](3.7 mg, 1.00ꢄ10ꢀ5 mol, 1 equiv) in CD3CN (0.4 mL) was
introduced with a syringe (total concentration of compound 9=10ꢀ2 m).
The brown-red color became darker as the ligand dissolved. The progress
of the threading reaction was followed by TLC and there was no remain-
ing starting material after 1 h. NMR spectroscopy samples were prepared
with the following concentrations: 10ꢀ2, 5ꢄ10ꢀ3, 10ꢀ3, and 10ꢀ4 m. The
mixture of [9+Cu]3·3PF6 and [9+Cu]4·4PF6 was obtained quantitatively.
1
For CuI complexes: H NMR data was published in our preliminary com-
Acknowledgements
munication;[19] DOSY: diffusion coefficients values were 380 mm2sꢀ1 for
[9+Cu]3·3PF6 and 320 mm2sꢀ1 for [9+Cu]4·4PF6 in CD3CN, at 298 K and
We thank the Ministry of Education for a fellowship to J.V. and the Eu-
ropean Commission for financial support (Marie Curie fellowship to
T.K.). Financial support from the IOCB (Z40550506) is also appreciated.
C=10ꢀ2 m; UV/Vis:
lACHTUNGTRENNUNG
(3MLCT)=449 nm; MS (ESI): m/z: calcd for
[C186H159N15O24Cu3]3+
:
1059.32;
found:
1059.29;
calcd
for
[C248H212N20O32Cu4]4+: 1059.32; found: 1059.32.
Silver(I) complexes: Compound 9 (10 mg, 0.01 mmol, 1 equiv) was intro-
duced in degassed round-bottomed flask and degassed CD3CN
(0.6 mL) was added by using a syringe. Then a degassed suspension of
a
5412
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5404 – 5414