and 1% MeCN) the title product 1+ (PF6ꢀ) was obtained
(brown–red solid, 25 mg, 14%). 1H NMR (CD2Cl2,
500 MHz): d = 8.91 (d, 1H, J = 1.5 Hz, bp6), 8.54 (s, 2H, bi2),
8.49 (s, 2H, bi1), 8.48 (d, 1H, J = 6.6 Hz, bp4), 8.42 (d, 1H,
J = 8.3 Hz, bp3), 8.38 (d, 1H, J = 1.5 Hz, bp1), 8.01 (dd, 1H,
J = 8.3, 2.4 Hz, bp5), 7.98 (d, 1H, J = 8.4 Hz, ph2), 7.96
(d, 2H, J = 8.4 Hz, bi3), 7.92 (d, 1H, J = 8.4 Hz, ph5), 7.84
(d, 1H, J = 7.3 Hz, ph6), 7.82 (t, 2H, J = 8.3 Hz, bi4),
7.80 (d, 1H, J = 8.3 Hz, ph1), 7.62 (d, 4H, J = 8.4 Hz,
sp3–sp5), 7.57 (dd, 2H, J = 6.4, 0.7 Hz, bi5), 7.47 (d, 2H, J =
8.6 Hz, sp2), 7.40 (d, 4H, J = 8.8 Hz, mc6), 7.35 (dd, 1H, J =
8.3, 2.2 Hz, bp2), 7.31 (d, 1H, J = 8.6 Hz, ph3), 7.26 (d, 6H,
J = 8.4 Hz, st9), 7.22 (d, 1H, J = 8.8 Hz, ph4), 7.19 (d, 6H,
J = 8.6 Hz, st4), 7.15 (d, 6H, J = 8.6 Hz, st8), 7.15 (d, 2H, J =
8.6 Hz, st2), 7.14 (d, 2H, J = 8.6 Hz, st7), 7.09 (d, 4H, J =
8.8 Hz, bi6), 7.09 (d, 6H, J = 8.8 Hz, st3), 7.08 (d, 2H, J = 9.5 Hz,
sp6), 6.96 (d, 2H, J = 8.1 Hz, sp4), 6.84 (d, 4H, J =
8.6 Hz, bi7), 6.79 (d, 4H, J = 8.8 Hz, mc5), 6.78 (d, 2H,
J = 9 Hz, st1), 6.73 (d, 2H, J = 9 Hz, st6), 6.18 (d, 2H, J =
8.6 Hz, sp1), 4.19 (t, 2H, J = 4.4 Hz, c12), 4.16 (t, 4H, J = 6.2 Hz,
mc1), 4.11 (t, 2H, J = 5 Hz, c7), 3.87 (t, 2H, J = 4.6 Hz, c1),
3.85 (t, 2H, J = 4.4 Hz, c11), 3.83 (t, 2H, J = 4.6 Hz, c8), 3.82
(t, 2H, J = 4.6 Hz, c2), 3.80 (t, 2H, J = 5.7 Hz, mc4), 3.73
(s, 8H, c3–c4–c9–c10), 3.67 (t, 2H, J = 5.3 Hz, c5), 3.59
(d, 2H, J = 5.3 Hz, c6), 1.85 (m, 8H, mc2-mc3), 1.77 (s, 6H,
mc7–mc8), 1.30 (s, 27H, st10), 3.73 (s, 27H, st5). ES-MS m/z =
2672.2933 (calculated 2672.3157 for C179H182CuN6O12+).w
electrochemical studies were performed without any further
purification, due to the relative air- and base- sensitivity of
these copper-based complexes.
1H NMR of [18+][PF6ꢀ] (CD2Cl2, 300 MHz): d = 8.6
(s, 2H), 8.51 (s, 2H), 8.06 (d, 2H, J = 8.3 Hz), 7.94 (d, 2H,
J = 8.5 Hz), 7.93 (t, 2H, J = 8.2, 7 Hz), 7.89 (d, 2H, J = 8.5 Hz),
7.80 (d, 2H, J = 8.3 Hz), 7.65 (d, 2H, J = 7 Hz), 7.51 (d, 4H,
J = 8.7 Hz), 7.41 (d, 4H, J = 8.7 Hz), 7.26 (s, 2H), 7.15
(d, 4H, J = 8.5 Hz), 6.87 (d, 4H, J = 8.7 Hz), 6.81 (d, 4H, J =
8.5 Hz), 6.22 (d, 4H, J = 8.7 Hz), 4.18 (t, 4H, J = 6, 5.7 Hz),
3.81 (t, 4H, J = 6 Hz), 3.4 (s, 6H), 1.83 (m, 8H), 1.3
(s, 6H). ES-MS m/z = 1231.4810 (calculated 1231.4429 for
C79H68CuN4O6+).w
1H NMR of [19+][PF6ꢀ] (CD2Cl2, 300 MHz): d = 9.06
(s, 2H), 9.0 (s, 2H), 8.76 (d, 2H), 8.15 (d, 2H, J = 8.3 Hz), 7.96
(t, 2H, J = 7.9, 7.5 Hz), 7.69 (d, 2H, J = 8.3 Hz), 7.65 (d, 2H,
J = 7.5 Hz), 7.57 (d, 4H, J = 8.5 Hz), 7.38 (d, 2H, J =
8.3Hz), 7.36 (d, 4H, J = 8.3 Hz), 7.20 (d, 4H, J = 8.2 Hz),
7.08 (d, 4H, J = 8.2 Hz), 6.89 (d, 4H, J = 8.3 Hz), 6.61 (d, 4H,
J = 8.2 Hz), 4.01 (m, 4H), 3.86 (m, 4H), 3.86 (s, 6H), 1.87
(m, 8H), 1.7 (s, 6H). ES-MS m/z = 1207.4818 (calculated
1207.4429 for C77H68CuN4O6+).w
Acknowledgements
We are grateful to the CNRS and the Region Alsace for
´
fellowships to F.D. and J.L.
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42 | New J. Chem., 2010, 34, 34–43