Journal of the American Chemical Society
Article
Macrocycle H8·1e. H8·1e was synthesized by the similar procedure
described for the synthesis of the macrocycle H8·1e (30 mg, 4.1 μmol,
22%). 1H NMR (400 MHz, CDCl3, TMS): δ 12.9 (s, 8H), 8.79
(s, 8H), 7.73 (s, 8H), 7.70 (s, 8H), 6.91 (s, 8H), 7.16 (s, 8H), 4.27
(s, 8H), 4.16 (d, J = 3.6 Hz, 16H), 3.68−3.60 (m, 128H), 3.55−3.53 (m,
32H), 3.43−3.36 (m, 80H), 2.52−2.49 (m, 8H), 1.62−1.53 (m, 56H),
1.40−1.22 (m, 336H), 0.87−0.83 (m, 84H). 13C NMR (100 MHz,
CDCl3/TMS): δ = 160.9, 154.4, 149.1, 138.3, 136.3, 126.4, 119.6,
112.5, 107.8, 103.2, 71.6, 71.2, 70.7, 70.5, 69.3, 69.1, 67.4, 47.4, 40.2,
31.9, 31.7, 29.8, 29.7, 29.6, 25.8, 22.7, 22.6, 14.1. MS (MALDI-TOF,
Matrix: (dithranol, RP-Mode) m/z 7391.9: calcd for C436H764N12O76H
[M + H]+, found: 7391.2. Anal. calcd for C436H764N12O76: C, 70.85; H,
10.42; N 2.27. Found: C, 71.05; H, 10.67; N, 2.25.
coordination with a variety of metals, and the inclusion of guest
molecules into the nanospaces.
EXPERIMENTAL SECTION
Materials and Methods. Synthetic procedures were carried out
under dry nitrogen atmosphere, unless otherwise specified. All reagents
and solvents were purchased at the highest commercial quality available
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and used without further purification, unless otherwise stated. H and
13C NMR spectra were recorded on a JEOL JNM-ECS400 (400 MHz
for H; 100 MHz for 13C) spectrometer at a constant temperature of
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298 K. Tetramethylsilane (TMS) was used as an internal reference for
1H and 13C NMR measurements in CDCl3. MALDI-TOF-MS was per-
formed with an ultraflex III, Bruker Daltonics, and α-CHCA was used as
the matrix. Elemental analyses were performed on a Yanaco MT-6
analyzer. Silica gel column chromatographies and thin-layer (TLC)
chromatography were performed using Merck silica gel 60 and Merck
silica gel 60 (F254) TLC plates, respectively. GPC was performed using
a JAI LC-9204 equipped with JAIGEL columns.
Macrocycle H8·1a. Carbazole 2a (0.17 g, 0.31 mmol) and 3a
(81 mg, 0.31 mmol) were stirred in dry EtOH (23 mL) at reflux for
48 h, then a red precipitate was obtained. The crude product was
filtered and purified by GPC (JAIGEL 2.5H-2.5H, CHCl3) and followed
by recrystallization from ethanol to obtain a red solid as a target
compound H8·1a (95 mg, 31 μmol, 40%) 1H NMR (400 MHz, CDCl3,
TMS): δ 12.8 (s, 8H), 8.78 (s, 8H), 7.72 (s, 8H), 7.67 (s, 8H), 6.96
(s, 8H), 4.31−4.26 (m, 24H), 3.85−3.82 (m, 16H), 3.48 (s, 24H), 3.41
(t, J = 6.4 Hz, 24H), 3.36 (s, 24H), 1.63−1.54 (m, 24H), 1.45−1.41
(m, 24H), 0.92 (t, J = 7.2 Hz, 36H). 13C NMR (100 MHz, CDCl3/
TMS): δ = 161.2, 154.3, 149.0, 138.4, 136.9, 126.4, 119.6, 112.7, 107.6,
104.5, 71.1, 71.0, 69.3, 59.2, 47.4, 43.5, 32.0, 29.7, 19.6, 14.0. MS
(MALDI-TOF, Matrix: dithranol, RP-Mode) m/z 3048.8: calcd for
C172H236N12O36H [M + H]+; found: 3048.0.
Macrocycle H8·1b. H8·1b was synthesized by the similar procedure
described for the synthesis of the macrocycle H8·1a (17 mg, 4.4 μmol,
38%). 1H NMR (400 MHz, CDCl3, TMS): δ 12.7 (s, 8H), 8.84
(s, 8H), 7.73 (s, 16H), 7.26 (s, 3H), 4.30 (s, 2H), 4.06 (m, 3H), 3.42−
3.39 (m, 6H), 3.36 (s, 5H), 1.64 (m, 8H), 1.25−1.21 (m, 54H), 0.88−
0.82 (m, 9H). 13C NMR (100 MHz, CDCl3/TMS): δ = 163.0, 154.5,
143.5, 127.7, 126.7, 119.5, 118.5, 113.0, 107.8, 71.4, 69.1, 47.4, 31.9,
30.0, 29.7, 29.3, 26.4, 22.7, 14.1. MS (MALDI-TOF, Matrix: α-CHCA,
RP-Mode) m/z 3802.8: calcd for C244H380N12O20H [M + H]+; found;
m/z 3801.6. Anal. calcd for C244H380N12O20: C, 77.09; H, 10.07; N
4.42. Found: C, 77.28; H, 10.15; N, 4.32.
Ni Complex Ni4·1d. H8·1d (27 mg, 5.1 mmol) and Ni(OAc)2·4H2O
(5.8 mg, 23 mmol) were dissolved in CHCl3 (3.8 mL) and EtOH
(3.8 mL). The reaction mixture was stirred at 90 °C for 5h. The reac-
tion mixture was filtrated, and a precipitate was washed with CHCl3.
The filtrate was evaporated to obtain a crude product. The crude
product was purified by GPC (JAIGEL 3H-2.5H, CHCl3) to obtain a
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reddish violet solid (25 mg, 4.6 mmol, 88%). H NMR (400 MHz,
CDCl3, TMS): δ 8.18 (s, 8H), 7.88 (s, 8H), 7.36 (s, 8H), 7.24
(s, including CHCl3 8H), 4.30−4.15 (m, 16H), 4.06 (s, 8H) 3.95−
3.85 (m, 16H), 3.82−3.68 (m, 16H), 3.66−3.54 (m, 16H), 3.53−3.32
(m, 64H), 1.72−1.66 (m, 16H), 1.62−1.52 (m, 24H), 1.51−1.36 (m,
24H), 1.38−1.10 (m, 256H), 0.92−0.78 (m, 60H). MS (MALDI-TOF,
Matrix: dithranol, RP-Mode) m/z 5535.6: calcd for C324H532N12Ni4O44H
[M + H]+, found: 5535.7. Anal. calcd for C324H532N12Ni4O44: C, 70.31;
H, 9.69; N 3.04. Found: C, 70.37; H, 9.93; N, 3.19.
Cu Complex Cu4·1d. H8·1d (14 mg, 2.6 mmol) was dissolved in
chloroform (1.9 mL) and ethanol (1.9 mL). Cu(OAc)2 (2.1 mg,
11 mmol) was added to the solution. The reaction mixture was
refluxed for 17.5 h. The solution was filtered through, and the GPC
(JAIGEL, 20 f, 3H-2.5H) was used for the purification. The resultant
residue was further purified by recrystallization from ethanol twice to
afford the target compound as a purple solid (11 mg, 2.0 mmol 75%).
MS (MALDI-TOF, Matrix: dithranol, RP-Mode) m/z 5555.0: calcd
for C324H532Cu4N12O44H [M + H]+, found: 5554.8. Anal. calcd for
C324H532Cu4N12O44: C, 70.07; H, 9.65; N 3.03. Found: C, 70.27; H,
9.72; N 2.83.
Ni Complex Ni4·1e. Ni4·1e was synthesized by the similar procedure
described for the synthesis of the macrocycle Ni4·1d (25 mg, 3.2 μmol,
79%). 1H NMR (400 MHz, CDCl3, TMS): δ 8.16 (s, 8H), 7.91
(s, 8H), 7.36 (s, 8H), 7.16 (s, 8H), 4.14 (s, 16H), 4.05 (s, 8H), 3.65−
3.61 (m, 128H), 3.56−3.54 (m, 32H), 3.45−3.40 (m, 80H), 2.53−
2.47 (m, 8H), 1.66−1.51 (m, 56H), 1.40−1.22 (m, 312H), 0.87−0.83
(m, 84H). 13C NMR (100 MHz, CDCl3/TMS): δ = 160.0, 153.6,
152.2, 150.8, 149.1, 138.6, 136.5, 131.9, 120.6126.4, 119.6, 112.5,
107.8, 103.2, 71.6, 71.2, 70.7, 70.5, 69.3, 69.1, 67.4, 47.4, 40.2, 31.9,
31.7, 29.8, 29.7, 29.6, 25.8, 22.7, 22.6, 14.1. MS (MALDI-TOF, Matrix:
dithranol, RP-Mode) m/z 7618.6: calcd for C436H756N12Ni4O76H
[M + H]+, found: 7617.6. (ESI-TOF MS, NaI was added, positive)
m/z 2562.1: calcd for C436H756N12Ni4O76 ([M + 3Na]3+), found:
2561.7, m/z 1927.3: calcd for C436H756N12Ni4O76 ([M + 4Na]4+),
found: 1927.3, m/z 1546.5: calcd for C436H756N12Ni4O76 ([M + 5Na]5+),
found: 1546.5. Anal. calcd for C436H756N12Ni4O76: C, 68.90; H, 10.00;
N 2.21. Found: C, 68.90; H, 10.16; N, 2.27.
Macrocycle H8·1c. H8·1c was synthesized by the similar procedure
described for the synthesis of the macrocycle H8·1a (37 mg, 27 μmol,
49%). 1H NMR (400 MHz, CDCl3, TMS): δ 12.9 (s, 8H), 8.80
(s, 8H), 7.72−7.70 (m, 16H), 6.89 (s, 16H), 4.28 (s, 8H), 4.09−4.08
(m, 16H), 3.44−3.42 (m, 24H), 3.36−3.35 (m, 24H), 1.89−1.86
(m, 16H), 1.67−1.64 (m, 16H), 1.56−1.21 (m, 368H), 0.90−0.84
(m, 60H). 13C NMR (100 MHz, CDCl3, TMS): δ = 160.6 154.3
149.3, 138.4, 126.4, 119.6, 112.5, 107.7, 103.2, 71.2, 69.7, 69.0, 47.4,
32.0, 30.0, 29.8, 29.7, 29.5, 29.4, 26.5, 26.2, 22.7, 14.1. MS (MALDI-
TOF, α-CHCA, RP-Mode): calcd for C340H572N12O28H [M + H]+,
m/z 5277.4, found; m/z 5277.4 Anal. calcd for C340H572N12O28: C,
77.40; H, 10.93; N 3.19. Found: C, 77.01; H, 10.95; N, 2.94.
Macrocycle H8·1d. H8·1d was synthesized by the similar procedure
described for the synthesis of the macrocycle H8·1a (0.18 g, 34 μmol,
Cu Complex Cu4·1e. Cu4·1e was synthesized by the similar proce-
dure described for the synthesis of the macrocycle Cu4·1d (18 mg,
2.4 μmol, 47%). MS (MALDI-TOF, Matrix: dithranol, RP-Mode) m/z
7638.0: calcd for C436H756Cu4N12O76H [M + H]+, found: 7637.6.
Anal. calcd for C436H756Cu4N12O76: C, 68.57; H, 9.98; N 2.20. Found:
C, 68.55; H, 10.14; N 2.25.
Structural and Thermal Measurements of the Macrocycles.
DSC measurements were carried out under N2 atmosphere with TA
Instruments Q2000 DSC equipped with a RCS 90 cooling accessory,
and the transition temperatures were determined from the second
heating run at a rate of 10 °C/min using Universal Analysis 2000
software. TGA analysis was performed under N2 atmosphere with TA
Instruments TGAQ50 with the temperature raised from 30 to 600 °C
at a rate of 10 °C/min. POM observations were performed with a
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48%). H NMR (400 MHz, CDCl3, TMS): δ 12.8 (s, 8H), 8.79 (s,
8H), 7.73 (s, 8H), 7.69 (s, 8H), 6.96 (s, 8H), 4.29−4.27 (m, 24H),
3.95−3.93 (m, 16H), 3.78−3.76 (m, 16H), 3.64−3.61 (m, 16H), 3.45
(t, J = 6.8 Hz, 16H), 3.41 (t, J = 6.3 Hz, 24H), 3.30 (s, 24H), 1.65−
1.54 (m, 40H), 1.36−1.23 (m, 288H), 0.88−0.84 (m, 60H). 13C NMR
(100 MHz, CDCl3/TMS): δ = 161.2, 154.4, 149.0, 138.4, 137.0, 126.5,
119.6, 112.6, 107.8, 104.6, 71.7, 71.3, 71.0, 70.2, 69.8, 69.5, 69.1, 47.4,
31.9, 31.7, 29.8, 29.7, 29.6, 29.4, 26.4, 25.8, 22.7, 22.6, 14.1, 14.0. MS
(MALDI-TOF, Matrix: α-CHCA, RP-Mode) m/z 5308.9: calcd for
C324H540N12O44H [M + H]+, found: 5310.0. Anal. calcd for
C324H540N12O44: C, 73.32; H, 10.25; N 3.17. Found: C, 73.50; H,
10.19; N, 3.19.
G
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX