Metallomacrocycles
FULL PAPER
which were isolated as purple solids. Multiple column chromatograph
separations were necessary to obtain the pure compounds, resulting in
relatively low overall yields.
PhH), 8.26 (s, 12H; PhH), 7.99–8.02 (m, 24H; PyH4,4’’), 7.42–7.43 (d, J=
5.0 Hz, 24H; PyH6,6’’), 7.23–7.25 (m, 24H; PyH5,5’’), 4.60 (m, 12H;
OCH2), 3.54 (m,12H; NCH2), 2.18–2.21 (m, 156H; CH2), 1.92–2.04 (m,
144H; CH2), 1.41 ppm (s, 486H; CH3); 13C NMR (CD3OD, 125 MHz):
d=175.6, 174.6, 162.8, 162.2, 160.4, 159.9, 154.3, 152.1, 141.3, 140.4, 129.1,
125.9, 123.7, 121.9, 117.5, 81.8, 68.5, 58.8, 57.9, 38.0, 33.3, 32.7, 32.4, 30.9,
Data for G1-5: Yield: 11.3 mg, 8%; 1H NMR (CD3OD, 500 MHz): d=
9.64 (s, 20H; PyH3’,5’), 8.95–8.96 (d, J=7.5 Hz, 20H; PyH3,3’’), 8.75 (s, 5H;
PhH), 8.22 (s, 10H; PhH), 7.96–7.99 (m, 20H; PyH4,4’’), 7.38–7.39 (d, J=
5.0 Hz, 20H; PyH6,6’’), 7.20–7.22 (m, 20H; PyH5,5’’), 4.57–4.60 (m, 10H;
OCH2), 3.53–3.55 (t, J=6.3 Hz, 10H; NCH2), 2.25–2.28 (m, 40H; CH2),
1.94–1.98 (m, 30H; CH2), 1.42 ppm (s, 135H; CH3); 13C NMR (CD3OD,
125 MHz): d=174.8, 162.8, 162.2, 160.1, 159.9, 154.3, 153.4, 141.6, 140.3,
128.9, 125.7, 123.9, 123.2, 117.0, 81.8, 68.4, 57.6, 37.9, 31.8, 31.5, 30.9,
ꢀ
5+
30.7, 28.6 ppm; ESI MS: m/z: 2766.1 [Mꢀ5PF6
2280.8 [Mꢀ6PF6 (calcd m/z: 2279.9), 1934.1 [Mꢀ7PF6
1933.5), 1674.3 [Mꢀ8PF6 (calcd m/z: 1673.7), 1472.2 [Mꢀ9PF6
(calcd m/z: 1471.6), 1310.5 [Mꢀ10PF6 (calcd m/z: 1310.0), 1178.2
[Mꢀ11PF6 (calcd m/z: 1177.7).
Synthesis of CdG1-6: A solution of CdACTHNUGTRNE(NGU NO3)2·4H2O (12 mg, 38 mmol) in
]
(calcd m/z: 2764.9),
ꢀ
6+
ꢀ 7+
]
]
(calcd m/z:
ꢀ
8+
ꢀ 9+
]
]
ꢀ
10+
]
ꢀ
11+
]
ꢀ
4+
28.5 ppm; ESI MS: m/z: 1606.7 [Mꢀ4PF6
]
(calcd m/z: 1606.3), 1256.4
ꢀ
5+
ꢀ 6+
MeOH (5 mL) was added to a solution of ligand G1tpy (40 mg, 38 mmol)
in MeOH (10 mL). The mixture was stirred at 258C for 1 h. After remov-
al of solvent in vacuo, white solid was generated. And then dissolved in
MeOH, and excess NH4PF6 was added to generate a white precipitate,
[Mꢀ5PF6 (calcd m/z: 1256.0), 1022.8 [Mꢀ6PF6
]
]
(calcd m/z:
ꢀ
7+
ꢀ 8+
1022.5), 855.9 [Mꢀ7PF6
]
(calcd m/z: 855.7), 730.8 [Mꢀ8PF6
]
(calcd
ꢀ
9+
ꢀ 10+
m/z: 730.7), 633.5 [Mꢀ9PF6
]
(calcd m/z: 633.4), 555.7 [Mꢀ10PF6
]
(calcd m/z: 555.5).
Data for G1-6: Yield: 29.1 mg, 21%; 1H NMR (CD3OD, 500 MHz): d=
9.70 (s, 24H; PyH3’,5’), 8.98–8.99 (d, J=8.0 Hz, 24H; PyH3,3’’), 8.94 (s, 6H;
PhH), 8.26 (s, 12H; PhH), 7.98–8.01 (m, 24H; PyH4,4’’), 7.42–7.43 (d, J=
5.5 Hz, 24H; PyH6,6’’), 7.22–7.24 (m, 24H; PyH5,5’’), 4.58–4.59 (s, J=
6.0 Hz, 12H; OCH2), 3.52–3.55 (t, J=6.5 Hz,12H; NCH2), 2.24–2.27 (m,
48H; CH2), 1.93–1.96 (m, 36H; CH2), 1.42 ppm (s, 162H; CH3);
13C NMR (CD3OD, 125 MHz): d=174.8, 162.8, 162.2, 160.1, 159.9, 154.3,
152.0, 141.3, 140.3, 129.0, 125.8, 123.6, 122.1, 117.4, 81.8, 68.5, 57.6, 37.9,
which was washed with MeOH and water to give the desire CdG1-6 pos-
sessing PF6
ꢀ
,
as the counterions (52 mg, 94%). 1H NMR (CD3CN,
500 MHz): d=9.15 (s, 24H; PyH3’,5’), 8.90–8.92 (d, J=6.9 Hz, 24H;
PyH3,3’’), 8.44 (s, 6H; PhH), 8.18–8.28 (m, 48H; PyH4,4’’, PyH6,6’’), 7.99 (s,
12H; PhH), 7.57 (m, 24H; PyH5,5’’), 4.99–5.03 (t, J=5.7 Hz, 6H; CONH),
4.65 (s, 6H; CONH), 4.47 (m, 12H; OCH2), 3.40–3.42 (m, 12H; NCH2),
2.18 (m, 48H; CH2), 1.82–1.88 (m, 36H; CH2), 1.38 ppm (s, 162H; CH3);
13C NMR (CD3CN, 125 MHz): d=174.1, 162.3, 158.5, 155.9, 151.9, 151.2,
150.2, 142.8, 140.6, 128.9, 125.3, 123.8,121.2, 117.9, 81.2, 68.5, 57.5, 38.1,
ꢀ
4+
31.8, 31.5, 30.9, 28.5 ppm; ESI MS: m/z: 1957.2 [Mꢀ4PF6
z:1956.6), 1536.8 [Mꢀ5PF6 (calcd m/z: 1536.3), 1256.4 [Mꢀ6PF6
(calcd m/z: 1256.1), 1056.1 [Mꢀ7PF6 (calcd m/z: 1056.0), 905.9
[Mꢀ8PF6 (calcd m/z: 905.8), 789.2 [Mꢀ9PF6
695.8 [Mꢀ10PF6 (calcd m/z: 695.7), 619.4 [Mꢀ11PF6
619.3), 555.7 [Mꢀ12PF6 (calcd m/z: 555.6).
]
(calcd m/
ꢀ
3+
ꢀ
5+
ꢀ 6+
31.7, 31.4, 30.9, 28.7; ESI MS: m/z: 2771.2 [Mꢀ3PF6
2770.1), 2042.2 [Mꢀ4PF6 (calcd m/z: 2041.3), 1604.6 [Mꢀ5PF6
(calcd m/z:1604.1), 1312.8 [Mꢀ6PF6 (calcd m/z: 1312.6), 1104.7
[Mꢀ7PF6 (calcd m/z:1104.4).
]
(calcd m/z:
]
]
ꢀ
4+
ꢀ 5+
ꢀ
7+
]
]
]
ꢀ
6+
ꢀ
8+
ꢀ
9+
]
]
]
(calcd m/z: 789.1),
ꢀ
7+
ꢀ
10+
ꢀ
11+
]
]
]
(calcd m/z:
ꢀ
12+
]
Data for G1-7: Yield: 7.1 mg, 5%; 1H NMR (CD3OD, 500 MHz): d=
9.73 (s, 28H; PyH3’,5’), 9.00–9.02 (d, J=7.5 Hz, 35H; PyH3,3’’), 8.28 (s,
14H; PhH), 7.99–8.02 (m, 28H; PyH4,4’’), 7.43–7.44 (d, J=5.0 Hz, 28H;
PyH6,6’’), 7.23–7.25 (m, 24H; PyH5,5’’), 4.57–4.61 (m, 14H; OCH2), 3.52–
3.55 (t, J=6.0 Hz, 14H; NCH2), 2.23–2.26 (m, 56H; CH2), 1.92–1.95 (m,
42H; CH2), 1.41 ppm (s, 189H; CH3); 13C NMR (CD3OD, 125 MHz): d=
174.8, 162.9, 162.2, 160.1, 159.9, 154.2, 151.9, 141.2, 140.4, 129.0, 125.9,
123.5, 121.7, 117.6, 81.8, 68.5, 57.6, 37.9, 31.9, 31.5, 30.9, 28.5 ppm; ESI
Acknowledgements
The authors gratefully thank the National Science Foundation (DMR-
0812337 and DMR-0705015 to G.R.N.; CHE-1012636 and DMR-0821313
to C.W.) and the Ohio Board of Regents for financial support.
ꢀ
6+
ꢀ 7+
MS: m/z: 1489.9 [Mꢀ6PF6
(calcd m/z: 1256.2), 1081.1 [Mꢀ8PF6
[Mꢀ9PF6 (calcd m/z: 944.8), 835.9 [Mꢀ10PF6
746.7 [Mꢀ11PF6 (calcd m/z: 746.7), 672.4 [Mꢀ12PF6
672.4), 609.6 [Mꢀ13PF6 (calcd m/z: 609.5).
Synthesis of G2-5 and G2-6: solution of FeCl2·4H2O (11.5 mg,
]
(calcd m/z: 1489.7), 1256.5 [Mꢀ7PF6
]
ꢀ
8+
[1] a) J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspectives,
VCH, Weinheim, 1995; b) D. Philp, J. F. Stoddart, Angew. Chem.
[2] a) G. S. Hanan, D. Volkmer, U. S. Schubert, J.-M. Lehn, G. Baum, D.
Ishido, S. Sato, T. Ozeki, Y. Sei, K. Yamaguchi, M. Fujita, Science
]
(calcd m/z: 1081.0), 944.9
ꢀ
9+
ꢀ 10+
]
]
(calcd m/z: 835.8),
ꢀ
11+
ꢀ 12+
]
]
(calcd m/z:
ꢀ
13+
]
A
58 mmol) in MeOH (200 mL) was added to a stirred solution of G2tpy
(114 mg, 55 mmol) in MeOH (200 mL). After the mixture was stirred at
258C for 10 h, the resultant purple solution was concentrated in vacuo to
give a residue, which was purified by flash column chromatography
(SiO2) using H2O/MeCN/sat. KNO3(aq), as the mobile phase to succes-
sively elute G2-5 with a 1:14:1 (v/v/v) mixture and G2-6 with a 1:12:1
mixture. A column chromatography separation was repeated several
times to obtain the pure compounds, which led to relatively low overall
yields.
Data for G2-5: Yield: 13.4 mg, 10%; 1H NMR (CD3OD, 500 MHz): d=
9.72 (s, 20H; PyH3’,5’), 8.96–8.98 (d, J=8.0 Hz, 20H; PyH3,3’’), 8.70 (s, 5H;
Ph-H), 8.22 (s, 10H; PhH), 7.96–7.99 (m, 20H; PyH4,4’’), 7.39–7.40 (d, J=
5.1 Hz, 20H; PyH6,6’’), 7.21–7.23 (m, 20H; PyH5,5’’), 4.60 (m, 10H;
OCH2), 3.55 (m,10H; NCH2), 2.18–2.25 (m, 130H; CH2), 1.91–2.02 (m,
120H; CH2), 1.42 ppm (s, 405H; CH3); 13C NMR (CD3OD, 125 MHz):
d=175.6, 174.6, 162.8, 162.2, 160.4, 159.9, 154.3, 152.4, 141.6, 140.3, 129.0,
125.8, 124.0, 123.1, 122.2, 117.1, 81.8, 68.5, 58.8, 57.9, 37.9, 33.3, 32.4, 32.1,
ꢀ
4+
30.9, 30.7, 28.6 ppm; ESI MS: m/z: 2887.5 [Mꢀ4PF6
2286.4), 2280.8 [Mꢀ5PF6 (calcd m/z: 2280.1), 1876.7 [Mꢀ6PF6
(calcd m/z: 1587.2), 1371.2
]
(calcd m/z:
ꢀ
5+
ꢀ 6+
]
]
ꢀ
7+
(calcd m/z: 1875.9), 1587.7 [Mꢀ7PF6
]
ꢀ
8+
ꢀ 9+
[Mꢀ8PF6
]
(calcd m/z: 1370.7), 1202.7 [Mꢀ9PF6
]
(calcd m/z:
1202.3).
Data for G2-6: Yield: 31 mg, 23%; 1H NMR (CD3OD, 500 MHz): d=
9.77 (s, 24H; PyH3’,5’), 9.00–9.02 (d, J=7.5 Hz, 24H; PyH3,3’’), 8.91 (s, 6H;
Chem. Eur. J. 2011, 17, 4830 – 4838
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4837