Design of Neutral Metallomesogens
OCH3), 3.64 (s, 12 H, lateral OCH3) 1.69 (s, 6 H, Hd) ppm. 13C
NMR (75.48 MHz, CDCl3, 298 K): δ = 158.5, 153.0, 152.4, 145.7,
136.3, 135, 9, 119.5, 108.2, 99.7, 60.8, 55.6, 43.1, 32.1 ppm. FAB
(LSI)MS: m/z = 664 [Pd(11)]+.
Characterisation of [Pd(110)]: A yellow solid (0.311 g, 93%).
C85H142N4O6Pd·H2O (1440.50): calcd. C 70.87, H 10.08, N 3.89;
found C 70.36, H 9.60, N 3.72. IR (KBr pellet): ν = 1589 (s, C=N)
˜
Figure 8. View of the ligands H2(2n), with selected hydrogen atoms
labelled a–g in reference to the NMR spectral assignments.
cm–1. 1H NMR (300.13 MHz, CDCl3, 298 K): δ = 7.58 (s, 2 H,
HaC=N), 6.89 (d, 3JAX = 3.9 Hz, 2 H, Hb), 6.30 (d, 3JAX = 3.9 Hz,
3
2 H, Hc), 6.08 (s, 4 H, He), 3.83 (t, JAX = 6.5 Hz, 4 H, central
3
OCH2), 3.63 (t, JAX = 6.5 Hz, 8 H, lateral OCH2) 1.74–1.28 (m,
3
6.57 (d, 3JAX = 3.7 Hz, 2 H, Hb), 6.15 (d, JAX = 3.7 Hz, 2 H, Hc),
96 H + 6 H, CH2 + Hd), 0.88 (overlapping triplets, 18 H, CH3)
ppm. 13C NMR (75.48 MHz, CDCl3, 298 K): δ = 158.4, 152.9,
152.0, 145.0, 136.3, 136.1, 119.0, 107.8, 100.4, 73.4, 68.5, 43.0, 32.0,
30.6, 29.9, 29.7, 29.5, 29.4, 26.3, 26.2, 22.7, 14.1 ppm. MALDI-
TOF MS: m/z = 1421 [Pd(110)]+.
4.77 (br. s, 2 H, NH), 3.87 (s, 12 H, OCH3), 1.76 (s, 6 H, Hd) ppm.
13C NMR (75.48 MHz, CDCl3, 298 K): δ = 149.3, 148.3, 147.2,
144.9, 144.1, 130.2, 117.0, 112.0, 111.5, 106.8, 105.0, 56.0, 55.8,
35.9, 28.4 ppm. ES MS: m/z = 501 [H2(21)]+.
Characterisation of [H2(216)]: A yellow solid (0.248 g, 96%).
C89H152N4O4·H2O (1360.20): calcd. C 78.59, H 11.41, N 4.12;
Characterisation of [Pd(112)]: A sticky brown solid (0.109 g, 99%).
C97H166N4O6Pd·CHCl3··H2O (1728.19): calcd. C 68.11, H 9.86, N
found C 78.41, H 11.40, N 4.38. IR (KBr pellet): ν = 1619 (s, C=N)
˜
3.24; found C 68.07, H 10.43, N 3.63. IR (KBr pellet): ν = 1586
cm–1. 1H NMR (300.13 MHz, CDCl3, 298 K): δ = 8.15 (s, 2 H,
˜
1
(m, C=N) cm–1. H NMR (300.13 MHz, CDCl3, 298 K): δ = 7.58 HaC=N), 6.84 (d, 3JAB = 8.5 Hz, 2 H, Hg), 6.72 (m, 4 H, He + Hf),
(s, 2 H, HaC=N), 6.89 (d, JAX = 3.7 Hz, 2 H, Hb), 6.30 (d, JAX 6.55 (d, 3JAX = 3.6 Hz, 2 H, Hb), 6.15 (d, JAX = 3.6 Hz, 2 H, Hc),
3
3
3
3
= 3.9 Hz, 2 H, Hc), 6.08 (s, 4 H, He), 3.85 (t, JAX = 6.4 Hz, 4 H,
3.99 (m, 8 H, OCH2), 1.83–1.25 (m, 112 H + 6 H, CH2 + Hd),
central OCH2), 3.63 (t, JAX = 6.6 Hz, 8 H, lateral OCH2) 1.71– 0.88 (overlapping triplets, 12 H, CH3) ppm. 13C NMR (75.48 MHz,
3
1.27 (m, 120 H + 6 H, CH2 + Hd), 0.88 (overlapping triplets, 18
H, CH3) ppm. 13C NMR (75.48 MHz, CDCl3, 298 K): δ = 158.4,
152.8, 152.0, 144.9, 136.2, 136.0, 119.0, 107.8, 100.3, 73.3, 68.4,
42.8, 32.1, 32.0, 31.8, 30.5, 29.6, 29.3, 26.2, 26.1, 22.6, 22.5,
14.0 ppm. MALDI-TOF MS: m/z = 1589 [Pd(112)]+.
CDCl3, 298 K): δ = 149.7 148.0, 147.3, 144.9, 144.2, 130.3, 117.0,
114.5, 112.5, 107.2, 102.7, 69.7, 69.1, 36.0, 31.9, 29.7, 29.6, 29.4,
29.3, 28.5, 26.0, 22.7, 14.1 ppm (signals of seven alkyl carbon atoms
obscured). ES MS: m/z = 1343 [H2(216)]+.
Characterisation of [Zn2(21)2]: A yellow solid (0.081 g, 60%).
C58H60N8O8Zn2·CH2Cl2·H2O (1230.87): calcd. C 57.57, H 5.24, N
Characterisation of [Pd(114)]: A brown solid (0.107 g, 98%).
C109H190N4O6Pd·H2O (1777.13): calcd. C 73.67, H 10.89, N 3.15;
9.10; found C 57.58, H 5.18, N 9.06. IR (KBr pellet): ν = 1609 (s,
˜
C=N) cm–1. 1H NMR (300.13 MHz, CDCl3, 298 K): δ = 8.16 (s, 2
found C 73.45, H 10.78, N 3.13. IR (KBr pellet): ν = 1586 (s, C=N)
˜
3
H, HaC=N), 6.67 (d, JAB = 8.7 Hz, 2 H, Hg), 6.59 (m, 4 H, He +
cm–1. 1H NMR (300.13 MHz, CDCl3, 298 K): δ = 7.58 (s, 2 H,
3
3
Hf), 6.23 (d, JAB = 2.4 Hz, 2 H, Hb), 6.13 (d, JAB = 2.4 Hz, 2 H,
Hc), 3.89 (s, 6 H, OCH3), 3.43 (s, 6 H, OCH3), 1.60 (s, 6 H, Hd)
ppm. 13C NMR (75.48 MHz, CDCl3, 298 K): δ = 157.9, 149.1,
146.2, 140.1, 135.9, 121.3, 111.3, 108.7, 106.1, 56.0, 55.3, 39.2,
29.8 ppm. MALDI-TOF MS: m/z = 1128 [Zn2(21)2]+.
HaC=N), 6.89 (d, 3JAX = 4.0 Hz, 2 H, Hb), 6.30 (d, 3JAX = 4.0 Hz,
3
2 H, Hc), 6.08 (s, 4 H, He), 3.83 (t, JAX = 6.4 Hz, 4 H, central
3
OCH2), 3.63 (t, JAX = 6.5 Hz, 8 H, lateral OCH2) 1.68–1.26 (m,
144 H + 6 H, CH2 + Hd), 0.88 (overlapping triplets, 18 H, CH3)
ppm. 13C NMR (67.93 MHz, CDCl3, 298 K): δ = 158.5, 153.0,
152.2, 145.1, 136.4, 136.2, 119.1, 107.9, 100.5, 73.5, 68.7, 43.0, 32.2,
31.9, 30.9, 30.6, 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.2, 26.3, 22.8,
14.2 ppm. MALDI-TOF MS: m/z = 1758 [Pd(114)]+.
Characterisation of [Zn2(216)2]: A yellow solid (0.099 g, 90%).
C178H300N8O8Zn2·1/2H2O (1423.57): calcd. C 75.57, H 10.76, N
3.96; found C 75.34, H 10.91, N 4.05. IR (KBr pellet): ν = 1606
˜
1
(m, C=N) cm–1. H NMR (300.13 MHz, CDCl3, 298 K): δ = 8.10
Characterisation of [Pd(116)]: A yellow solid (0.191 g, 93%).
C121H214N4O6Pd·H2O (1945.45): calcd. C 74.70, H 11.19, N 2.88;
3
(s, 2 H, HaC=N), 6.66 (d, JAB = 8.7 Hz, 2 H, Hg), 6.53 (m, 4 H,
He + Hf), 6.20 (d, 3JAB = 2.4 Hz, 2 H, Hb), 6.10 (d, JAB = 3.4 Hz,
3
3
3
found C 74.73, H 11.40, N 2.77. IR (KBr pellet): ν = 1585 (m,
˜
2 H, Hc), 3.87 (t, JAX = 6.7 Hz, 4 H, OCH2), 3.42 (t, JAX
=
C=N) cm–1. 1H NMR (300.13 MHz, CDCl3, 298 K): δ = 7.58 (s, 2
6.6 Hz, 4 H, OCH2), 1.75–1.26 (m, 112 H + 6 H, CH2 + Hd), 0.88
(2 overlapping triplets, 12 H, CH3) ppm. 13C NMR (75.48 MHz,
CDCl3, 298 K): δ = 158.1, 152.2, 149.1, 146.0, 140.1, 135.9, 121.1,
114.3, 111.1, 108.6, 107.9, 69.8, 67.8, 39.3, 32.0, 29.9, 29.8, 29.7,
29.6, 29.5, 29.2, 26.1, 22.8, 14.2 ppm (signals of six alkyl carbon
atoms obscured). MALDI-TOF MS: m/z = 2811 [Zn2(216)2]+.
3
3
H, HaC=N), 6.89 (d, JAX = 3.9 Hz, 2 H, Hb), 6.30 (d, JAX
=
3
3.9 Hz, 2 H, Hc), 6.07 (s, 4 H, He), 3.83 (t, JAX = 6.5 Hz, 4 H,
central OCH2), 3.62 (t, JAX = 6.3 Hz, 8 H, lateral OCH2) 1.71–
3
1.26 (m, 168 H, CH2), 1.57 (s, 6 H, Hd), 0.88 (overlapping triplets,
18 H, CH3) ppm. 13C NMR (75.48 MHz, CDCl3, 298 K): δ =
158.9, 152.9, 152.1, 145.0, 136.3, 136.1, 119.0, 107.8, 100.5, 73.4,
68.6, 43.0, 32.2, 31.9, 30.9, 30.6, 29.8, 29.3, 26.3, 26.2, 22.7,
14.1 ppm. (six alkyl carbon atoms obscured). MALDI-TOF MS:
m/z = 1926 [Pd(116)]+.
Characterisation of [Pd(21)]: An orange microcrystalline solid
(0.065 g, 53%). C29H30N4O4Pd·CHCl3 (724.37): calcd. C 49.74, H
4.31, N 7.73; found C 50.12, H 4.78, N 8.01. IR (KBr pellet): ν =
˜
1
1592 (m, C=N) cm–1. H NMR (300.13 MHz, CDCl3, 298 K): δ =
3
Synthesis of the Tetracatenar Ligands H2(2n) (Figure 8).
7.58 (s, 2 H, HaC=N), 6.90 (d, JAX = 3.9 Hz, 2 H, Hb), 6.48 (d,
3JAB = 8.4 Hz, 2 H, Hg), 6.41 (dd, JAB = 8.4, JAM = 2.4 Hz, 2 H,
Hf), 6.32 (overlapping doublets, 4 H, He + Hc), 3.81 (s, 6 H, OCH3),
3.60 (s, 6 H, OCH3), 1.70 (s, 6 H, Hd) ppm. 13C NMR (75.48 MHz,
CDCl3, 298 K): δ = 158.1, 152.1, 148.8, 147.0, 143.1, 136.2, 118.9,
3
4
Characterisation of H2(21):
C29H32N4O4·CHCl3·H2O (637.98): calcd. C 56.48, H 5.53, N 8.78;
found C 56.66, H 5.27, N 8.78. IR (KBr pellet): ν = 1620 (s, C=N)
A yellow solid (0.496 g, 74%).
˜
cm–1. 1H NMR (300.13 MHz, CDCl3, 298 K): δ = 8.16 (s, 2 H, 113.5, 110.9, 107.7, 106.4, 56.1, 55.4, 43.1, 32.2 ppm. MALDI-TOF
HaC=N), 6.84 (d, 3JAB = 8.4 Hz, 2 H, Hg), 6.76 (m, 4 H, He + Hf), MS: m/z = 604 [Pd(21)]+.
Eur. J. Inorg. Chem. 2008, 5056–5066
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5063