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M. Zalas et al./Chemical Papers 66 (8) 733–740 (2012)
Table 2. (continued)
Compound
Spectral data
VI
VII
VIII
1H NMR (CDCl3), δ: 0.33 (s, 18H, CH3Si), 1.43 (t, 3H, CH3CH2), 4.42 (q, 2H, CH3CH2), 7.78 (t, 1H, H-4), 8.10
(d, 2H, H-2,6)
13
—
—
C NMR (CDCl3), δ: 0.20 (CH3Si), 14.28 (CH3), 61.41 (CH2), 96.04 (—C—Si), 102.95 (—C—C), 123.75 (C-3,5),
130.82 (C-1), 132.58 (C-2,6), 138.97 (C-4), 165.18 (C O)
HRMS (EI), m/z (found/calc.): 341.1499/341.1471 (M+, C19H26O2Si2)
—
—
—
—
1
—
H NMR (CDCl3), δ: 1.41 (t, 3H, CH3CH2), 3.17 (s, 2H, —CH), 4.41 (q, 2H, CH3CH2), 7.79 (t, 1H, H-4), 8.17 (d,
—
2H, H-2,6)
13
—
—
C NMR (CDCl3), δ: 29.70 (CH3), 61.55 (CH2), 78.85 (—CH), 82.44 (—C—), 122.88 (C-3,5), 131.11 (C-1), 133.21
—
—
—
—
(C-2,6), 139.20 (C-4), 164.96 (C O)
HRMS (EI), m/z (found/calc.): 198.0660/198.0681 (M+, C13H10O2)
1H NMR (CDCl3), δ: 1.43 (t, 3H, CH3CH2), 4.42 (q, 2H, CH3CH2), 7.36 (ddd, 2H, H-5ꢀꢀ), 7.42 (d, 2H, H-6ꢀ), 7.43
(dd, 2H, H-5ꢀ), 7.85 (td, 2H, H-4ꢀꢀ), 7.92 (t, 1H; H-4), 8.24 (d, 2H, H-2,6), 8.58 (d, 2H, H-3ꢀ), 8.71ꢀꢀ(m, 2H, H-3ꢀꢀ,6ꢀꢀ)
13
ꢀꢀ
—
—
C NMR (CDCl3), δ: 14.31 (CH3CH2), 61.68 (CH3CH2), 88.57 (—C), 91.59 (—C), 121.16 (C-3 ), 123.27 (C-5 ),
—
—
123.32 (C-3,5), 124.10 (C-5ꢀ), 125.23 (C-3ꢀ),ꢀ131.53 (C-1), 131.67 (C-4ꢀ), 133.21 (C-2,6), 137.04 (C-4ꢀꢀ), 138.49 (C-4),
149.29 (C-6ꢀa), 149.30 (C-6ꢀꢀa), 155.41 (C-2 ), 156.39 (C-2 ), 164.91 (C O)
ꢀꢀ
—
—
HRMS (ESI+), m/z (found/calc.): 507.1799/507.1821 ([M + H]+, C33H23N4O2)
IX
Xb
1H NMR (DMSO-d6), δ: 7.51 (ddd, 2H, H-5ꢀꢀ), 7.66 (dd, 2H, H-5ꢀ), 8.00 (td, 2H, H-4ꢀꢀ), 8.17 (t, 1H, H-4), 8.22 (bs,
2H, H-2,6), 8.42 (d, 2H, H-6ꢀ), 8.55 (bd, 2H, H-3ꢀ), 8.73 (ddd, 2H,ꢀꢀH-6ꢀꢀ), 8.79 (m, 2H, H-3ꢀꢀ), 12.2 (bs, 1H, COOH)
13
ꢀꢀ
ꢀ
—
—
C NMR (DMSO-d6), δ: 88.11 (—C), 91.82 (—C), 120.63 (C-3 ), 122.11 (C-5 ), 122.32 (C-3,5), 124.72 (C-5 ),
—
—
125.53 (C-3ꢀ), 129.46 (C-1), 130.88 (C-2,6), 132.07 (C-4ꢀ), 133.15 (C-1), 137.54 (C-4ꢀꢀ), 137.70 (C-4), 149.44 (C-6ꢀ),
149.90 (C-6ꢀꢀ), 154.34 (C-2ꢀ), 155.69 (C-2ꢀꢀ), 165.72 (COOH)
HRMS (ESI+), m/z (found/calc.): 479.1535/479.1508 ([M + H]+, C31H19N4O2)
1
ꢀ
—
H NMR (CDCl3), δ: 4.42 (s, 2H, CH2), 6.98 (s, 1H, CH), 7.41 (ddd, 1H, H-5), 7.50 (ddd, 1H, H-5 ), 7.83 (td,
—
1H, H-4), 7.86 (td, 1H, H-4ꢀ), 8.17 (dt, 1H, H-3), 8.20 (dt, 1H, H-3ꢀ), 8.66 (d, 1H, H-6), 8.69 (d, 1H, H-6ꢀ), 15.35
(bs, 1H, OH)
HRMS (ESI+), m/z (found/calc.): 269.0970/269.0926 ([M + H]+, C15H13N2O3)
1
Xc
XI
H NMR (CDCl3), δ: 6.80 (s, 2H, CH), 7.40 (ddd, 2H, H-5), 7.83 (dt, 2H, H-4), 8.02 (dt, 2H, H-3), 8.68 (d, 2H,
—
—
H-6), 14.62 (bs, 2H, OH)
1H NMR (CDCl3), δ: 7.31 (s, 2H, H-3ꢀ,5ꢀ), 7.46 (H-5ꢀ,5ꢀꢀ), 7.73 (dd, 2H, H-4ꢀ,4ꢀꢀ), 7.92 (d, 2H, H-3ꢀ,3ꢀꢀ), 8.76 (d,
2H, C-6ꢀ,6ꢀꢀ), 9.34 (bs, 1H, NH)
HRMS (ESI+), m/z (found/calc.): 250.0901/250.0980 ([M + H]+, C15H12N3O)
XII
1H NMR (CDCl3), δ: 7.56 (ddd, 2H, H-5ꢀ,5ꢀꢀ), 7.87 (td, 2H, H-4ꢀ,4ꢀꢀ), 8.58 (dt, 2H, H-3ꢀ,3ꢀꢀ), 8.65 (s, 2H, H-3,5),
8.70 (d, 2H, H-6ꢀ,6ꢀꢀ)
13C NMR (CDCl3), δ: 121.36 (C-3ꢀ,3ꢀꢀ), 124.10 (C-5ꢀ,5ꢀꢀ), 127.27 (C-3,5), 135.05 (C-4), 136.95 (C-4ꢀ,4ꢀꢀ), 149.17
(C-6ꢀ,6ꢀꢀ), 154.82 (C-2ꢀ,2ꢀꢀ), 156.37 (C-2,6)
HRMS (EI), m/z (found/calc.): 311.0007/311.0058 (M+, C15H10N3Br)
XIII
1H NMR (CDCl3), δ: 1.42 (t, 3H, CH3CH2), 4.44 (q, 2H, CH3CH2), 7.37 (ddd, 4H, H-5ꢀꢀ,5ꢀꢀꢀ), 7.90 (t, 1H, H-4),
7.91 (td, 4H, H-4ꢀꢀ,4ꢀꢀꢀ), 8.23 (d, 2H, H-2,6), 8.60 (s, 4H, H-3ꢀ,5ꢀ), 8.62 (d, 4H, H-3ꢀꢀ,3ꢀꢀꢀ), 8.74 (d, 4Hꢀ,ꢀ H-6ꢀꢀ,6ꢀꢀꢀ
)
13
C NMR (CDCl3), δ: 14.33 (CH3CH2), 61.65 (CH3CH2), 88.62 (—C), 91.68 (—C), 121.22 (C-3 ,3ꢀꢀꢀ), 123.32
—
—
—
—
(C-3,5), 123.90 (C-3ꢀ,5ꢀ), 124.34 (C-5ꢀꢀ,5ꢀꢀꢀ), 131.53 (C-1), ꢀ132.45 (C-4ꢀ), 133.21 (C-2,6), 136.73 (C-4ꢀꢀ,4ꢀꢀꢀ), 138.49
(C-4), 149.06 (C-6ꢀꢀ,6ꢀꢀꢀ), 155.12 (C-2ꢀꢀ,2ꢀꢀꢀ), 155.33 (C-2 ,6 ), 164.95 (C O)
ꢀ
—
—
HRMS (ESI+), m/z (found/calc.): 661.2414/661.2353 ([M + H]+, C43H29N6O2)
XIV
1H NMR (DMSO-d6), δ: 7.49 (ddd, 4H, H-5ꢀꢀ,5ꢀꢀꢀ), 8.04 (td, 4H, H-4ꢀꢀ,4ꢀꢀꢀ), 8.12 (t, 1H, H-4), 8.24 (d, 2H, H-2,6),
8.61 (s, 4H, H-3ꢀ,5ꢀ), 8.68 (d, 4H, H-3ꢀꢀ,3ꢀꢀꢀ), 8.72 (d, 4H, H-6ꢀꢀ,6ꢀꢀꢀꢀ)ꢀ, 12.9 (bs, 1H, COOH)
13
C NMR (DMSO-d6), δ: 88.09 (—C), 91.99 (—C), 120.86 (C-3 ,3ꢀꢀꢀ), 122.29 (C-3,5), 123.60 (C-5ꢀꢀ,5ꢀꢀꢀ), 124.11
—
—
—
—
(C-3ꢀ,5ꢀ), 129.67 (C-1), 131.00 (C-2,6), 133.13 (C-4ꢀ), 136.84 (C-4ꢀꢀ,4ꢀꢀꢀ), 137.87 (C-4), 149.74 (C-6ꢀꢀ,6ꢀꢀꢀ), 154.50
(C-2ꢀ,6ꢀ), 154.92 (C-2ꢀꢀ,2ꢀꢀꢀ), 164.95 (C O)
—
—
HRMS (ESI+), m/z (found/calc.): 633.19849/633.20390 ([M + H]+, C41H25N6O2)
a) Uncertain assignments; b) mono-enolic form, minor component; c) bis-enolic form, major component.
cedure presented by Matsuda et al. (2002). Carboxylic
group of the “clipper” molecule plays the role of an
anchoring group during the adsorption of the poten-
tial dye, prepared with the use of the ligands stud-
ied, on the working electrode of DSSC. Preparation
of 4-bromo-2,6-bis(2-pyridyl)pyridine (XII ), which is
a precursor of the “black dye” ligand dendritic ana-
logue, is shown in Fig. 3. The synthesis starts from
2-picolinic acid and it is a modification of the proce-
dures presented by Huang and Han (2006) and Muro
and Castellano (2007). Final synthesis of the dendritic
ligands (IX and XIV ) is presented in Fig. 4. Char-
acterisation and spectral data of the prepared com-
pounds are given in Tables 1 and 2.
It was found (see Table 3) that the obtained com-
pounds are practically insoluble in water or hex-
ane. Ethyl esters of the obtained polypyridine lig-
ands were moderately soluble in polar solvents, such