and the solution was evaporated after drying over Na2SO4 to
yield the crude complex. Further purification was achieved by
recrystallization from acetonitrile–diethyl ether and/or column
chromatography (alumina).16
[2,6-Bis(11-undecanol-1-yl-1H-1,2,3-triazol-4-yl)pyridine] [4¢-(4-
bromophenyl)-2,2¢:6¢,2¢¢-terpyridine] ruthenium(II) hexafluorophos-
phate (4). Yield: 42% (after purification by column chromatog-
raphy (alumina, CH2Cl2–acetone 1 : 1). 1H NMR (400 MHz,
CD3CN) d/ppm: 8.89 (s, 2H, H5a,5¢¢a), 8.66 (s, 2H, H3¢,5¢), 8.59 (d,
[2,6-Bis(1-decyl-1H-1,2,3-triazol-4-yl)pyridine] [2,2¢:6¢,2¢¢-ter-
pyridine] ruthenium(II) hexafluorophosphate (1). Yield: 81% (after
3
3J = 8 Hz, 2H, H3,3¢¢), 8.35 (m, 3H, H3¢a,4¢a,5¢a), 8.11 (d, J = 8.4
Hz, 2H, HAA¢/BB¢), 7.97 (dt, 3J = 8 Hz, 2H, H4,4¢¢), 7.91 (d, 3J = 8.4
Hz, 2H, HBB¢/AA¢), 7.48 (dd, 3J = 5.6 Hz, 2H, H6,6¢¢), 7.26 (dt, 3J =
1
re-precipitation from acetonitrile into diethyl ether). H NMR
3
(400 MHz, CD3CN) d/ppm: 8.68 (s, 2H, H5a,5¢¢a), 8.64 (d, J =
3
6.8 Hz, 2H, H5,5¢¢), 4.18 (t, J = 7.0 Hz, 4H, N–CH2), 3.47 (mc,
3
8 Hz, 2H, H3¢,5¢), 8.46 (d, J = 8 Hz, 2H, H3,3¢¢), 8.40–8.31 (m,
3
4H, CH2–OH), 2.47 (t, J = 5.4 Hz, 2H, OH), 1.65 (mc, 4H, N–
3
3
H4, H4¢,3¢a,4¢a,5¢a), 7.96 (dt, J = 8 Hz, 2H, H4,4¢¢), 7.47 (dd, J =
6.4 Hz, 2H, H6,6¢¢), 7.25 (dt, 3J = 6.6 Hz, 2H, H5,5¢¢), 4.18 (t, 3J =
7.2 Hz, 4H, N–CH2), 1.65 (mc, 4H, N–CH2–CH2), 1.30–0.93 (m,
28H, CH2), 0.88 (t, 3J = 7.0 Hz, 6H, CH3). 13C NMR (100 MHz,
CD3CN) d/ppm: 158.1, 156.5, 152.9, 149.6, 149.3, 138.1, 137.5,
136.1, 127.6, 125.5, 124.0, 122.8, 120.6, 52.1, 31.6, 29.1, 29.0, 28.9,
28.98, 28.3, 25.5, 22.4, 13.4. MALDI-ToF MS (dithranol): m/z =
973.46 ([M - PF6]+). Anal. calcd for C44H58F12N10P2Ru (1118.00):
C 47.27, H 5.23, N 12.53%. Found: C 47.46, H 5.44, N 12.46%. UV-
vis (CH3CN) lmax/nm (e/L mol-1 cm-1): 432 (11 500), 356 (5500),
303 (39 000) 286 (41 500), 226 (41 500).
CH2CH2), 1.45 (mc, 4H, CH2CH2–OH), 1.34–0.91 (m, 28H, CH2).
13C NMR (100 MHz, CD3CN) d/ppm: 158.2, 156.8, 153.0, 149.6,
149.3, 147.1, 138.1, 137.6, 135.7, 132.6, 129.7, 127.6, 125.5, 124.5,
124.2, 120.6, 120.5, 61.6, 52.1, 32.6, 29.2, 29.1, 29.0, 28.9, 28.2,
25.6, 25.4. MALDI-ToF MS (dithranol): m/z = 1187.14 ([M -
PF6]+). Anal. calcd for C52H65BrF12N10O2P2Ru (1333.04): C 46.85,
H 4.91, N 10.51%. Found: C 46.63, H 4.99, N 10.54%. UV-vis
(CH2Cl2) lmax/nm (e/L mol-1 cm-1): 456 (16 500), 438 (16 000),
356 (6500), 287 (67 000).
[2,6-Bis(1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl)pyridine] [4¢-
(4-bromophenyl)-2,2¢:6¢,2¢¢-terpyridine] ruthenium(II) hexafluoro-
phosphate (5). Yield: 53% (after purification by column chro-
matography (silica, CH3CN–water 9 : 1, saturated with KNO3).
Single crystals were obtained by slow diffusion of diethyl ether
into a concentrated solution of 5 in CD3CN. 1H NMR (400 MHz,
CH3CN) d/ppm: 9.08 (s, 2H, H5a,5¢¢a), 8.92 (s, 2H, H3¢,5¢), 8.62
[2,6-Bis(11-undecanol-1-yl-1H-1,2,3-triazol-4-yl)pyridine] [2,2¢:
6¢,2¢¢-terpyridine] ruthenium(II) hexafluorophosphate (2). Yield:
1
3
90%. H NMR (400 MHz, CD3CN) d/ppm: 8.66 (d, J = 8 Hz,
3
2H, H3¢,5¢), 8.64 (s, 2H, H5a,5¢¢a), 8.47 (d, J = 8 Hz, 2H, H3,3¢¢),
8.33 (m, 4H, H4¢,3¢a,4¢a,5¢a), 7.96 (dt, 3J = 8 Hz, 2H, H4,4¢¢), 7.45 (dd,
3
3J = 5.2 Hz, 2H, H6,6¢¢), 7.25 (dt, J = 6.6 Hz, 2H, H5,5¢¢), 4.17
3
3
3
(d, J = 8 Hz, 2H, H3,3¢¢), 8.43 (m, 3H, H3¢a,4¢a,5¢a), 8.12 (d, J =
(t, J = 7.0 Hz, 4H, N–CH2), 3.48 (mc, 4H, CH2–OH), 2.47 (t,
3J = 5.2 Hz, 2H, OH), 1.64 (mc, 4H, N–CH2CH2), 1.48 (mc, 4H,
CH2CH2–OH), 1.35–0.90 (m, 28H, CH2). 13C NMR (100 MHz,
CD3CN) d/ppm: 158.2, 156.5, 152.8, 149.6, 149.3, 138.1, 137.5,
136.1, 127.5, 125.4, 124.0, 122.8, 120.6, 61.6, 52.1, 32.6, 29.2, 29.1,
29.0, 28.9, 28.8, 28.2, 25.6, 25.4. MALDI-ToF MS (dithranol):
m/z = 1033.33 ([M - PF6]+). Anal. calcd for C46H62F12N10O2P2Ru
(1178.05): C 46.9, H 5.3, N 11.89%. Found: C 46.96, H 5.66, N
11.82%. UV-vis (CH2Cl2) lmax/nm (e/L mol-1 cm-1): 435 (10 000),
356 (4500), 305 (36 000), 287 (37 500).
3
8.4 Hz, 2H, HAA¢/BB¢), 8.02 (dt, J = 8 Hz, 2H, H4,4¢¢), 7.93 (d,
3
3J = 8.4 Hz, 2H, HBB¢/AA¢), 7.57 (dd, J = 5.6 Hz, 2H, H6,6¢¢),
3
3
7.44 (d, J = 9.2 Hz, 4H, HCC¢/DD¢), 7.30 (dt, J = 6.4 Hz, 2H,
3
H
5,5¢¢), 7.02 (d, J = 9.2 Hz, 4H, HDD¢/CC¢), 3.80 (s, 6H, Hmethoxy).
13C NMR (100 MHz, CD3CN) d/ppm: 160.8, 158.3, 156.8, 153.2,
150.0, 149.5, 147.4, 138.2, 137.8, 135.9, 132.6, 129.7, 129.1, 127.6,
124.4, 124.3, 123.6, 122.4, 120.9, 120.8, 114.9, 55.5. MALDI-ToF
MS (dithranol): m/z = 1061.34 ([M - PF6]+). Anal. calcd for
C44H33BrF12N10O2P2Ru (1204.70): C 43.87, H 2.76, N 11.63%.
Found: C 44.03, H 2.84, N 11.53%. UV-vis (CH2Cl2) lmax/nm
(e/L mol-1 cm-1): 456 (14 500), 435 (13 500), 300 (73 000).
[2,6-Bis(1-decyl-1H-1,2,3-triazol-4-yl)pyridine] [4¢-(4-bromo-
phenyl)-2,2¢:6¢,2¢¢-terpyridine] ruthenium(II) hexafluorophosphate
(3). Yield: 53% (after successive purification by column
chromatography (alumina, CH2Cl2/acetone, elution of the
product with CH2Cl2–methanol, 1 : 1), gel filtration (silica,
CH3CN, elution of the product with CH3CN–water 9 : 1,
saturated with KNO3) and re-precipitation into diethyl ether). 1H
NMR (400 MHz, CD3CN) d/ppm: 8.86 (s, 2H, H5a,5¢¢a), 8.68 (s,
[2,6-Bis(1-(4-tert-butyl)benzyl-1H-1,2,3-triazol-4-yl)pyridine] [4¢-
(4-bromophenyl)-2,2¢:6¢,2¢¢-terpyridine] ruthenium(II) hexafluoro-
phosphate (6). Yield: 28% (after purification by column chro-
matography (silica, CH3CN–water 9 : 1, saturated with KNO3).
1H NMR (400 MHz, CD3CN) d/ppm: 8.75 (s, 2H, H5a,5¢¢a), 8.57 (s,
2H, H3¢a,5¢a), 8.38 (m, 3H, H3¢,5¢,4¢a), 8.12 (d, 3J = 8 Hz, 2H, H3,3¢¢), 7.81
(d, 3J = 8 Hz, 2H, HAA¢/BB¢), 7.77 (dt, 3J = 8 Hz, 2H, H4,4¢¢), 7.62 (d,
3J = 8 Hz, 2H, HBB¢/AA¢), 7.48 (dd, 3J = 5.6 Hz, 2H, H6,6¢¢), 7.23 (dt,
3J = 6.8 Hz, 2H, H5,5¢¢), 7.19 (d, 3J = 8 Hz, 4H, HCC¢/DD¢), 6.98 (d,
3J = 8 Hz, 4H, HDD¢/CC¢), 5.36 (s, 2H, CH2), 1.11 (s, 18H, Htert-butyl).
13C NMR (100 MHz, CD3CN) d/ppm: 157.8, 156.8, 153.2, 152.1,
149.7, 149.5, 146.3, 138.1, 137.7, 134.7, 132.6, 130.4, 129.1, 128.1,
127.6, 126.0, 125.9, 124.7, 123.8, 121.0, 119.7, ~55 (with solvent),
34.1, 30.3. MALDI-ToF MS (dithranol): m/z = 1139.165 ([M -
PF6]+). Anal. calcd for C52H49BrF12N10P2Ru (1284.92): C 48.61, H
3.84, N 10.9%. Found: C 48.4, H 4.13, N 10.82%. UV-vis (CH2Cl2)
3
2H, H3¢,5¢), 8.53 (d, J = 8 Hz, 2H, H3,3¢¢), 8.37 (m, 3H, H3¢a,4¢a,5¢a),
8.09 (d, 3J = 8.4 Hz, 2H, HAA¢/BB¢), 7.95 (dt, 3J = 8 Hz, 2H, H4,4¢¢),
3
3
7.86 (d, J = 8.4 Hz, 2H, HBB¢/AA¢), 7.50 (dd, J = 5.6 Hz, 2H,
3
3
H
6,6¢¢), 7.27 (dt, J = 6.8 Hz, 2H, H5,5¢¢), 4.19 (t, J = 7.2 Hz,
4H, N–CH2), 1.66 (mc, 4H, N–CH2CH2), 1.30–0.93 (m, 28H,
CH2), 0.86 (t, 3J = 7.0 Hz, 6H, CH3). 13C NMR (100 MHz,
CD3CN) d/ppm: 158.2, 156.8, 153.0, 149.6, 149.3, 147.1, 138.1,
137.6, 135.7, 132.6, 129.7, 127.6, 125.5, 124.5, 124.2, 120.6, 120.5,
52.1, 31.6, 29.1, 29.0, 28.9, 28.2, 25.5, 22.4, 13.4. MALDI-ToF
MS (dithranol): m/z = 1129.05 ([M - PF6]+). Anal. calcd for
C50H61BrF12N10P2Ru (1272.99): C 47.18, H 4.83, N 11%. Found:
C 47.11, H 4.63, N 10.91%. UV-vis (CH2Cl2) lmax/nm (e/L mol-1
cm-1): 456 (16 500), 438 (16 000), 356 (6500), 287 (67 000).
l
max/nm (e/L mol-1 cm-1): 455 (17 500), 435 (16 500), 357 (6000),
288 (73 000).
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 787–794 | 789
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