Article
Organometallics, Vol. 29, No. 23, 2010 6265
UV-visible spectra were recorded using a Shimadzu UV-1700
spectrophotometer. Elemental analyses were performed using
an Elementar Vario EL analyzer. Cyclic voltammetry was
performed with a CH Instrument model 600C series electro-
chemical analyzer/workstation. The glassy-carbon electrode
was polished with 0.05 μm alumina on a microcloth, sonicated
for 5 min in deionized water, and rinsed with acetonitrile before
use. An Ag/AgNO3 (0.1 M in CH3CN) electrode was used as
reference electrode. All solutions were degassed with argon
before experiments. E1/2 values are the average of the cathodic
and anodic peak potentials for the oxidative and reductive
waves. The E1/2 value of the ferrocenium/ferrocene couple
(Cp2Feþ/0) measured in the same solution was used as an
internal reference. Steady-state emission spectra were obtained
on a Jobin Yvon Fluorolog-3-TCSPC spectrophotometer. Sam-
ple and standard solutions were degassed with at least three
freeze-pump-thaw cycles. The emission quantum yields were
measured by the method of Demas and Crosby46 with [Ru(bpy)3]-
(PF6)2 in degassed CH3CN as standard (Φr = 0.062) and calculated
by Φs = Φr(Br/Bs)(ns/nr)2(Ds/Dr), where the subscripts s and r refer
to sample and reference standard solution, respectively, n is the
refractive index of the solvents, D is the integrated intensity, and Φ is
the luminescence quantum yield. The quantity B is calculated by
B = 1 - 10-AL, where A is the absorbance at the excitation
wavelength and L is the optical path length.
[([9]aneS3)(diimine)Ru(Cl)](PF6) (1-3a). [Ru([9]aneS3)(dmso)-
Cl2]47 (0.1 g, 0.2 mmol) was added in methanol (20 mL) containing
aromatic diimine ligand (0.4 mmol), and the reaction mixture was
refluxed for 90 min. Upon cooling to room temperature, a saturated
aqueous solution of NH4PF6 (2 mL) was added, and the reaction
mixture was concentrated to afford an orange or red precipitate.
The precipitate was filtered off, washed with Et2O, and recrystal-
lized by slow diffusion of Et2O into an acetonitrile solution to give
bright orange crystals.
[([9]aneS3)(bpy)Ru(Cl)](PF6) (1a). Yield: 0.13 g, 90%. Anal.
Calcd for C16H20N2S3ClRuPF6: C, 31.07; H, 3.26; N, 4.53. Found:
C, 31.02; H, 3.38; N, 4.58. 1H NMR (400 MHz, CD3CN): δ
2.40-2.70, 2.77-2.86, 2.91-3.04 (m, 12H, [9]aneS3); 7.57 (dd, 2H,
J = 6.0, 1.3 Hz, bpy); 8.07 (t, 2H, J = 6.7 Hz, bpy); 8.39 (d, 2H,
J = 8.0 Hz, bpy); 9.00 (d, 2H, J = 5.5 Hz, bpy). 13C NMR (100
MHz, CD3CN): δ 32.4, 33.5, 35.9 ([9]aneS3); 124.5, 128.0, 138.9,
154.1, 157.4 (bpy). IR (KBr, cm-1): νP-F = 843. ESI-MS: m/z 473
[Mþ].
was added, and the reaction mixture was concentrated to afford
a yellow precipitate. The precipitate was filtered off, washed
with Et2O, and recrystallized by slow diffusion of Et2O into an
acetonitrile solution to give bright yellow crystals.
[([9]aneS3)(bpy)Ru(CN)](PF6) (1b). Yield: 0.05 g, 52%. Anal.
Calcd for C17H20N3S3RuPF6: C, 33.50; H, 3.31; N, 6.90. Found:
1
C, 33.29; H, 3.43; N, 6.82. H NMR (400 MHz, CD3CN): δ
2.42-2.56, 2.59-2.77, 2.84-2.99 (m, 12H, [9]aneS3); 7.56 (dd,
2H, J = 6.0, 1.3 Hz, bpy); 8.09 (dd, 2H, J = 6.5, 1.5 Hz, bpy);
8.40 (d, 2H, J = 8.3 Hz, bpy); 8.86 (d, 2H, J = 5.3 Hz, bpy). 13
C
NMR (100 MHz, CD3CN): δ 32.5, 32.9, 35.9 ([9]aneS3); 124.7,
128.2, 139.0, 153.9, 157.0 (bpy); 138.3 (CN). IR (KBr, cm-1):
ν
CꢁN = 2089, νP-F = 843. ESI-MS: m/z 464 [Mþ].
[([9]aneS3)(4,40-Me2bpy)Ru(CN)](PF6) (2b). Yield: 0.05 g,
53%. Anal. Calcd for C19H24N3S3RuPF6: C, 35.79; H, 3.88;
N, 6.60. Found: C, 35.59; H, 4.10; N, 6.42. 1H NMR (400 MHz,
CD3CN): δ 2.40-2.77, 2.80-2.97 (m, 18H, [9]aneS3 and CH3 in
Me2bpy); 7.37 (d, 2H, J = 4.8 Hz, Me2bpy); 8.26 (s, 2H,
Me2bpy); 8.64 (d, 2H, J = 5.5 Hz, Me2bpy). 13C NMR (100
MHz, CD3CN): δ 21.3 (Me2 in Me2bpy); 32.5, 32.9, 35.8
([9]aneS3); 125.4, 128.9, 151.5, 153.1, 156.6 (Me2bpy); 139.0
(CN). IR (KBr, cm-1): νCꢁN = 2083, νP-F = 844. ESI-MS: m/z
492 [Mþ].
[([9]aneS3)(dpq)Ru(CN)](PF6) (3b). Yield: 0.06 g, 62%. Anal.
Calcd for C21H20N5S3RuPF6: C, 36.79; H, 2.94; N, 10.22.
Found: C, 36.83; H, 3.14; N, 10.10. 1H NMR (400 MHz,
CD3CN): δ 2.49-2.58, 2.68-2.85, 2.95-3.10 (m, 12H, [9]aneS3);
8.05 (dd, 2H, J = 5.3, 3.0 Hz, dpq); 9.19 (s, 2H, dpq); 9.31 (dd, 2H,
J=4.0, 1.3Hz, dpq);9.61(dd, 2H,J=7.0, 1.3Hz, dpq). 13CNMR
(100 MHz, CD3CN): δ 32.5, 33.1, 36.1 ([9]aneS3); 127.9, 130.7,
134.7, 140.5, 147.6, 149.5, 155.4 (dpq); 137.9 (CN). IR (KBr, cm-1):
ν
CꢁN = 2089, νP-F = 842. ESI-MS: m/z 540 [Mþ].
[([9]aneS3)(diimine)Ru(CtCPh)](PF6) (1-3c). Excess pheny-
lacetylene (0.8 mL) was added to a methanolic solution contain-
ing [([9]aneS3)(diimine)RuCl](PF6) (0.16 mmol) and KOH
(2 mmol), and the reaction was refluxed for 12 h. Upon cooling
to room temperature, the reaction mixture was concentrated
and then precipitated by addition of saturated aqueous NH4PF6
(1 mL). The red precipitate was washed with Et2O and recrys-
tallized by slow diffusion of Et2O into an acetonitrile solution to
give red crystals.
[([9]aneS3)(bpy)Ru(CtCPh)](PF6) (1c). Yield: 0.06 g, 58%.
Anal. Calcd for C24H25N2S3RuPF6: C, 42.11; H, 3.68; N, 4.09.
Found: C, 41.96; H, 3.82; N, 4.19. 1H NMR (400 MHz,
[([9]aneS3)(4,40-Me2bpy)Ru(Cl)](PF6) (2a). Yield: 0.13 g,
89%. Anal. Calcd for C18H24N2S3ClRuPF6: C, 33.44; H, 3.74;
N, 4.34. Found: C, 33.30; H, 3.78; N, 4.10. 1H NMR (400 MHz,
CD3CN): δ 2.38-2.66, 2.74-2.83, 2.88-3.00 (m, 12 H,
[9]aneS3); 2.54 (s, 6H, Me2 in 4,40-Me2bpy); 7.39 (d, 2H, J =
4.8 Hz, 4,40-Me2bpy); 8.24 (s, 2H, 4,40-Me2bpy); 8.79 (d, 2H, J =
5.8 Hz, 4,40-Me2bpy). 13C NMR (100 MHz, CD3CN): δ 21.3
(Me2 in 4,40-Me2bpy); 32.3, 33.4, 35.9 ([9]aneS3); 125.2, 128.7,
151.3, 153.3, 157.0 (4,40-Me2bpy). IR (KBr, cm-1): νP-F = 842.
ESI-MS: m/z 501 [Mþ].
CD3CN):
δ 2.41-2.75, 2.82-3.06 (m, 12H, [9]aneS3);
6.83-7.13 (m, 5H, Ph); 7.51 (dd, 2H, J = 6.0, 1.3 Hz, bpy);
8.02 (dd, 2H, J = 6.8, 1.3 Hz, bpy); 8.37 (d, 2H, J = 8.0 Hz,
bpy); 8.90 (d, 2H, J = 4.8 Hz, bpy). 13C NMR (100 MHz,
CD3CN): δ 32.5, 33.0, 35.8 ([9]aneS3); 106.7, 117.0 (CR and Cβ);
124.3, 125.2, 127.7, 128.8, 129.7, 131.8, 138.0, 153.5, 156.9 (Ph
and bpy). IR (KBr, cm-1): νCꢁC = 2081, νP-F = 849. ESI-MS:
m/z 539 [Mþ].
[([9]aneS3)(4,40-Me2bpy)Ru(CtCPh)](PF6) (2c). Yield: 0.07
g, 60%. Anal. Calcd for C26H29N2S3RuPF6: C, 43.82; H, 4.10;
N, 3.93. Found: C, 44.05; H, 4.17; N, 4.04. 1H NMR (400 MHz,
CD3CN): δ 2.41-2.69, 2.81-3.01 (m, 18 H, [9]aneS3 and Me2 in
Me2bpy), 6.86-7.10 (m, 5H, Ph); 7.34 (dd, 2H, J = 4.8, 1.0 Hz,
Me2bpy); 8.23 (s, 2H, Me2bpy); 8.70 (d, 2H, J = 5.8 Hz,
Me2bpy). 13C NMR (100 MHz, CD3CN): δ 21.2 (Me2 in
Me2bpy); 32.5, 33.0, 35.8 ([9]aneS3); 106.8 (CR); 125.0, 125.1,
128.4, 128.8, 129.8, 131.7, 150.3, 152.8, 156.6 (Ph and Me2bpy);
Cβ not resolved. IR (KBr, cm-1): νCꢁC = 2084, νP-F = 838.
ESI-MS: m/z 567 [Mþ].
[([9]aneS3)(dpq)Ru(CtCPh)](PF6) (3c). Yield: 0.07 g, 68%.
Anal. Calcd for C28H25N4S3RuPF6: C, 44.21; H, 3.32; N, 7.37.
Found: C, 44.08; H, 3.48; N, 7.49. 1H NMR (400 MHz,
CD3CN): δ 2.56 (t, 4H, J = 6.5, [9]aneS3); 2.63-2.81, 2.97-
3.13 (m, 8H, [9]aneS3), 6.79-6.85, 6.88-7.02 (m, 5H, Ph); 8.00
(dd, 2H, J = 5.3, 3.0 Hz, dpq), 9.16 (s, 2H, dpq), 9.35 (dd, 2H,
J = 4.02, 1.3 Hz, dpq), 9.54 (dd, 2H, J = 7.0, 1.3 Hz, dpq).
[([9]aneS3)(dpq)Ru(Cl)](PF6) (3a). Yield: 0.11 g, 76%. Anal.
Calcd for C20H20N4S3ClRuPF6: C, 34.59; H, 2.90; N, 8.07.
Found: C, 34.48; H, 3.08; N, 8.04. 1H NMR (400 MHz,
CD3CN):
[9]aneS3); 8.06 (dd, 2H, J = 5.3, 3.0 Hz, dpq); 9.18 (s, 2H, dpq);
9.44 (d, 2H, J = 5.3 Hz, dpq); 9.59 (d, 2H, J = 8.3 Hz, dpq). 13
δ 2.51-2.58, 2.60-2.77, 2.90-3.10 (m, 12H,
C
NMR (100 MHz, CD3CN): δ 32.5, 33.7, 35.9 ([9]aneS3); 127.8,
130.6, 134.6, 140.6, 147.5, 149.8, 155.6 (dpq). IR (KBr, cm-1):
ν
P-F = 840. ESI-MS: m/z 549 [Mþ].
[([9]aneS3)(diimine)Ru(CN)](PF6) (1-3b). A mixture of [Ru-
([9]aneS3)(diimine)Cl](PF6) (0.16 mmol), KCN (0.2 mmol), and
methanol (20 mL) was refluxed for 20 h. Upon cooling to room
temperature, a saturated aqueous solution of NH4PF6 (2 mL)
(46) Demas, J. N.; Crosby, G. A. J. Phys. Chem. 1971, 75, 991.
(47) Landgrafe, C.; Sheldrick, W. S. J. Chem. Soc., Dalton Trans.
1994, 1885.