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[23] General procedure for synthesis of complexes 1–3: under nitrogen atmosphere, a
mixture of RuCl3·3H2O (0.136 g, 0.5 mmol) and L (0.284 g, 0.55 mmol) in EtOH
was refluxed for 5 h. The color of the solution changed from black brown to red-
brown slowly and further generated the red-brown precipitates. After being
cooled to room temperature, the precipitates were filtered, washed with EtOH
and Et2O, and dried under vacuum. Without purification, this compound was used
in the following synthesis. An EtOH (10 mL) slurry of red-brown precipitates and
MOTPP/TPP/TFTPP (0.387/0.288/0.513 g, 1.1 mmol) was treated with excess Et3N
(1 mL). The solid substance slowly dissolved and the color of the solution changed
to red-orange. After being refluxed for 6 h, the red-orange solution was cooled to
room temperature and the solvent was removed under vacuum to give a solid red
substance. The solid was extracted with CH2Cl2 (25 mL) and filtered through
Celite. The volume of the filtrate was reduced to approximately 10 mL under
vacuum and hexane of 30 mL was carefully layered and allowed to slowly diffuse
into the CH2Cl2 solution. Over 24 h, some red crystals were obtained. The crystals
were filtered, washed with Et2O, and dried under vacuum. 1: yield (0.454 g, 67%).
FT-IR (KBr, cm−1): 1954. 31P{1H} NMR (161.98 MHz, CDCl3): δ (ppm) 38.16 (s).
1H NMR (400.1 MHz, DMSO-d6): δ (ppm) −6.14 (t, J=22.4 Hz, 1H); 3.66 (s,
18H); 6.48–7.41 (m, 46H); 8.10–8.20 (m, 3H). Anal. Calc. for C77H68N5O6P2-
RuCl·CH2Cl2 (%): C, 64.93; H, 4.89; N, 4.85. Found (%): C, 64.83; H, 4.89; N, 4.85. 2:
yield (0.370 g, 63% yield). FT-IR (KBr, cm−1): 1991. 31P{1H} NMR (161.98 MHz,
CDCl3): δ (ppm) 41.65 (s). 1H NMR (400.1 MHz, DMSO-d6): δ (ppm) −6.13 (t,
J=22.4 Hz, 1H); 6.24–7.38 (m, 52H); 8.14–8.25 (m, 3H). Anal. Calc. for
C71H56N5P2RuCl·CH2Cl2 (%): C, 68.49; H, 4.63; N, 5.55. Found (%): C, 68.57; H,
4.85; N, 5.40. 3: yield (0.554 g, 70%). FT-IR (KBr, cm−1): 1977. 31P{1H} NMR
(161.98 MHz, CDCl3): δ (ppm) 45.90 (s). 1H NMR (400.1 MHz, DMSO-d6): δ
(ppm) −6.47 (t, J=22.4 Hz, 1H); 6.36–7.60 (m, 46H); 8.29–8.47 (m, 3H). Anal.
Calc. for C77H50N5F18P2RuCl·CH2Cl2 (%): C, 56.08; H, 3.14; N, 4.19. Found (%): C,
56.00; H, 3.30; N, 4.29.
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