aqueous KNO3/H2O). The major red fraction was collected and
reduced to half its volume in vacuo and treated with aqueous
NH4PF6. The precipitate was collected by filtration. The solid was
redissolvedinCH3CN, to which water was addeduntilaprecipitate
was obtained. The precipitate was dried under vacuum to give a
red solid.
(t, J = 7.4 Hz, 4 H, a(-CH2)), 1.58 (m, 4 H, b(-CH2)), 1.32 (m, 4 H,
g(-CH2)), 0.85 (t, J = 7.3 Hz, 6 H, –CH3); 13C NMR (75 MHz,
DMSO-d6): d 159.1, 155.7, 152.9, 150.5, 147.8, 147.2, 138.7, 130.7,
129.6, 128.5, 126.0, 125.4, 120.6, 117.1, 52.2 (a(–CH2)), 30.1
(b(-CH2)), 20.5 (g(-CH2)), 14.7 (–CH3).
[Ru(L14)2](PF6)2. obtained as deep red solid in 74% yield;
[Ru(L7)2](PF6)2. obtained as red solid in 67% yield; Found: C,
54.95; H, 3.87; N, 8.20. Calc. for C64H56F12N8O4P2Ru: C, 55.21;
H, 4.05; N, 8.05%; 1H NMR (300 MHz, DMSO-d6): d 9.46 (s, 4 H;
Found: C, 61.72; H, 5.36; N, 8.51. Calc. for C82H82F12N10P2Ru:
1
C, 61.61; H, 5.17; N, 8.76%; H NMR (300 MHz, DMSO-d6): d
9.34 (s, 4 H; H3¢, 5¢, terpy), 9.04 (d, J = 8.1 Hz, 4 H; H3, 3¢¢, terpy),
8.27 (d, J = 8.5 Hz, 4 H), 8.05 (t, J = 7.7 Hz, 4 H; H4, 4¢¢, terpy), 7.51
(d, J = 5.3 Hz, 4 H), 7.35 – 7.20 (m, 12 H), 7.08 – 6.99 (m, 14 H; Ar),
3.83 – 3.72 (m, 8 H, a (-CH2)), 1.69 – 1.60 (m, 8 H, b(-CH2)),
1.45 – 1.37 (m, 8 H, g(-CH2)), 0.99 – 0.90 (m, 12 H, –CH3); 13C
NMR (75 MHz, DMSO-d6): d 158.3, 154.8, 152.1, 150.2, 147.5,
147.0, 145.0, 139.0, 137.8, 129.4, 128.7, 127.6, 127.3, 124.5, 124.1,
121.5, 121.2, 120.8, 119.4, 114.7, 67.0, 51.3 (a(-CH2)), 29.2
(b(-CH2)), 19.6 (g(-CH2)), 13.9 (–CH3).
H
3¢, 5¢, terpy), 9.09 (d, J = 8.2 Hz, 4 H; H3, 3¢¢, terpy), 8.39 (d, J =
8.6 Hz, 4 H), 8.07 (t, J = 7.9 Hz, 4 H; H4, 4¢¢, terpy), 7.60 – 7.45 (m,
10 H), 7.37 – 7.04 (m, 12 H; Ar), 1.48 (s, 18 H, –OC(CH3)3); 13
C
NMR (75 MHz, DMSO-d6): d 158.9, 155.9, 153.7 (–C=O), 153.1,
147.2, 145.6, 143.4, 138.9, 134.0, 130.0, 129.1, 128.6, 128.1, 127.2,
125.7, 122.0, 81.8 (–OC(CH3)3), 28.7 (CH3).
[Ru(L8)2](PF6)2. obtained as red solid in 60% yield; Found: C,
57.97; H, 4.56; N, 7.83. Calc. for C86H82F12N10O8P2Ru: C, 58.20;
1
H, 4.66; N, 7.89%; H NMR (300 MHz, DMSO-d6): d 9.46 (s,
General method for homo-dinuclear complexes
4 H; H3¢, 5¢, terpy), 9.08 (d, J = 8.2 Hz, 4 H; H3, 3¢¢, terpy), 8.39
(d, J = 8.6 Hz, 4 H), 8.07 (t, J = 7.5 Hz, 4 H; H4, 4¢¢, terpy),
7.60 – 7.53 (m, 8 H), 7.43–7.38 (m, 4 H), 7.34–7.24 (m, 18 H;
Ar), 1.48 (s, 18 H, –OC(CH3)3), 1.41 (s, 18 H, –OC(CH3)3);
13C NMR (75 MHz, DMSO-d6): d 158.9, 155.9, 153.8 (-C=O),
153.6 (-C=O), 153.0, 147.2, 145.4, 143.5, 141.6, 140.8, 138.9,
134.1, 129.8, 129.2, 128.5, 128.3, 128.0, 126.9, 125.7, 122.0, 82.0
(-OC(CH3)3), 81.4 (-OC(CH3)3), 28.7 (CH3).
[(PTPY)Ru(L)Ru(PTPY)](PF6)4 (L = L11 and L12)
A suspension of ligand L11 or L12 and 2 eq. [(PTPY)RuCl3] was
heated at reflux in EtOH (200 cm3) containing several drops of
N-ethylmorpholine for 12 h. The reaction mixture was poured
into aqueous NH4PF6, and the precipitated solid was purified
by column chromatography (silica gel, CH3CN/sat. aqueous
KNO3/H2O). The major fraction was concentrated and ion-
exchanged with aqueous NH4PF6 to precipitate the product as
a red solid.
[Ru(L9)2](PF6)2. obtained as deep red solid in 63% yield;
Found: C, 59.74; H, 4.99; N, 7.74. Calc. for C108H108F12N12O12P2Ru:
[(PTPY)Ru(L11)Ru(PTPY)](PF6)4. obtained as deep red solid
in 58% yield; Found: C, 51.37; H, 3.49; N, 8.21. Calc. for
C100H80F24N14O4P4Ru2: C, 51.69; H, 3.47; N, 8.44%; 1H NMR
(300 MHz, DMSO-d6): d 9.51 (s, 4 H; H3¢, 5¢, terpy), 9.49 (s, 4 H;
1
C, 60.13; H, 5.05; N, 7.79%; H NMR (300 MHz, DMSO-d6):
d 9.46 (s, 4 H; H3¢, 5¢, terpy), 9.08 (d, J = 8.1 Hz, 4 H; H3, 3¢¢
,
terpy), 8.39 (d, J = 8.2 Hz, 4 H), 8.08 (t, J = 7.73 Hz, 4 H;
H
4, 4¢¢, terpy), 7.60 – 7.53 (m, 8 H), 7.40 – 7.23 (m, 30 H; Ar), 1.47
H
3¢, 5¢, terpy), 9.12 (dd, J = 8.52 Hz, 8 H; H3, 3¢¢, terpy), 8.45 (d, J =
(s, 18 H, –OC(CH3)3), 1.41 (s, 18 H, –OC(CH3)3), 1.39 (s, 18 H,
–OC(CH3)3); 13C NMR (75 MHz, DMSO-d6): d 158.9, 155.9, 153.8
(–C=O), 153.6 (–C=O), 153.0, 147.2, 145.4, 143.5, 141.3, 140.9,
138.9, 134.1, 129.8, 129.2, 128.6, 128.4, 128.1, 128.0, 126.9, 125.6,
122.0, 82.0 (–OC(CH3)3), 81.6 (–OC(CH3)3), 81.4 (–OC(CH3)3),
28.6 (CH3).
7.59 Hz, 8 H), 8.09 (t, J = 7.55 Hz, 8 H; H4, 4¢¢, terpy), 7.78 (d, J =
7.11 Hz, 4 H), 7.67 (m, 6 H), 7.57 (s, 8 H), 7.32 (s, 4 H), 7.30
(t, J = 6.08 Hz, 8 H; Ar), 1.51 (s, 18 H, –OC(CH3)3); 13C NMR
(75 MHz, DMSO-d6): d 158.9, 156.0, 153.7 (-C=O), 153.1, 148.0,
147.2, 145.4, 141.3, 138.9, 137.1, 134.3, 131.2, 130.3, 129.2, 128.6,
128.2, 125.7, 122.1, 82.0 (–OC(CH3)3), 28.8 (–CH3).
[Ru(L10)2](PF6)2. obtained as deep red solid in 57% yield;
[(PTPY)Ru(L12)Ru(PTPY)](PF6)4. obtained as deep red solid
Found: C, 61.19; H, 5.41; N, 7.51. Calc. for C130H134F12N14O16P2Ru:
1
in 83% yield; Found: C, 53.87; H, 3.86; N, 8.59. Calc. for
C, 61.48; H, 5.32; N, 7.72%; H NMR (300 MHz, DMSO-d6): d
1
9.46 (s, 4 H; H3¢, 5¢, terpy), 9.08 (d, J = 8.3 Hz, 4 H; H3, 3¢¢, terpy), 8.38
(d, J = 8.6 Hz, 4 H), 8.06 (t, J = 7.5 Hz, 4 H; H4, 4¢¢, terpy), 7.59 – 7.53
(m, 8 H), 7.33 – 7.19 (m, 38 H; Ar), 1.46 (s, 18 H, –OC(CH3)3), 1.40
(s, 18 H, –OC(CH3)3), 1.37 (s, 18 H, –OC(CH3)3), 1.35 (s, 18 H,
–OC(CH3)3); 13C NMR (75 MHz, DMSO-d6): d 158.9, 155.9, 153.8
(–C=O), 153.6 (–C=O), 153.1, 147.2, 145.4, 143.5, 141.3, 141.2,
141.1, 140.8, 138.9, 134.1, 129.7, 129.2, 128.5, 128.4, 128.1, 127.9,
126.8, 125.7, 122.0, 81.9 (–OC(CH3)3), 81.6 (–OC(CH3)3), 81.5
(–OC(CH3)3), 81.3 (–OC(CH3)3), 28.7, 28.6 (CH3).
C122H106F24N16O8P4Ru2: C, 54.15; H, 3.95; N, 8.28%; H NMR
(300 MHz, DMSO-d6): d 9.50 (s, 4 H; H3¢, 5¢, terpy), 9.46 (s, 4 H;
H
3¢, 5¢, terpy), 9.11 (dd, J = 8.2 Hz, 8 H; H3, 3¢¢, terpy), 8.43 (dd, J =
7.6 Hz, 8 H), 8.07 (t, J = 7.4 Hz, 8 H; H4, 4¢¢, terpy), 7.79 (t, J =
7.1 Hz, 4 H), 7.68 (t, J = 8.1 Hz, 2 H), 7.57 (m, 12 H), 7.31 (m, 20 H;
Ar), 1.46 (s, 18 H, –OC(CH3)3), 1.41 (s, 18 H, -OC(CH3)3); 13C
NMR (75 MHz, DMSO-d6): d 158.9, 156.0, 153.8 (–C=O), 153.6
(–C=O), 153.1, 147.9, 147.2, 145.4, 141.3, 141.1, 140.9, 138.9,
137.0, 134.1, 131.2, 130.3, 129.2, 128.6, 128.2, 128.0, 125.7, 122.1,
82.0 (–OC(CH3)3), 81.6 (–OC(CH3)3), 28.7 (–CH3).
[Ru(L13)2](PF6)2. obtained as red solid in 74% yield; Found: C,
56.97; H, 4.52; N, 8.36. Calc. for C62H56F12N8P2Ru: C, 57.10; H,
General procedure for deprotection of ligands or complexes by
thermolysis or by treatment with TMSI
1
4.33; N, 8.59%; H NMR (300 MHz, DMSO-d6): d 9.25 (s, 4 H;
H
3¢, 5¢, terpy), 8.95 (d, J = 8.1 Hz, 4 H; H3, 3¢¢, terpy), 8.17 (d, J =
8.9 Hz, 4 H), 7.94 (t, J = 8.4 Hz, 4 H; H4, 4¢¢, terpy), 7.42 – 7.35 (m,
The protected ligands or complexes were heated in a Schlenk
tube under argon for 12 h at 185 ◦C, and then cooled to
8 H), 7.22 – 7.01 (m, 10 H), 6.99 (d, J = 8.9 Hz, 4 H; Ar), 3.78
3258 | Dalton Trans., 2009, 3247–3261
This journal is
The Royal Society of Chemistry 2009
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