Octupolar Bipyridyl Metal Complexes
4454 – 4466
3J(H,H)=15.5 Hz, 6H; H8), 7.26 (d, 3J(H,H)=5.5, 6H; H5), 7.01 (d,
(CDCl3): d=8.54 (d, 4J(H,H)=1.5 Hz, 6H; H3), 7.62 (d, 3J(H,H)=
6.1 Hz, 6H; H6), 7.58 (d, 3J(H,H)=8.8 Hz, 12H; H10); 7.50 (d,
3J(H,H)=16.3 Hz, 6H; H8), 7.45 (dd, 3J(H,H)=6.1 4J(H,H)=1.5 Hz,
6H; H5), 7.10 (d, 3J(H,H)=16.3 Hz, 6H; H7), 6.91 (d, 3J(H,H)=8.8 Hz,
12H; H11), 3.96 (t, 3J(H,H)=6.5 Hz, 12H; H13), 1.74 (m, 12H; H14),
1.27 (m, 60H; H15–19), 0.86 ppm (t, 3J(H,H)=6.0 Hz, 18H; H20); 13C
NMR (CD2Cl2): d=160.7 (C4), 157.0 (C2), 150.4 (C6), 147.3 (C12), 136.6
(C8), 129.2 (C10), 122.9 (C9), 123.6 (C7), 121.1 and 120.9 (C3 or C5),
114.9 (C11), 68.2 (C13), 31.8 (C14), 29.3 (C15), 29.2 (C16), 29.1 (C17),
26.0 (C18), 22.7 (C19), 13.9 ppm (C20); UV/Vis (CH2Cl2): lmax (e)=
387 nm (125000 Lmolꢀ1 cmꢀ1); lMLCT (e)=482 nm (41000 Lmolꢀ1 cmꢀ1);
elemental analysis calcd (%) for C126H156N6O6P2F12Ru·CH2Cl2: C 65.56,
H 6.85, N 3.61; found: C 65.05, H 7.00, N 3.57.
3
3J(H,H)=4.1 Hz, 6H; H10), 6.32 (d, J(H,H)=15.5 Hz, 6H; H7), 5.77 (d,
3J(H,H)=4.1 Hz, 6H; H11), 3.29 (t, 3J(H,H)=7.3 Hz, 24H; H13), 1.58
(m, 24H; H14), 1.28 (m, 24H; H15), 0.93 ppm (t, 3J(H,H)=7.3 Hz, 36H;
H16); 13C NMR(CD2Cl2): d=161.3 (C12), 151.0 (C4), 149.6 (C2), 146.8
(C6), 139.5 (C10), 131.5 (C8), 122.9 (C9), 121.4 (C5), 117.7 (C3), 114.1
(C7), 101.8 (C11), 53.6 (C13), 29.2 (C14), 20.2 (C15), 13.7 ppm (C16);
UV/Vis (CH2Cl2): lmax (e)=519 nm (50000 Lmolꢀ1 cmꢀ1); LRMS (only
fragmentation peaks were observed): calcd for C76H100N8FS4Zn
[Zn(d)2F]+: 1335.6; found: 1335.7; calcd for C38H50N4FS2Zn [Zn(d)F]+:
709.3; found: 709.3.
[Zn(a)3][TRISPHAT] (1a): Unclean [Zn(a)3][PF6]2 (290 mg, 0.13 mmol),
resulting from the reaction between Zn(OAc)2·2H2O and a (3 equiv) in
refluxing methanol followed by an anion exchange with NaPF6, was dis-
solved in CH2Cl2 (20 mL) in a round-bottom flask. [HNBu3][TRISPHAT]
(251 mg, 0.26 mmol) was added, and the yellow solution was stirred for
2 h. The solvent was evaporated, and the product was filtered through a
column of silica gel (eluent: CH2Cl2). After evaporation of the solvent
under vacuum and recrystallization from CH2Cl2/pentane (v/v=1:10), the
product was recovered as a yellow powder (266 mg, 58%). 1H NMR
[Ru(b)3][PF6]2 (2b): This complex was prepared following the same pro-
cedure as for 2a, but from bipyridyl ligand b. Yield: 96%; 1H NMR
(CD2Cl2): d=8.41 (brs, 6H; H3), 7.56 (d, 3J(H,H)=6 Hz, 6H; H6), 7.48
(d, 3J(H,H)=8.9 Hz, 12H; H10), 7.47 (d, 3J(H,H)=16.0 Hz, 6H; H8),
3
3
7.36 (d, J(H,H)=6 Hz, 6H; H5), 6.96 (d, J(H,H)=16 Hz, 6H; H7), 6.65
3
3
(d, J(H,H)=9 Hz, 12H; H11), 3.31 (t, J(H,H)=7.4 Hz, 24H; H13), 1.57
(m, 24H; H14), 1.35 (m, 24H; H15), 0.95 ppm (t, 3J(H,H)=7.3 Hz, 36H;
H16); 13C NMR (CD2Cl2): d=157.0 (C2), 150.0 (C12), 149.6 (C6), 147.6
(C4), 137.1 (C8), 129.4 (C10), 122.7 (C9), 122.1 (C5), 120.0 (C3), 117.5
(C7), 111.5 (C11), 50.7 (C13), 29.4 (C14), 20.3 (C15), 13.7 ppm (C16);
UV/Vis (CH2Cl2): lmax (e)=446 nm (135000 Lmolꢀ1 cmꢀ1); lMLCT (e)=
513 nm (145000 Lmolꢀ1 cmꢀ1); TGA: Td5 =3608C, Td10 =3858C; elemen-
tal analysis calcd (%) for C126H162N12P2F12Ru·4H2O: C 65.58, H 7.42, N
7.28; found: C 65.63, H 7.26, N 6.96.
3
(CD2Cl2): d=8.65 (d, J(H,H)=5 Hz, 6H; H6), 8.41 (s, 6H; H3), 7.40 (d,
3J(H,H)=8.9 Hz, 12H; H10), 7.22 (d, 3J(H,H)=5 Hz, 6H; H5), 7.13 (d,
3J(H,H)=16.1 Hz, 6H; H8), 6.89 (d, 3J(H,H)=8.9 Hz, 12H; H11) 6.71
(d, 3J(H,H)=16.1 Hz, 6H; H7), 6.91, 3.97 (t, 3J(H,H)=6.5 Hz, 12H;
H13), 1.75 (m, 12H; H14), 1.5–1.2 (m, 60H; H15–19), 0.86 ppm (t,
3J(H,H)=6.5 Hz, 18H; H20); 13C NMR (CD2Cl2): d=161.2 (C4), 150.6
(C2), 149.8 (C6), 149.7 (C12), 141.9 (d, J(C,P)=6 Hz; TRISPHAT), 136.7
(C8), 129.7 (C10), 128.4 (C9), 123.2 (TRISPHAT), 123.1 (C7), 121.1 and
119.7 (C3 or C5), 115.2 (C11), 114.6 (d, J(C,P)=19 Hz; TRISPHAT),
68.7 (C13), 32.3 (C14), 29.8 (C15), 29.7 (C16), 29.6 (C17), 26.5 (C18),
23.1 (C19), 14.4 ppm (C20); 31P NMR (CD2Cl2): d=ꢀ79.5 ppm; UV/Vis
(CH2Cl2): lmax (e)=382 nm (128000 Lmolꢀ1 cmꢀ1); emission (CH2Cl2):
lem =501 nm; TGA: Td5 =3308C, Td10 =3358C; elemental analysis calcd
(%) for C162H156N6O18Cl24P2Zn: C 55.93, H 4.52, N 2.42, found: C 55.94,
H 4.64, N 2.38.
[Ru(a)3][TRISPHAT]2 (2a): In a Schlenk flask, [RuCl2(dmso)4] (48.3 mg,
0.10 mmol) and ligand a (185 mg, 0.3 mmol) were dissolved in ethanol
(15 mL). The white suspension turned red upon heating under reflux for
10 h. After cooling to room temperature, [HNBu3][TRISPHAT] (189 mg,
0.2 mmol) was added, and the solution was stirred for 1 h. After precipi-
tation in water (200 mL), the red solid was filtered off, washed with pen-
tane and dried under vacuum. The solvent was evaporated and the prod-
uct was filtered through a column of silica gel (eluent: CH2Cl2). After
evaporation of the solvent under vacuum, the product was recovered as a
[Zn(e)3][TRISPHAT]2 (1e): Zn(OAc)2·2H2O (45 mg, 0.2 mmol) and
ligand e (0.5 g, 0.6 mmol) were dissolved in ethanol (20 mL). The mixture
was heated under reflux for 15 h. The solution was then cooled to room
temperature, and [HNBu3][TRISPHAT] (389 mg, 0.4 mmol) was added.
The orange solution was stirred for 2 h and then poured into water
(150 mL). The resulting red precipitate was filtered, dissolved in CH2Cl2,
and dried with MgSO4. After filtration and evaporation of the solvent,
the solid was purified further by precipitating it several times from
CH2Cl2/pentane (v/v=1:10). The solvents were removed under vacuum
to afford the desired product as a microcrystalline powder (0.6 g, 73%).
1H NMR (500.13 MHz, CD2Cl2): d=8.74 (d, 3J(H,H)=5.4 Hz, 6H; H6),
8.49 (s, 6H; H3), 7.42–7.38 (m, 24H; H10 and H11), 7.32 (d, 3J(H,H)=
8.5 Hz, 12H; H16), 7.31 (d, 3J(H,H)=5.8 Hz, 6H; H5), 7.26 (d,
3J(H,H)=16.2 Hz, 6H; H8), 7.16 (d, 3J(H,H)=16.2 Hz, 6H; H14), 6.89
(d, 3J(H,H)=16.2 Hz, 12H; H7 and H13), 6.64 (d, 3J(H,H)=8.6 Hz,
12H; H17), 3.31 (t, 3J(H,H)=7.2 Hz, 24H; H19), 1.61–1.58 (m, 24H;
H20), 1.37 (st, 3J(H,H)=7.2 Hz, 24H; H21), 0.96 ppm (t, J=7.5 Hz,
36H; H22); 13C NMR (125.77 MHz, CD2Cl2): d=150.4 (C2), 149.8 (C6),
148.7 (C18), 142.0 (d, J(C,P)=6 Hz; TRISPHAT), 140.6 (C4), 136.8 (C8),
133.6 (C12), 130.7 (C14), 128.6 (C16, C9), 128.4 (C10), 126.6 (C11), 124.3
(C15), 123.4 (C7 TRISPHAT), 122.8 (C13), 122.5 (C5), 119.9 (C3), 114.6
(d, J(C,P)=19.9 Hz; TRISPHAT), 112.0 (C17), 51.1 (C19), 29.8 (C20),
20.7 (C21), 14.2 ppm (C22); 31P NMR (121.49 MHz, CD2Cl2): d=
ꢀ80.57 ppm; UV/Vis (CH2Cl2): lmax (e)=482 nm (132000 Lmolꢀ1 cmꢀ1);
1
red powder (120 mg, 34%). H NMR (CD2Cl2): d=8.48 (s, 6H; H3), 8.33
3
3
(d, J(H,H)=6 Hz, 6H; H6), 7.42 (d, 12H; J(H,H)=9 Hz, H10), 7.21 (d,
3J(H,H)=6 Hz, 6H; H5), 7.18 (d, 3J(H,H)=16.1 Hz, 6H; H8), 6.93 (d,
3J(H,H)=9 Hz, 12H; H11), 6.75 (d, 3J(H,H)=16.1 Hz, 6H; H7), 4.03 (t,
3J(H,H)=6.5 Hz, 12H; H13), 1.82 (m, 12H; H14), 1.5–1.2 (m, 60H;
H15–19), 0.92 ppm (t, 3J(H,H)=6.5 Hz, 18H; H20); 13C NMR (CD2Cl2):
d=160.6 (C4), 156.9 (C2), 151.6 (C6), 146.4 (C12), 141.5 (d, J(C,P)=
6 Hz; TRISPHAT), 135.5 (C8), 129.1 (C10), 127.6 (C9), 122.9 (TRIS-
PHAT), 122.8 (C7), 120.3 (C3 and C5), 114.7 (C11), 114.0 (d, J(C,P)=
19 Hz; TRISPHAT), 68.1 (C13), 31.7 (C14), 29.3 (C15), 29.2 (C16), 29.1
(C17), 25.9 (C18), 22.6 (C19), 13.8 ppm (C20); 31P NMR (CD2Cl2): d=
ꢀ80.6 ppm; UV/Vis (CH2Cl2): lmax (e)=387 nm (124000 Lmolꢀ1 cmꢀ1);
lMLCT (e)=510 nm (51000 Lmolꢀ1 cmꢀ1); emission (CH2Cl2): lem
=
678 nm; TGA: Td5 =3558C, Td10 =3658C; elemental analysis calcd (%)
for C162H156N6O18Cl24P2Ru: C 55.77, H 4.51, N 2.41; found: C 56.28, H
4.71, N 2.24.
[Fe(a)3][TRISPHAT]2 (3a): Unclean [Fe(a)3][PF6]2 (175 mg, 0.08 mmol),
resulting from the reaction between FeCl2 and a (3 equiv) in refluxing
methanol (10 mL), followed by anion exchange with NaPF6, was dis-
solved in CH2Cl2 (10 mL) in a round-bottom flask. [HNBu3][TRISPHAT]
(152 mg, 0.16 mmol) was added, and the greenish solution was stirred for
2 h. The solvent was evaporated, and the product was filtered through a
column of silica gel (eluent: CH2Cl2). After evaporation of the solvent
under vacuum and recrystallisation from CH2Cl2/pentane (1:10), the
product was recovered as a yellow powder (90 mg, 32%). 1H NMR
TGA:
Td10 =2858C;
elemental
analysis
calcd
(%)
for
C210H198N12O12Cl24P2Zn·CH2Cl2: C 61.14, H 4.86, N 4.05; found: C 61.22,
H 4.98, N 3.83.
3
(CD2Cl2): d=8.52 (s, 6H; H3), 7.95 (d, J(H,H)=6 Hz, 6H; H6), 7.42 (d,
[Ru(a)3][PF6]2: Ruthenium trichloride hydrate (130 mg, 0.5 mmol) and
ligand a (3 equiv) were dissolved in dry DMF (20 mL). The mixture was
heated at reflux under nitrogen for 7 h, and the solution was allowed to
cool to room temperature. A solution of NaPF6 (0.2 g, 1.2 mmol) in
water (20 mL) was added to afford a dark brown precipitate. The crude
product was dissolved in CH2Cl2 and washed with water. The organic
layer was dried with MgSO4 and concentrated by evaporation, and the
product was precipitated by addition of pentane (v/v=1:10). Finally, the
red microcrystalline powder (95%) was dried under vacuum. 1H NMR
3J(H,H)=8.6 Hz, 12H; H10), 7.25 (d, 3J(H,H)=6 Hz, 6H; H5), 7.22 (d,
3J(H,H)=16.2 Hz, 6H; H8), 6.94 (d, 3J(H,H)=8.6 Hz, 12H; H11) 6.76
(d, 3J(H,H)=16.2 Hz, 6H; H7), 4.04 (t, 3J(H,H)=6.5 Hz, 12H; H13),
1.82 (m, 12H; H14), 1.5–1.2 (m, 60H; H15–19), 0.92 ppm (t, 3J(H,H)=
6.5 Hz, 18H; H20); 13C NMR (CD2Cl2): d=160.6 (C4), 159.1 (C2), 154.2
(C6), 147.4 (C12), 141.5 (d, J(C,P)=6 Hz; TRISPHAT), 135.7 (C8), 129.1
(C10), 127.5 (C9), 122.8 (C7, TRISPHAT), 120.2 and 120.0 (C3 or C5),
114.8 (C11), 114.6 (d, J(C,P)=19 Hz; TRISPHAT), 68.2 (C13), 31.8
(C14), 29.3 (C15), 29.2 (C16), 29.1 (C17), 25.9 (C18), 22.7 (C19),
Chem. Eur. J. 2004, 10, 4454 – 4466
ꢁ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4463