(500 MHz, CDCl3, d): 8.72 (d, 3J ¼ 4.5 Hz, 1H, H6(A)), 8.69 (d, 3J ¼ 7.9 Hz,
1H, H3(A)), 8.62 (d, 4J ¼ 1.2 Hz, 1H, H3(B)), 8.20 (d, 3J ¼ 7.4 Hz, 2H, H2(C)),
7.93 (d, 4J ¼ 1.2 Hz, 1H, H5(B)), 7.87 (td, 3J ¼ 7.7 Hz, 4J ¼ 1.7 Hz, 1H,
7.74 (d, J ¼ 5.7 Hz, 1H), 7.70 (d, J ¼ 1.7 Hz, 1H), 7.63 (d, J ¼ 5.6 Hz, 1H),
7.58 (d, J ¼ 7.7 Hz, 1H), 7.45 (t, J ¼ 6.5 Hz, 1H), 7.29 (d, J ¼ 7.8 Hz, 1H),
7.14–7.07 (m, 2H), 7.01 (t, J ¼ 7.5 Hz, 2H), 6.97 (d, J ¼ 2.0 Hz, 2H), 6.87
(td, J ¼ 7.6 Hz, J ¼ 1.1 Hz, 1H), 6.80 (t, J ¼ 7.6 Hz, 2H), 6.70–6.53 (m, 4H),
6.44 (t, J ¼ 7.4 Hz, 1H), 6.01 (d, J ¼ 7.7 Hz, 1H), 5.63 (d, J ¼ 7.5 Hz, 1H),
4.07 (t, J ¼ 6.5 Hz, 4H), 1.87–1.80 (m, 4H), 1.54–1.47 (m, 4H), 1.44–1.26
(m, 24H), 0.92 (t, J ¼ 6.9 Hz, 6H); 13C NMR (126 MHz, CD2Cl2, d): 169.23,
167.64, 166.33, 161.76, 157.53, 157.20, 151.65, 151.28, 150.82, 149.28,
149.20, 147.21, 143.33, 143.13, 139.64, 138.55, 138.42, 138.11, 137.44,
131.78, 131.18, 130.64, 129.99, 129.47, 128.27, 128.20, 127.80, 125.35,
125.00, 124.87, 123.74, 123.18, 122.78, 121.31, 121.17, 120.29, 120.25,
106.28, 103.59, 68.96, 32.30, 29.98, 29.96, 29.78, 29.72, 29.62, 26.39,
23.08, 14.28; IR (solid): n ¼ 3047 (w), 2922 (w), 2853 (w), 1587 (m), 1541
(w), 1477 (m), 1441 (m), 1412 (m), 1400 (m), 1369 (w), 1298 (w), 1269 (w),
1229 (w), 1161 (s), 1061 (w), 1030 (w), 829 (s), 789 (s), 754 (s), 727 (s), 696
(s), 669 (s), 623 (m), 555 (m) cmꢀ1; MS (ESI, m/z): 1121.6 [M-PF6]þ (calc.
1121.5); Anal. calcd. for C64H72F6IrN4O2Pꢄ0.5H2O (1275.47): C 60.27,
H 5.77, N 4.39; found: C 60.32, H 5.52, N 4.23.
H
4(A)), 7.54 (t, 3J ¼ 7.6 Hz, 2H, H3(C)), 7.46 (t, 3J ¼ 7.3 Hz, 1H, H4(C)), 7.35
(dd, 3J ¼ 7.0 Hz, 3J ¼ 5.2 Hz, 1H, H5(A)), 7.05 (d, 4J ¼ 2.1 Hz, 2H, H2(D)),
6.71 (t, 4J ¼ 2.0 Hz, 1H, H4(D)), 6.61 (d, 4J ¼ 2.0 Hz, 4H, H2(E)), 6.43 (t,
4J ¼ 2.0 Hz, 2H, H4(E)), 5.05 (s, 4H, ArDOCH2ArE), 3.95 (t, 3J ¼ 6.6 Hz, 8H,
OCH2CH2CH2), 1.80–1.73 (m, 8H, OCH2CH2CH2), 1.48–1.40 (m, 8H,
OCH2CH2CH2), 1.37–1.21 (m, 64H, OCH2CH2CH2(CH2)8CH3), 0.88 (t,
3J ¼ 6.9 Hz, 12H, O(CH2)11CH3); 13C NMR (126 MHz, CDCl3, d): 160.72
(C3(E)), 160.56 (C3(D)), 157.24 (C6(B)), 156.49 (C2(A)/C2(B)), 156.42 (C2(A)
C
/
2(B)), 150.30 (C4(B)), 149.20 (C6(A)), 141.06 (C1(D)), 139.54 (C1(C)), 138.94
(C1(E)), 137.02 (C4(A)), 129.24 (C4(C)), 128.90 (C3(C)), 127.22 (C2(C)), 123.96
(C5(A)), 121.69 (C3(A)), 118.72 (C5(B)), 117.64 (C3(B)), 106.86 (C2(D)), 105.90
(C2(E)), 102.51 (C4(D)), 101.10 (C4(E)), 70.54 (ArDOCH2ArE), 68.25
(OCH2(CH2)10CH3), 32.07 (OCH2(CH2)10CH3), 29.82 (OCH2(CH2)10CH3),
29.79
(OCH2(CH2)10CH3), 29.57 (OCH2(CH2)10CH3), 29.50 (OCH2(CH2)10CH3),
29.42 (OCH2(CH2)10CH3), 26.21 (OCH2CH2CH2), 22.84
(OCH2(CH2)10CH3),
29.76
(OCH2(CH2)10CH3),
29.74
g) Preparation of 4. A yellow suspension of tetrakis(2-phenylpyridine-
C,N)di(m-chloro)diiridium(III) (75 mg, 0.0704 mmol, 1.00 eq.) and
G1ppbpy (177 mg, 0.141 mmol, 2.00 eq.) in MeOH (25 mL) and CH2Cl2
(25 mL) was refluxed under an inert atmosphere of N2 in the dark for 15 h.
The orange solution was then cooled down to room temperature and solid
ammonium hexafluorophosphate (115 mg, 0.704 mmol, 10.0 eq.) was
added to the solution. The mixture was stirred for 30 min at room
temperature and then evaporated to dryness. The crude material was
purified by column chromatography (Alox 90, CH2Cl2:hexane ¼ 1:1 !
CH2Cl2 ! CH2Cl2:MeOH ¼ 100:2), followed by a subsequent column
chromatography (silica gel 60; CH2Cl2:hexane ¼ 1:1 ! CH2Cl2 ! CH2Cl2:
MeOH ¼ 100:2) yielding the desired product as an orange solid (253 mg,
0.133 mmol, 96%). 1H NMR (500 MHz, CD2Cl2, d): 8.66–8.62 (m,
J ¼ 11.6 Hz, 2H), 8.19 (t, J ¼ 7.9 Hz, 1H), 7.95 (d, J ¼ 5.5 Hz, 1H), 7.92–
7.86 (m, 3H), 7.80 (t, J ¼ 7.8 Hz, 1H), 7.74 (d, J ¼ 5.6 Hz, 1H), 7.69 (s, 1H),
7.64 (d, J ¼ 5.9 Hz, 1H), 7.59 (d, J ¼ 7.8 Hz, 1H), 7.45 (t, J ¼ 6.6 Hz, 1H),
7.29 (d, J ¼ 7.8 Hz, 1H), 7.14–7.07 (m, 4H), 7.01 (t, J ¼ 7.5 Hz, 2H), 6.87 (t,
J ¼ 7.5 Hz, 1H), 6.84–6.78 (m, 3H), 6.69–6.57 (m, 7H), 6.47–6.42 (m, 3H),
6.01 (d, J ¼ 7.7 Hz, 1H), 5.63 (d, J ¼ 7.6 Hz, 1H), 5.11 (s, 4H), 3.97 (t,
J ¼ 6.5 Hz, 8H), 1.82–1.74 (m, 8H), 1.51–1.43 (m, 8H), 1.43–1.24 (s, 64H),
0.92 (t, J ¼ 6.7 Hz, 12H); 13C NMR (126 MHz, CD2Cl2, d): 169.23, 167.63,
166.35, 161.22, 161.02, 157.60, 157.19, 151.38, 151.27, 150.80, 149.31,
149.21, 147.18, 143.32, 143.12, 139.66, 139.12, 138.54, 138.41, 138.09,
137.85, 137.63, 131.79, 131.19, 130.64, 130.00, 129.49, 128.27, 128.18,
127.79, 125.46, 125.00, 124.87, 123.74, 123.20, 122.77, 121.37, 121.18,
120.28, 120.23, 107.01, 106.08, 104.50, 100.97, 70.76, 68.54, 32.32, 30.07,
30.04, 30.01, 29.99, 29.80, 29.75, 29.65, 26.42, 23.09, 14.28; IR (solid):
n ¼ 2922 (w), 2853 (w), 1593 (m), 1543 (w), 1454 (w), 1371 (w), 1300 (w),
1269 (w), 1157 (m), 1057 (w), 831 (s), 787 (s), 754 (s), 729 (s), 694 (s), 621
(s) cmꢀ1. MS (ESI, m/z): 1758.4 [M-PF6]þ (calc. 1758.0). Anal. calcd. for
C106H140F6IrN4O6P (1903.45): C 66.89, H 7.41, N 2.94; found: C 66.92,
H 7.20, N 2.75.
Device preparation: PEDOT:PSS was purchased from HC-Starck and
solvents used were obtained from Aldrich. ITO-coated glass plates
(15 V &ꢀ1) were patterned using conventional photolithography (obtained
from Naranjosubstrates). The substrates were extensively cleaned using
sonification in subsequently water-soap, water, and 2-propanol baths. After
drying, the substrates were placed in a UV-ozone cleaner (Jelight 42-220)
for 20 min.
The electroluminescent devices were prepared as follows. Transparent
thin films of complexes 1–3 containing different amounts of the ionic liquid
(1-butyl-3-methylimidazolium hexafluorophosphate) were obtained by
spinning from acetonitrile solutions using concentrations of 20mg mLꢀ1
at 2000 rpm for 40 s, resulting in 80-nm-thick films. Prior to the deposition of
the emitting layer, a 100-nm layer of PEDOT:PSS was deposited to increase
the device preparation yield. The thickness of the films was determined
using an Ambios XP1 profilometer. After spinning the organic layers, the
samples were transferred to an inert atmosphere glovebox (< 0.1 ppm O2
and H2O, MBraun) and dried on a hot plate at 80 8C for 1 h. Aluminum
metal electrodes (80 nm) were thermally evaporated using a shadow mask
(OCH2(CH2)10CH3), 14.28 (O(CH2)11CH3); IR (solid): n ¼ 3059 (w),
2918 (s), 2849 (s), 1593 (s), 1553 (w), 1450 (m), 1377 (m), 1346 (w), 1325
(w), 1296 (m), 1155 (s), 1053 (s), 1014 (w), 825 (m), 793 (w), 775 (w), 737
(w), 719 (w), 689 (w), 609 (w), 582 (w) cmꢀ1; MS (ESI, m/z): 1281.0
[MþNa]þ (calc. 1279.9); Anal. calcd. for C84H124N2O6 (1257.89): C 80.21,
H 9.94, N 2.23; found: C 80.03, H 9.80, N 2.06.
e) Preparation of 2. A yellow suspension of tetrakis(2-phenylpyridine-
C,N)di(m-chloro)diiridium(III) (300 mg, 0.280 mmol, 1.00 eq.) and
Meppbpy (208 mg, 0.565 mmol, 2.00 eq.) in MeOH (30 mL) and CH2Cl2
(30 mL) was refluxed under an inert atmosphere of N2 in the dark for 12 h.
The orange solution was then cooled down to room temperature, and solid
ammonium hexafluorophosphate (456 mg, 2.80 mmol, 10.0 eq.) was
added to the solution. The mixture was stirred for 45 min at room
temperature and then evaporated to dryness. The crude material was
purified by column chromatography (Alox 90, CH2Cl2 ! CH2Cl2:
MeOH ¼ 100:1) yielding the desired product as an orange solid
(519 mg, 0.512 mmol, 91%). 1H NMR (500 MHz, CD2Cl2, d): 8.65 (d,
J ¼ 1.3 Hz, 1H), 8.63 (d, J ¼ 8.2 Hz, 1H), 8.15 (t, J ¼ 7.9 Hz, 1H), 7.92–7.81
(m, 4H), 7.77 (t, J ¼ 7.8 Hz, 1H), 7.70 (d, J ¼ 5.7 Hz, 1H), 7.66 (s, 1H), 7.63
(d, J ¼ 5.7 Hz, 1H), 7.54 (d, J ¼ 7.7 Hz, 1H), 7.40 (t, J ¼ 6.5 Hz, 1H), 7.25 (d,
J ¼ 7.8 Hz, 1H), 7.12–7.02 (m, 2H), 6.99–6.94 (m, 4H), 6.83 (t, J ¼ 7.5 Hz,
1H), 6.77 (t, J ¼ 7.5 Hz, 2H), 6.68–6.50 (m, 4H), 6.40 (t, J ¼ 7.4 Hz, 1H),
5.97 (d, J ¼ 7.6 Hz, 1H), 5.59 (d, J ¼ 7.6 Hz, 1H), 3.88 (s, 6H); 13C NMR
(126 MHz, CD2Cl2, d): 169.21, 167.58, 166.30, 162.23, 157.59, 157.18,
151.58, 151.34, 150.75, 149.36, 149.22, 147.26, 143.36, 143.13, 139.70,
138.56, 138.41, 138.12, 137.68, 131.81, 131.15, 130.64, 129.99, 129.46,
128.26, 128.17, 127.83, 127.82, 125.54, 124.99, 124.85, 123.78, 123.16,
122.79, 121.46, 121.15, 120.26, 120.23, 105.87, 102.89, 56.16; IR (solid):
n ¼ 3043 (w), 2947 (w), 2843 (w), 1595 (s), 1539 (w), 1477 (m), 1394 (m),
1308 (w), 1269 (w), 1204 (m), 1155 (s), 1061 (m), 1030 (w), 935 (w), 829
(s), 789 (s), 754 (s), 725 (s), 694 (m), 667 (w), 615 (w), 579 (w), 555 (s)
cmꢀ1; MS (ESI, m/z): 869.2 [M-PF6]þ (calc. 869.2). Anal. calcd. for
C46H36F6IrN4O2Pꢄ0.5H2O (1013.98): C 54.49, H 3.58, N 5.53; found:
C 54.52, H 3.71, N 5.45.
f) Preparation of 3. A yellow suspension of tetrakis(2-phenylpyridine-
C,N)di(m-chloro)diiridium(III) (200 mg, 0.187 mmol, 1.00 eq.) and
C10ppbpy (232 mg, 0.373 mmol, 2.00 eq.) in MeOH (30 mL) and CH2Cl2
(30 mL) was refluxed under an inert atmosphere of N2 in the dark for 12 h.
The orange solution was then cooled down to room temperature and solid
ammonium hexafluorophosphate (304 mg, 1.87 mmol, 10.0 eq) was added
to the solution. The mixture was stirred for 30 min at room temperature
and then evaporated to dryness. The crude material was purified by column
chromatography (Alox 90, CH2Cl2:hexane ¼ 1:1 ! CH2Cl2 ! CH2Cl2:
MeOH ¼ 100:2), followed by a subsequent column chromatography (silica
gel 60; CH2Cl2 ! CH2Cl2: MeOH ¼ 100:2) yielding the desired product as
an orange solid (454 mg, 0.358 mmol, 96%). Rf (TLC, silica gel,
CH2Cl2:MeOH ¼ 100:1): 0.3; 1H NMR (500 MHz, CD2Cl2, d): 8.66 (d,
J ¼ 1.6 Hz, 1H), 8.63 (d, J ¼ 8.2 Hz, 1H), 8.18 (t, J ¼ 7.9 Hz, 1H), 7.95 (d,
J ¼ 4.8 Hz, 1H), 7.91–7.86 (m, 3H), 7.81 (td, J ¼ 8.0 Hz, J ¼ 1.3 Hz, 1H),
Adv. Funct. Mater. 2010, 20, 1511–1520
1518
ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim