wiley-vchbond lengths [Å] and angles [ ] for c 32h 20f 4n 4pt 2s 2. table 4. anisotropic...
TRANSCRIPT
��������� ����� ����
���
�������� ������� ������ �� ��������
� ��������� ��� �� ��������� �������
Supporting Materials for:Platinum Binuclear Complexes as Phosphorescent Dopants for
Monochromatic and White OLEDs*
Biwu Ma†, Peter I. Djurovich, Simona Garon, Bert Alleyne‡ and Mark E. Thompson§
Departments of Chemical Engineering and Material Science and Department of ChemistryUniversity of Southern California, Los Angeles, California 90089
Titles: Dr. Ma, Dr. Djurovich, Dr. Garon, Dr. Alleyne, Professor Thompson
Figure 1. Cyclic voltammograms of compounds 1, 2 and 3 in DMF with 0.1 M [(n-Bu)4N]PF6
using ferrocene as internal reference.
Figure 2. EL spectra for devices with 8% dopant of FPt1 and 1, the molecular geometry for FPt1
and 1 are shown besides the spectra.
Figure 3. Comparison between the photoluminescence spectrum of a neat sample of 1 taken at
77K and the electroluminescence spectrum of 50% 1 in mCP.
Figure 4. Two views showing π-π interactions in the two unique dimers found in crystal packing
structure of 1.
Figure 5. Applied voltage-luminance (filled symbols) and applied voltage-current density
characteristics (open symbols) for three white OLEDs with different emissive layers.
Figure 6. The external quantum efficiency as a function of current density for white OLEDs.
* We thank the Universal Display Corporation and the Department of Energy for financialsupport of this work.† Current address: Materials Science Division, Lawrence Berkeley National Laboratory,Berkeley, CA 94720‡ Current address: Universal Display Corporation, Ewing, NJ 08618§ Corresponding Author, [email protected]
2
Figure 7. ORTEP drawing of the asymmetric unit of FPt2.
Figure 8. ORTEP drawing of the full molecular structure of FPt2.
Figure 9. Absorption (in acetonitrile) and photoluminescence (in polystyrene) spectra of FPt2.
X-Ray Crystallography of FPt2
Table 1. Crystal data and structure refinement for C32H20F4N4Pt2S2.
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x
103) for C32H20F4N4Pt2S2. U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor.
Table 3. Bond lengths [Å] and angles [°] for C32H20F4N4Pt2S2.
Table 4. Anisotropic displacement parameters (Å2x 103) for C32H20F4N4Pt2S2. The anisotropic
displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ].
Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for C32H20F4N4Pt2S2.
3
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
1 2 3
Cu
rren
t (m
A)
Volts (vs. Fc+/Fc)
Figure 1. Cyclic voltammograms of compounds 1, 2 and 3 in DMF with 0.1 M [(n-Bu)4N]PF6
using ferrocene as internal reference.
400 500 600 700 800
0.0 0.2 0.4 0.6 0.8
0.0
0.2
0.4
0.6
0.8 8% FPt in CBP 8% 1 in mCP
EL
Wavelength, nm
y
x
Figure 2. EL spectra for devices with 8% dopant of FPt1 and 1, the molecular geometry for FPt1
and 1 are shown besides the spectra.
4
450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
EL
or
PL
(a.u
.)
Wavelength (nm)
neat 1 PL EL 50% 1 in mCP
Figure 3. Comparison between the photoluminescence spectrum of a neat sample of 1 taken at
77K and the electroluminescence spectrum of 50% 1 in mCP.
Figure 4. Two views showing π-π interactions in the two unique dimers found in crystal packing
structure of 1.
5
0 2 4 6 8 10 120
20
40
60
80
Cur
rent
Den
sity
(mA
/cm
2 )
Voltage (V)
10-3
10-2
10-1
100
101
102
103
104
two-dopant, dual EML single-dopant, dual EML two-dopant, single EML
Lu
min
ance
(cd/
m2 )
Figure 5. Applied voltage-luminance (filled symbols) and applied voltage-current density
characteristics (open symbols) for three white OLEDs with different emissive layers.
0.1 1 10 1000.1
1
10
Qua
ntu
m E
ffic
ienc
y (%
)
Current Density (mA/cm2)
two-dopant, dual EML single-dopant, dual EML two-dopant, single EML
Figure 6. The external quantum efficiency as a function of current density for white OLEDs.
6
Figure 7. ORTEP drawing of the asymmetric unit of FPt2.
Figure 8. ORTEP drawing of the full molecular structure of FPt2.
Pt1
S1
N1
N2
F1
C11
C18
C15C13
C12C14
C10
C3
C2 C21
C17
C16
C23C22
C19
C20
F2
7
300 400 500 600 700 8000
5k
10k
15k
20k
25k
30k
35k
abs abs x 5
Wavelength (nm)
Mo
lar
abso
rpti
vity
(M
-1cm
-1)
0
1
τ = 2.3 µs em
Em
issi
on
(a.u
.)
Figure 9. Absorption (in acetonitrile) and photoluminescence (in polystyrene) spectra of FPt2.
X-Ray Crystallography of FPt2
Diffraction data was collected at room temperature (T = 23 C) on a Bruker SMART
APEX CCD diffractometer with graphite-monochromated Mo K radiation ( = 0.71073 Å). The
cell parameters for the FPt2 were obtained from the least-squares refinement of the spots (from
60 collected frames) using the SMART program. A hemisphere of the crystal data was collected
up to a resolution of 0.75 Å, and the intensity data was processed using the Saint Plus program.
All calculations for structure determination were carried out using the SHELXTL package
(version 5.1). Initial atomic positions were located by Patterson methods using XS, and the
structure was refined by least-squares methods using SHELX with 6983 independent reflections
and within the range of 1.38-24.71 (completeness 98.8%). Absorption corrections were
applied by using SADABS. Calculated hydrogen positions were input and refined in a riding
manner along with the attached carbons.
8
Table 1. Crystal data and structure refinement for C32H20F4N4Pt2S2.
Identification code nambertm
Empirical formula C32H20F4N4Pt2S2
Formula weight 990.82
Temperature 273(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C2/c
Unit cell dimensions a = 21.8745(14) Å α= 90°.
b = 11.7316(8) Å β= 124.0430(10)°.
c = 13.6165(9) Å γ = 90°.
Volume 2895.4(3) Å3
Z 4
Density (calculated) 2.273 Mg/m3
Absorption coefficient 9.854 mm-1
F(000) 1856
Crystal size 0.30 x 0.15 x 0.10 mm3
Theta range for data collection 2.07 to 27.48°.
Index ranges -28<=h<=28, -14<=k<=14, -17<=l<=16
Reflections collected 8557
Independent reflections 3171 [R(int) = 0.0229]
Completeness to theta = 27.48° 95.4 %
Transmission Factors min/max ratio: 0.697
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 3171 / 0 / 200
Goodness-of-fit on F2 1.027
Final R indices [I>2σ(I)] R1 = 0.0250, wR2 = 0.0572
R indices (all data) R1 = 0.0302, wR2 = 0.0593
Extinction coefficient 0.00000(2)
Largest diff. peak and hole 1.037 and -0.608 e.Å-3
9
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x
103) for C32H20F4N4Pt2S2. U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor.
______________________________________________________________________________
x y z U(eq)
______________________________________________________________________________
Pt(1) 9997(1) 6627(1) 3550(1) 40(1)
S(2) 11081(1) 7619(1) 4388(1) 50(1)
N(1) 9075(2) 5689(3) 2992(3) 45(1)
N(2) 9415(2) 8197(3) 2875(3) 44(1)
C(2) 10460(2) 5092(3) 4077(4) 42(1)
C(3) 8393(3) 6112(4) 2457(4) 54(1)
F(1) 9720(2) 2206(2) 3535(3) 76(1)
C(14) 9947(2) 4204(4) 3728(3) 46(1)
C(10) 11205(2) 4824(4) 4623(4) 48(1)
C(13) 10208(3) 3083(4) 3922(4) 57(1)
C(15) 9175(3) 4537(4) 3161(4) 50(1)
C(16) 8564(3) 3837(4) 2796(4) 64(1)
C(11) 11406(3) 3701(4) 4782(4) 60(1)
C(12) 10919(3) 2809(4) 4424(4) 62(1)
C(18) 7779(3) 5444(5) 2074(5) 67(1)
C(17) 7879(3) 4296(5) 2260(5) 75(2)
F(2) 12133(2) 3436(2) 5315(3) 85(1)
C(19) 8981(2) 8485(3) 1709(4) 44(1)
C(22) 9034(3) 9877(4) 3384(4) 57(1)
C(20) 8561(2) 9472(4) 1372(4) 57(1)
C(23) 9435(2) 8907(4) 3682(4) 48(1)
C(21) 8586(3) 10173(4) 2196(5) 67(1)
______________________________________________________________________________
10
Table 3. Bond lengths [Å] and angles [°] for C32H20F4N4Pt2S2.
_____________________________________________________
Pt(1)-C(2) 1.993(4)
Pt(1)-N(1) 2.036(3)
Pt(1)-N(2) 2.132(3)
Pt(1)-S(2) 2.2909(11)
Pt(1)-Pt(1)#1 2.8660(3)
S(2)-C(19)#1 1.747(4)
N(1)-C(3) 1.336(5)
N(1)-C(15) 1.368(5)
N(2)-C(19) 1.359(5)
N(2)-C(23) 1.360(5)
C(2)-C(10) 1.396(6)
C(2)-C(14) 1.404(6)
C(3)-C(18) 1.381(6)
F(1)-C(13) 1.359(5)
C(14)-C(13) 1.399(6)
C(14)-C(15) 1.463(6)
C(10)-C(11) 1.367(6)
C(13)-C(12) 1.341(7)
C(15)-C(16) 1.401(6)
C(16)-C(17) 1.358(7)
C(11)-F(2) 1.365(6)
C(11)-C(12) 1.373(7)
C(18)-C(17) 1.365(7)
C(19)-C(20) 1.388(5)
C(19)-S(2)#1 1.747(4)
C(22)-C(23) 1.353(6)
C(22)-C(21) 1.388(7)
C(20)-C(21) 1.367(6)
C(2)-Pt(1)-N(1) 80.99(15)
C(2)-Pt(1)-N(2) 175.03(15)
N(1)-Pt(1)-N(2) 94.47(13)
C(2)-Pt(1)-S(2) 95.97(12)
N(1)-Pt(1)-S(2) 173.60(10)
11
N(2)-Pt(1)-S(2) 88.74(10)
C(2)-Pt(1)-Pt(1)#1 94.24(11)
N(1)-Pt(1)-Pt(1)#1 100.65(9)
N(2)-Pt(1)-Pt(1)#1 84.56(9)
S(2)-Pt(1)-Pt(1)#1 85.15(3)
C(19)#1-S(2)-Pt(1) 107.81(14)
C(3)-N(1)-C(15) 119.0(4)
C(3)-N(1)-Pt(1) 124.9(3)
C(15)-N(1)-Pt(1) 116.0(3)
C(19)-N(2)-C(23) 118.5(3)
C(19)-N(2)-Pt(1) 125.2(3)
C(23)-N(2)-Pt(1) 116.0(3)
C(10)-C(2)-C(14) 119.1(4)
C(10)-C(2)-Pt(1) 127.0(3)
C(14)-C(2)-Pt(1) 113.5(3)
N(1)-C(3)-C(18) 123.2(5)
C(13)-C(14)-C(2) 118.0(4)
C(13)-C(14)-C(15) 125.3(4)
C(2)-C(14)-C(15) 116.7(4)
C(11)-C(10)-C(2) 118.5(4)
F(1)-C(13)-C(12) 116.8(5)
F(1)-C(13)-C(14) 119.4(5)
C(12)-C(13)-C(14) 123.7(5)
N(1)-C(15)-C(16) 119.2(4)
N(1)-C(15)-C(14) 112.4(4)
C(16)-C(15)-C(14) 128.4(4)
C(17)-C(16)-C(15) 120.4(5)
F(2)-C(11)-C(10) 118.6(5)
F(2)-C(11)-C(12) 117.2(5)
C(10)-C(11)-C(12) 124.1(5)
C(13)-C(12)-C(11) 116.5(4)
C(17)-C(18)-C(3) 118.0(5)
C(16)-C(17)-C(18) 120.3(5)
N(2)-C(19)-C(20) 119.6(4)
N(2)-C(19)-S(2)#1 121.6(3)
C(20)-C(19)-S(2)#1 118.8(3)
12
C(23)-C(22)-C(21) 118.5(4)
C(21)-C(20)-C(19) 121.1(4)
C(22)-C(23)-N(2) 123.4(4)
C(20)-C(21)-C(22) 118.9(4)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 –x + 2, y, -z + 1/2
13
Table 4. Anisotropic displacement parameters (Å2x 103) for C32H20F4N4Pt2S2. The
anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b*
U12 ].
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________________________________________
Pt(1) 47(1) 43(1) 32(1) 1(1) 23(1) -2(1)
S(2) 51(1) 54(1) 36(1) 0(1) 19(1) -8(1)
N(1) 47(2) 53(2) 34(2) -4(2) 23(2) -9(2)
N(2) 53(2) 42(2) 40(2) -1(2) 28(2) 0(1)
C(2) 55(2) 44(2) 34(2) 4(2) 30(2) 4(2)
C(3) 56(3) 62(3) 47(3) 3(2) 31(2) -1(2)
F(1) 99(2) 50(2) 69(2) -4(1) 42(2) -15(2)
C(14) 62(3) 48(2) 31(2) 4(2) 29(2) 2(2)
C(10) 57(3) 50(2) 34(2) 1(2) 24(2) 2(2)
C(13) 82(4) 44(2) 40(2) 2(2) 31(2) -7(2)
C(15) 61(3) 58(3) 32(2) -2(2) 28(2) -9(2)
C(16) 75(4) 63(3) 56(3) -7(3) 38(3) -20(3)
C(11) 63(3) 70(3) 47(3) 6(2) 31(3) 16(3)
C(12) 89(4) 48(3) 49(3) 5(2) 40(3) 12(3)
C(18) 53(3) 92(4) 54(3) 0(3) 28(2) -8(3)
C(17) 62(3) 100(4) 64(3) -14(3) 36(3) -29(3)
F(2) 69(2) 78(2) 91(3) 4(2) 34(2) 25(2)
C(19) 41(2) 49(2) 39(2) 3(2) 21(2) 3(2)
C(22) 64(3) 53(2) 56(3) -16(2) 34(2) 0(2)
C(20) 60(3) 60(3) 43(3) 1(2) 24(2) 12(2)
C(23) 55(3) 54(2) 42(2) -6(2) 31(2) -6(2)
C(21) 69(3) 58(3) 66(3) -3(3) 33(3) 18(2)
______________________________________________________________________________
14
Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for C32H20F4N4Pt2S2.
______________________________________________________________________________
x y z U(eq)
______________________________________________________________________________
H(3) 8329 6896 2336 65
H(10) 11556 5397 4874 57
H(16) 8628 3055 2922 77
H(12) 11074 2055 4525 74
H(18) 7311 5766 1702 81
H(17) 7476 3826 2017 90
H(22) 9058 10334 3963 69
H(20) 8257 9659 573 69
H(23) 9741 8716 4481 58
H(21) 8307 10839 1963 80