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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, met@usc.edu

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