Supporting Information

Synthesis and structure-properties correlation of

blue fluorescence isomer emitters based on rigid

pyrazine-bridged carbazole frameworks Lingjuan Wei, Jie Li, Kai Xue, Shanghui Ye and Hongji Jiang *

(Nanjing University of Posts and Telecommunications, Institute of Advanced Materials, Key Laboratory for

Organic Electronics and Information Displays and Jiangsu Key Laboratory for Biosensors, Jiangsu National

Synergetic Innovation Center for Advanced Materials, Nanjing 210023)

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019

Table S1. Data results of linear fitting of the Lippert–Magada equation for the compounds TCz-3PA-TCz, TCz-3,9PA-TCz and

TCz-9PA-TCz

λabs, max (nm) a λem, max (nm)

toluen

e

CHCl3 EA THF toluen

e

CHCl3 EA THFIntercep

tslope b R2 c a(Å) μge(D)

TCz-3PA-TCz 392 396 390 391 424 453 431 433 1926.92 2829.34 0.84 7.19 1.02

TCz-3,9PA-

TCz388 400 389 390 431 464 438 440 2576.85 1718.55 0.78 7.19 0.80

TCz-9PA-TCz 391 404 391 390 451 482 458 458 3393.85 1966.82 0.90 7.19 0.85

a Excitation wavelength =315 nm. b R2 represents a linear correlation coefficient. c a is the onsagar cavity radius

Figure S1. The 1H-NMR spectrum of 9-(4-(tert-butyl)phenyl)-9H-carbazole (CDCl3, 400 MHz, ppm)

Figure S2. The 1H-NMR spectrum of 3,6-dibromo-9-(4-(tert-butyl)phenyl)-9H-carbazole (CDCl3, 400 MHz,

ppm)

Figure S3. The MALDI-TOF spectrum of 3,6-dibromo-9-(4-(tert-butyl)phenyl)-9H-carbazole

Figure S4. The 1H-NMR spectrum of 3-bromo-6,9-bis(4-(tert-butyl)phenyl)-9H-carbazole (CDCl3, 400

MHz, ppm)

Figure S5. The MALDI-TOF spectrum of 3-bromo-6,9-bis(4-(tert-butyl)phenyl)-9H-carbazole

Figure S6. The 1H-NMR spectrum of 3,9-bis(4-(tert-butyl)phenyl)-6-(4,4,5,5-tetramethyl-1,3,2-

dioxaborolan-2-yl)-9H-carbazole (CDCl3, 400 MHz, ppm)

Figure S7. The MALDI-TOF spectrum of 3,9-bis(4-(tert-butyl)phenyl)-6-(4,4,5,5-tetramethyl-1,3,2-

dioxaborolan-2-yl)-9H-carbazole

Figure S8. The 1H-NMR spectrum of L1 (CDCl3, 400 MHz, ppm)

Figure S9. The 1H-NMR spectrum of 3,6-bis(4-(tert-butyl)phenyl)-9H-carbazole (CDCl3, 400 MHz, ppm)

Figure S10. The 1H-NMR spectrum of TCz-3PA-TCz (CDCl3, 400 MHz, ppm)

Figure S11. The 13C-NMR spectrum of TCz-3PA-TCz (CDCl3, 100 MHz, ppm)

Figure S12. The MADI-TOF spectrum of TCz-3PA-TCz

Figure S13. The 1H-NMR spectrum of TCz-3,9PA-TCz (CDCl3, 400 MHz, ppm)

Figure S14. The 13C-NMR spectrum of TCz-3,9PA-TCz (CDCl3, 100 MHz, ppm)

Figure S15. The MALDI-TOF spectrum of TCz-3,9PA-TCz

Figure S16. The 1H-NMR spectrum of TCz-9PA-TCz (CDCl3, 400 MHz, ppm)

Figure S17. The 13C-NMR spectrum of TCz-9PA-TCz (CDCl3, 100 MHz, ppm)

Figure S18. The MALDI-TOF spectrum of TCz-9PA-TCz

400 5000

200

400

600

aTCz-3PA-TCz

Water fraction (fw)/vol%

Wavelength(nm)

inte

nsity

90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

400 5000

200

400

600b

TCz-3,9PA-TCzWater fraction (fw)/vol%

inte

nsity

Wavelength(nm)

90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

400 480 5600

100

200

300

400

inte

nsity

Wavelength(nm)

cTCz-9PA-TCz

Water fraction (fw)/vol%

90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

0 20 40 60 80 100

0.0

0.2

0.4

0.6

0.8

1.0

TCz-3PA-TCz TCz-3,9PA-TCz TCz-9PA-TCz

d

I/I0

Water fraction (fw)/vol%

Figure S19. The PL emission spectra of compounds TCz-3PA-TCz (a), TCz-3,9PA-TCz (b) and TCz-9PA-TCz

(c) in the tetrahydrofuran and water mixtures with different water fractions (fw) at a fixed concentration of 1

× 10−5 mol/L. The plot of relative PL emission intensity (I/I0) versus fw (I and I0 are PL emission intensity in the

mixture and pure tetrahydrofuran solution(d)

300 400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0

EL In

tens

ity (a

.u.)

Wavelength (nm)

10V 9V 8V 7V 6V

TCz-3PA-TCz

300 400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0 TCz-3,9PA-TCz

EL In

tens

ity (a

.u.)

Wavelength (nm)

9V 8V 7V 6V

300 400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0 TCz-9PA-TCz

EL In

tens

ity (a

.u.)

Wavelength (nm)

10V 9V 8V 7V 6V

Figure S20. The electroluminescent spectra of devices based on TCz-3PA-TCz, TCz-3,9PA-TCz and TCz-

9PA-TCz by solution spin coating.

N

PCz-BuPh

0 100 200 300 400 5000

20

40

60

80

100

Mas

s (%

)

Temperature (oC)

PCz-BuPh

100 200 300 4000

2

4

6

8

10

DSC

(uV/

mg)

Temperature (oC)

PCz-BuPh

Figure S21. The TGA and DSC curves of emitter 3,6-Bis-(4-tert-butyl-phenyl)-9-phenyl-9H-carbazole

(PCz-BuPh) in the solid powder state

OLED devices performance based on PCz-BuPh fabricated by solution spin coating method

Device structure: ITO/PEDOT:PSS（30 nm）/CBP:pvk:OXD-7:15% PCz-BuPh(55 nm) /TPBi(35 nm)/Ca:Ag,

CIEx,y /V 11 10 9 8 7 6

x 0.2238 0.2066 0.1933 0.1852 0.1801 0.1772

y 0.2044 0.1678 0.1402 0.1245 0.1157 0.1136

400 450 500 550 600 650 700

0.0

0.2

0.4

0.6

0.8

1.0

Elec

trolu

min

esce

nt In

tens

ity

Wavelength (nm)

11V 10V 9V 8V 7V 6V

Figure S22. The electroluminescent spectra of the device based on PCz-BuPh

0 2 4 6 8 10 120

200

400

600

800

1000

1200

1400

Voltage (V)

Curr

ent D

ensi

ty (m

A/cm

2 )

0

500

1000

1500

2000

2500

3000

Luminance (cd/m

2)

Figure S23. Current density-voltage-luminance characteristics of the device based on PCz-BuPh

1 10 100 100010-2

10-1

100

Exte

rnal

Qua

ntum

Effi

cien

cy (%

)

Luminance (cd/m2)

Figure S24. The external quantum efficiency-luminance characteristics of the device based on PCz-BuPh

OLED devices performance based on PCz-BuPh fabricated by thermal deposition in vacuum

Device structure:

(1) ITO/MoO3(1 nm)/TAPC (20 nm)/mCP(10 nm)/DPEPO: PCz-BuPh (30%, 25nm)/TmPyPB (40 nm)/LiF (0.7

nm)/Al(120nm)

(2)ITO/MoO3(1 nm)/TAPC (20 nm)/mCP(10 nm)/DPEPO: PCz-BuPh (20%, 25nm)/TmPyPB (40 nm)/LiF (0.7

nm)/Al(120nm)

2 4 6 8 10 120

50

100

150

200

250

300

30% 20%

Voltage (V)

Curre

nt D

ensit

y (m

A/cm

2 )

1

10

100

1000

Lum

inan

ce (c

d/m

2 )500 1000 1500 2000 2500 3000

0

1

2

3

4

Curre

nt E

fficie

ncy

(cd/

A)

Luminance (cd/m2)

30% 20%

500 1000 1500 2000 2500 3000 35000

1

2

Powe

r Effi

cienc

y (lm

/W)

Luminance (cd/m2)

30% 20%

500 1000 1500 2000 2500 3000 35000.0

0.5

1.0

1.5

2.0

EQE

Luminance (cd/m2)

30% 20%

100cd/m2 1000cd/m2

DevicesVon

(V)

λems

(nm)

PEmax

(lm/w)

CEmax

(cd/A)PE

(lm/w)

CE

(cd/A)

PE

(lm/w)

CE

(cd/A)

EQE @100 cd/m2

30% 3.7 398 1.82 3.14 1.82 3.14 0.84 2.09 1.72

20% 3.5 399 1.23 2.05 1.23 2.05 0.38 1.02 1.31

Figure S25. Current density−voltage−luminance characteristics, current efficiency-luminance characteristics,

power efficiency-luminance characteristics, the external quantum efficiency-luminance characteristics of the

devices and summary of blue OLED performance of the devices PCz-BuPh fabricated by thermal deposition

in vacuum