S1

Supplementary Information for

3D hole-transporting materials based on coplanar

quinolizino acridine for highly efficient perovskite solar

cells†

Mingdao Zhang,*ab Gang Wang,c Danxia Zhao,a Chengyan Huang,ad Hui

Cao*a and Mindong Chen*a

a. Department of Chemistry, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, Jiangsu, PR China. E-mail: yccaoh@hotmail.com; chenmd@nuist.edu.cn.

b. Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106, USA. E-mail: mxz372@case.edu.

c. Beijing Institute of Information Technology, Beijing 100094, PR China.d. School of Chemistry & Life Science, Nanjing University Jinling College, Nanjing 210089, Jiangsu, PR China.

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2017

S2

Syntheses of TTPA-OMeTPA and compound 3:

Fig. S1. Synthesis of TTPA-OMeTPA.

Fig. S2. Synthetic route of TDT-OMeTPA.

Materials All reagents and solvents were used as received. Methylbenzene, tetrahydrofuran

(THF) and N,N’-dimethylformamide (DMF) were distilled with CaH2. O.O’.O’’-

amino-trisbenzoic acid-trimethylester (1) was synthesized by a reported method [26].

NMR spectra were measured using Bruker 400 MHz FT-NMR and 500 NMR

spectrometers. MALDI-TOF (matrix-assisted laser desorption ionization time-of-

flight) analysis was performed on Bruker Daltonics Ultraflex MALDI TOF/TOF Mass

Spectrometer, using α-Cyano-4-hydroxycinnamic acid as matrix.

Synthetic procedures4,4,8,8,12,12-hexakis(4-hexylphenyl)-8,12-dihydro-4H-

benzo[1,9]quinolizino[3,4,5,6,7-def-g]acridine (3)

To a solution of p-bromotoluene (3.87 g, 22.6 mmol) in dry diethyl ether (30 ml)

was added slowly a 2.45 M n-butyllithium/hexane solution (9.3 ml, 22.8 mmol) at -10

°C (ice-salt bath). The resulting mixture was allowed to stir for 1 h at -10 °C , and

then a solution of O.O’.O’’-amino-trisbenzoic acid-trimethylester (1) (0.90 g, 2.15

mmol) in 20 ml dry THF was added dropwise. After the addition, the mixture was

allowed to warm to room temperature and stirred overnight. Then adding minimum

water to the mixture solution to quench the reaction, and excess solvent was

evaporated. The crude product was treated with boiling ethanol and filtered after

cooling. The residue was washed with water and ethanol, then dried under vacuum.

The dried solid was dissolved in boiling acetic acid (30 ml) and concentrated HCl (aq)

(3 ml) was added dropwise. After refluxed for 3 hours, the mixture was poured into

ice water (200 ml). The sediment was collected and washed twice with ethanol, then

purified by column chromatography on silica gel using 10 : 1 petroleum ether/ethyl

acetate as the eluent. Recrystallization from ethanol to afford the product as white

crystals (yield: 85%). 1H NMR (500 MHz, CDCl3): δ, [ppm]: 6.97 (t, 3H, J = 7.60

Hz), 6.86 (d, 18H, J = 7.85 Hz), 6.56 (d, 12H, J = 8.05 Hz), 2.31 (s, 18H).

2,6,10-tribromo-4,4,8,8,12,12-hexakis(4-hexylphenyl)-8,12-dihydro-4H-

benzo[1,9]quinolizi-no[3,4,5,6-defg]zcridine (4)

To a solution of 3 (1.0 g, 1.22mmol) in 20 mL of chloroform was added NBS

(0.68 g, 3.82 mmol) at 0 °C. The mixture was stirred for 12 h at room temperature and

then filtered. The filtrate was washed with water three times, and the organic layers

were dried with anhydrous sodium sulfate. After removal of organic solvent, the

resulting solid was recrystallized from ethanol to give a white solid (Yield: 97%). 1H

NMR (500 MHz, CDCl3): δ, [ppm]: 6.94 (s, 6H), 6.88 (d, 12H, J = 7.85 Hz), 6.57 (d,

12H, J = 8.05 Hz), 2.33 (s, 18H).

Measurements1H and 13C NMR spectra were measured using Bruker 400 MHz FT-NMR and

500 NMR spectrometers. Ultraviolet-visible (UV-vis) spectroscopy was investigated

with a Shimadzu UV-3600 in dichloromethane solution using a 10 mm quartz cuvette

that dissolves the corresponding HTMs. The cyclic voltammetry (CV) was

determined with a CorrTest electrochemical workstation using a three-electrode cell

with a glassy carbon disk electrode, a platinum wire, Ag/AgCl were used as the

working electrode, auxiliary electrode, and reference electrode, respectively. 0.1 M

tetrabutylammonium perchlorate (TBAP) was applied as the electrolyte in DMF

solution at a scan rate of 50 mV s-1. Ferrocene was added to each sample solution, and

the ferrocenium/ferrocene (Fc/Fc+) redox couple was used as a potential internal

reference. Fluorescent emission spectra were recorded on an Agilent Cary100

spectrometer. The morphologies of HTM films were investigated using FE-SEM

(Tescan Mira 3 LMU FEG) and Agilent 5500 AFM. Differential scanning calorimetry

(DSC) of HTMs was recorded with scan rate of 10 °C min-1 (DSC, TA Instruments-

Waters LLC, USA, Q2000).

Fig. S3. HOMO and LUMO of TTPA-OMeTPA.

Fig. S4. DFT calculated molecule structure of TTPA-OMeTPA in vertical (a) and parallel (b) directions of the whole 2D meolecule.

Fig. S5. DFT calculated molecule structure of TDT-OMeTPA in parallel direction of the 2D coplanar triphenylamine.

Fig. S6. Photo-luminance emission of TDT-OMeTPA, TTPA-OMeTPA and Spiro-OMeTAD.

Fig. S7. SEM image of Spiro-OMeTAD layer accumulated on perovskite layer.

Fig. S8. Line profiles of AFM amplitude images for three HTM layers.

Fig. S9. DSC curves of TDT-OMeTPA and Spiro-OMeTAD.

Fig. S10. J–V characteristics of space-charge-limited current of TDT-OMeTPA, TTPA-OMeTPA and Spiro-OMeTAD.

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Norm

alize

d Cu

rrent

(mA)

E (V vs Ag/Ag+)

TDT-OMeTPA TTPA-OMeTPA Spiro-MOeTAD

Fig. S11. Cyclic voltammetry (CV) curves of TDT-OMeTPA, TTPA-OMeTPA and Spiro-OMeTAD.

Fig. S12. Energy level diagram for the corresponding materials and HTMs used in TiO2/mixed-perovskite/HTM/Ag devices. Calculated HOMO and LUMO values are presented as dashed lines, experimental levels as solid lines, respectively.

0.51.52.53.54.55.56.57.58.59.5f1 (ppm)

0

50

100

150

200

250

300

350

18.0

8

12.2

718

.08

3.00

0.03

2

2.31

3

6.65

56.

671

6.82

36.

857

6.87

26.

953

6.96

86.

983

7.28

67.

293

N

CH3

CH3

CH3 CH3

CH3

CH3

Fig. S13. The 1H NMR spectrum of compound 3 in CDCl3.

0.01.02.03.04.05.06.07.08.09.010.0f1 (ppm)

-50

0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

750

800

850

18.0

4

12.0

412

.13

6.00

0.02

9

1.29

21.

577

2.33

0

6.56

16.

577

6.87

76.

893

6.94

47.

288

N

CH3

CH3

CH3 CH3

CH3

CH3

Br Br

Br

Fig. S14. The 1H NMR spectrum of compound 4 in CDCl3.

0.01.53.04.56.07.59.011.0f1 (ppm)

-100

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

23.8

0

23.7

5

6.35

12.0

024

.06

12.2

9

2.18

42.

501

3.31

83.

682

6.22

26.

434

6.45

56.

701

6.79

66.

816

N

CH3 CH3

CH3

CH3

CH3

CH3

N

N

N

O

CH3

OCH3

OCH3

O CH3

O CH3O

CH3

Fig. S15. The 1H NMR spectrum of TDT-OMeTPA in CDCl3.

Fig. S16. FT-IR spectra of TDT-OMeTPA and TTPA-OMeTPA.

2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.5f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

18.0

0

21.8

916

.07

3.81

3

6.85

26.

875

6.89

77.

061

7.28

6N

N N

N

OCH3

OCH3

OCH3

OCH3

OCH3

OCH3

Fig. S17. The 1H NMR spectrum of TTPA-OMeTPA in CDCl3.