Supporting Information

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1 Supporting Information Solution-processed core-extended naphthalene diimides toward organic n-type and ambipolar semiconductors Hewei Luo, Zhengxu Cai, Luxi Tan, Yunlong Guo, Ge Yang, Zitong Liu,* Guanxin Zhang, Deqing Zhang,* Wei Xu and Yunqi Liu Beijing National Laboratory for Molecular Sciences, Organic Solids Laboratory, Institute of Chemistry, Chinese Academy of Sciences, Beijing , China. Contents 1. Materials and general methods...s2 2. Synthesis of compounds 5 and 6 S2-S3 3. TGA and DSC analysis data for 1-4. S3-S4 4. Cyclic voltammogram of N,N -hexyl NDI.....S4 5. Absorption spectra of S5-S6 6. DFT calculation data.... S6-S11 7. OFETs characteristics of 1-2 under ambient conditions.... S12 8. Complementary inverters of 2..S13 9. Variation of mobilities and on/off ratios of OFETs of 3 and 4 in air S Possible intermolecular packing for molecules 1-4 on the substrate surface...s H- and 13 C-NMR spectra of S14-S18 S1

2 1. Materials and general methods Materials. The reagents and starting materials were commercially available and used without any further purification if not specified elsewhere. TBNDI and sodium 1,1-dicyanoethylene-2,2-dithiolate were synthesized according to the reported procedures. S1-S2 Compounds 5-6 were also synthesized according to the previous report S3 and the crude compounds were used without further purification. General methods. 1 H NMR (400 MHz) and 13 C NMR (100 MHz) spectra were obtained on a Bruker DMX-400 NMR Spectrometer using tetramethylsilane as an internal standard. Elemental analysis was performed on a Carlo Erba model 1160 elemental analyzer. MALDI-TOF MS were recorded with BEFLEX III spectrometer. Thin films absorption spectra were measured with JASCO V-570 UV-Vis spectrophotometer. TGA-DTA measurements were carried out on a SHIMADZU DTG-60 instruments under a dry nitrogen flow, heating from room temperature to 500 o C, with a heating rate of 10 o C/min. Cyclic voltammetric measurements were carried out in a conventional three-electrode cell using Pt button as working electrodes of 2 mm diameter, a platinum wire as counter electrode, and an Ag/AgCl reference electrode on a computer-controlled CHI660C instrument at room tempera-ture. X-ray diffraction (XRD) measurements were carried out in the reflection mode at room temperature using a 2 kw Rigaku X-ray diffraction system. Atomic force microscopy (AFM) images of the thin films were obtained on a Nanoscope IIIa AFM (Digital In struments) operating in tapping mode. The molecular structures of the compounds were optimized using the DFT method at B3LYP/6-31G(d) level. All calculations were performed with the programs Gaussian 03. S1. X. Gao, W. Qiu, X. Yang, Y. Liu, Y. Wang, H. Zhang, T. Qi, Y. Liu, K. Lu, C. Du, Z. Shuai, G. Yu and D. Zhu, Org. Lett., 2007, 9, S2. C. Rögerr and F. Würthner, J. Org. Chem., 2007, 72, S3. B. Chenard, R. Harlow, A. Johnson and S. Valduchick, J. Am. Chem. Soc., 1985, 107, Synthesis of compounds 5 and 6 Compound 5. Under nitrogen atmosphere 1,2-benzenedithiol (500 mg, 3.5 mmol) was dissolved in 10 ml of NaOH (5%, wt%) solution. After 5.0 min, tetra-n-butylammonium bromide (1.15 g, 3.57 mmol) in 5 ml of water was added, followed by addition of zinc chloride ( mg, 1.75 mmol) in 5.0 ml of ethanol. The reaction mixture was stirred at room temperature for 2.0 h and then filtered and dried. The collected white solid (1.4 g, 96%) was used in following steps without further purification. 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.16 (s, 4H), 6.37 (s, 4H), 3.15 (t, J = 7.48 Hz, 16H), 1.56 (b, 16H), 1.31 (b, 16H), 0.93 (t, J = 7.08, 24H). MS (ESI) S2

3 m/z: [M-2(n-Bu 4 N)] 2-, 242.2[n-Bu 4 N] +, [M- (n-bu 4 N)] -. Compound 6. A portion of 5.4 ml of n-butyllithium (1.3 M in hexane, 7.0 mmol) was added dropwise to a solution of 2, 3-dibromonaphthalene (500 mg, 1.75 mmol) and sublimed sulfur (112 mg, 3.5 mmol) in anhydrous THF (10 ml) under argon atmosphere at -78 o C. After 30 min, the reaction was quenched by 2.0 ml of NaOH solution (1.0 M). Tetra-n-butylammonium bromide (675 mg, 2.1 mmol) in 5.0 ml of water and zinc chloride (182 mg, 0.88 mmol) in 5 ml of ethanol was injected to the reaction mixture in sequence. The mixture was warmed up to room temperature and stirred 2.0 h and then filtered and dried. The collected yellow solid (350 mg, 22%) was used in following steps without further purification. 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.69 (s, 4H), 7.34 (s, 4H), 6.99 (s, 4H), 3.15 (t, J = 7.36 Hz, 16H), 1.55 (b, 16H), 1.30 (b, 16H), 0.93 (t, J = 7.02, 24H). MS (ESI) m/z: [M-2(n-Bu 4 N)] 2-, 242.2[n-Bu 4 N] +, [M- (n-bu 4 N)] TGA and DSC analysis data for1-4 Figure S1. TGA curves of 1-4 S3

4 Figure S2. DSC curves of Cyclic voltammograms of N,N -hexyl NDI Figure S3. Cyclic voltammogram of N,N -hexyl NDI (1.0 mm) in CH 2 Cl 2 at a scan rate of 50 mvs -1, with Pt as the working and counter electrodes and Ag/AgCl electrode (saturated KCl) as the reference electrode, and n-bu 4 NPF 6 (0.1 M) as supporting electrolyte. S4

5 5. Absorption spectra of 1-4 and N, N -hexyl NDI S5

6 Figure S4. Absorption spectra of solutions of 1-4 ( M) in CH 2 Cl 2 and those of their thin-films. 6. DFT calculation data Table S1. Coordinates and energy of compound 1 X Y Z 1 C C C C C C C C C C C N C C N C S C C S S C S6

7 23 C S C C C C C C C C O O O O C C H H H H H H H H H H H H H H Total energy: Hartrees Table S2. Coordinates and energy of compound 2 X Y Z 1 C C C C C C C C C S7

8 10 C C N C C N C S C C S S C C S C C C C C C C C O O O O C C C C C C C C C H H H H H H H H S8

9 54 H H H H H H H H Total energy: Hartrees Table S3. Coordinates and energy of compound 3 X Y Z 1 C C C C C C C C C C C N C C N C S C C S C C C C O O O O C C S S9

10 32 C S C C N C N H H H H H H H H H H Total energy: Hartrees Table S4. Coordinates and energy of compound 4 X Y Z 1 C C C C C C C C C C C N C C N C S C C S C C S10

11 23 C C O O O O C C S C S C C N C N C C C C H H H H H H H H H H H H Total energy: Hartrees S11

12 7. OFETs characteristics of 1 and 2 under ambient conditions Figure S5 The transfer characteristics of OTFT devices based on 1 (a) annealed at 120 o C (V DS for transfer characteristics is -80 V) and 2 (b) annealed at 140 o C (V DS for transfer characteristics is -80 V) under ambient conditions; the transistor channel width and channel length were 1400 μm and 50 μm, respectively. S12

13 8. Complementary inverters of 2 Figure S6. Complementary inverters fabricated from thin-films of 2: (a) Schematic electrical layout of the inverters; (b) Static switching characteristics of a spin-coated inverter on OTS-treated Si / SiO 2 substrate annealed at 140 o C; (c) Gain data for the devices. 9. Variation of mobilities and on/off ratios for OFETs of 3 and 4 in air Figure S7. Variation of the electron mobilities and on/off ratios for OFETs of 3 and 4 in air for 30 days. 10. Possible intermolecular packing for molecules 1-4 on the substrate surface Figure S8. The proposed intermolecular packing on the substrate surface for molecules 1-4. S13

14 11. 1 H- and 13 C-NMR spectra of 1-6 Compound 1 S14

15 Compound 2 S15

16 Compound 3 S16

17 Compound 4 S17

18 Compound 5 Compound 6 S18