Supporting Information. for. Advanced Materials, adma Wiley-VCH 2007

Transcription

1 Supporting Information for Advanced Materials, adma Wiley-VCH Weinheim, Germany

2 Supporting information Dibenzotetrathiafulvalene Bisimides: New Building Blocks for Organic Electronic Materials Xike Gao, Ying Wang, Xiaodi Yang, Yunqi Liu,* Wenfeng Qiu, Weiping Wu, Hengjun Zhang, Ting Qi, Ying Liu, Kun Lu, Chunyan Du, Zhigang Shuai, Gui Yu and Daoben Zhu* Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing , China S1

3 Experimental section General Chemicals were purchased from Aldrich, Alfa Aesar and used as received. Solvents and other common reagents were obtained from the Beijing Chemical Plant. 4,5-dichlorophthalic anhydride 1 was synthesized according to the literature. 1 H-NMR (300 MHz) and 13 C-NMR (75 MHz) spectra were obtained on a Bruker DMX-300 NMR Spectrometer using tetramethylsilane as internal standard. High-resolution mass spectra (HRMS) and EI MS were both recorded on Micromass GCT-MS spectrometer. Elemental analyses were performed on a Carlo Erba model 1160 elemental analyzer. FT-IR spectra were determined using a Perkin-Elmer Tensor 27 spectrometer. Electronic absorption spectra were measured on a Jasco V570 UV-vis spectrophotometer. TGA-DTA measurements were carried out on a TA SDT 2960 instruments under a dry nitrogen flow, heating from room temperature (R.T.) to 500 C, with a heating rate of 10 C/min. DSC analyses were performed on a TA DSC 2010 instruments under a dry N 2 flow, heating from R.T. to 400 C, at a heating rate of 10 C/min. Cyclic voltammetric measurements were carried out in a conventional three-electrode cell using Pt button working electrodes of 2 mm diameter, a platinum wire counter electrode, and a Ag/AgCl reference electrode on a computer-controlled CHI660C instruments at R.T. X-ray diffraction (XRD) measurements were carried out in the reflection mode at R.T. using a 2-kW Rigaku X-ray diffraction system. SEM was performed on a Hitachi S-4300 field-emission scanning electron microscope at R.T. Reference 1. L. R. Caswell, M. Guevara, L. D. Corley, A. V. Martínez, T. Hollis, K. Largess, D. L. Thornley, Synthesis. 1992, 823. S2

4 The EI-MS and HR-MS spectra of 1 and 2 are listed as follows: S3

5 S4

6 S5

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8 The FT-IR spectra of 1 and 2 are shown below: S7

9 S8

10 Cyclic voltammetry measurements. Table S1 Oxidation potentials (V) of DBTTF, 1 and 2. compound a Eox 1 Eox 2 DBTTF b c c a All oxidation potentials are determined in CH 2 Cl 2 containing TBAPF 6 (0.1 mol/l) with Ag/AgCl as the reference electrode and platinum as working and counter electrodes at r.t (50 mv/s). b Measured in CH 2 Cl 2 solution containing 1 mmol/l DBTTF. c Measured as the thin film of 1 or I (A) Voltage (V) Figure S1. Cyclic voltammogram for thin film of 2 vs Ag/AgCl in 0.1M/TBAPF 6 /CH 2 Cl 2 (50 mv/s). S9

11 Figure S2. TGA-DTA spectrum of 1. Figure S3. TGA-DTA spectrum of 2. S10

12 I DS ( A) V 60 V 20 V 20 V 60 V 100 V V DS (V) Figure S4 Drain-source (I DS ) versus drain-source voltage (V DS ) characteristics for a FET device based on DBTTF. The mobility was cm 2 /Vs, with on/off ratio of I DS ( A) V 80 V 60 V 40 V 20 V V DS (V) I DS (A) V DS = 100 V V GS (V) I DS 0.5 (A 0.5 ) Figure S5. Drain-source (I DS ) versus drain-source voltage (V DS ) characteristics for a FET device based on 1 (left); I DS and I DS 1/2 versus V GS plots at V DS = 100 V for the same device (right). The mobility was cm 2 /Vs, with on/off ratio of (cm 2 /Vs) E-3 1E-4 1E Number of Device (cm 2 /Vs) Time (day) I On/Off Figure S6. The statistical mobilities of FET devices based on 1 (left); Mobilities and on/off ratios for a FET device based on 1 tested over a period of three weeks in air (right). S11

13 Intensity / a.u Intensity / a.u / degree / degree Figure S7. X-ray diffraction of thin films of 1 (left) and 2 (right) deposited on OTS treated Si/SiO 2 substrate at room temperature. SEM images of 1 and 2 Figure S8. SEM images of the organic thin film of 1 (left) and 2 (right) deposited on OTS treated Si/SiO 2 substrate at room temperature. S12

14 Figure S9. HOMO orbital (top) and LUMO orbital (bottom) of DBTTF obtained by DFT calculations Figure S10. HOMO orbital (top) and LUMO orbital (bottom) of 2 obtained by DFT calculations S13