PDF《Transistor》

1 Supporting Information for Dramatic Enhancement of Carrier Mobility via Effective Secondary Structural Arrangement Resulted from the Substituents on Porphyrin Transistor Soojung Choi,a Seung Hyun Chae,a Jicheol Shin,a Youngmee Kim,b Sung-Jin Kim,b Dong Hoon Choi,*a and Suk Joong Lee*a a Department of Chemistry, Research Institute for Natural Sciences, Korea University, Seoul 136-701, South Korea.

b Department of Chemistry and NanoScience, Ewha Womans University, Seoul 136-701, South Korea E-mail: either slee1@korea.ac.kr or dhchoi8803@korea.ac.kr Tel: (+82-2) 3290-3145. Fax: (+82-2) 925-4284 1. Instrumentations

1 H NMR spectra were recorded on a Varian AS400 (399.937 MHz for

1 H and 100.573 MHz for

13 C) spectrometer.

1 H chemical shifts are referenced to the proton resonance resulting from protic residue in deuterated solvent and

13 C chemical shift recorded downfield in ppm relative to the carbon resonance of the deuterated solvents. Absorbance and emission spectra were obtained using an Agilent UV-Vis-NIR spectrophotometer and Hitachi F-7000 fluorescence spectrophotometer. Matrix Assisted Laser Desorption IonizationCTime of Flight (MALDI-TOF) mass spectra were obtained on a Bruker Daltonics LPF20 MALDI TOF Mass Spectrometer Industry-Academic Cooperation Foundation, Yonsei University. The X-ray diffraction experiments were performed using Bruker SMART APEX and Bruker SMART APEX II diffractometers equipped with a monochromator in the Mo K? (λ = 0.71073 A) incident beam. The measurements were obtained in a scanning interval of 2? between 1o and 60o . Powder X-ray diffraction (XRD) measurements were recorded with a Rigaku D/MAX Ultima III using nickel-filtered Cu Kα radiation (λ = 1.5418 ?) over a range of 2° <

2θ <

40° and X'

celerator detector operating at

40 kV and

30 mA. The redox properties of the molecules were examined by using cyclic voltammetry (Model: EA161eDAQ). Thin films were prepared on a platinum plate using acetonitrile as a solvent. The employed electrolyte solution was 0.10 M

2 tetrabutylammonium hexafluorophosphate (Bu4NPF6) in a freshly dried acetonitrile. The Ag/AgCl and Pt wire (0.5 mm in diameter) electrodes were utilized as reference and counter electrodes, respectively. The scan rate was at

50 mV/s. Optical micrographs of crystals was obtained from Metallurgical Microscope (Model: KSM-BA3(T)). Scheme S1. 2. Synthesis Materials: All commercially available starting materials and solvents were purchased from Aldrich, TCI, and Acros Co. and used without further purification. All of the reactions and manipulations were carried out under N2 with standard inert-atmosphere and Schlenk techniques unless otherwise noted. Solvents used in inert-atmosphere reactions were dried using standard procedures. Flash column chromatography was carried out with 230-400 mesh silica-gel from Aldrich using wet- packing method. All deuterated solvents were purchased from Sigma-Aldrich. The porphyrin precursors of 4-hexylbenzaldehyde (L1), 2,2'

-dipyrrolemethane, 2,6-diethoxybenzaldehyde (L5), 10,20-bis[2,6-di(ethoxy)phenyl]porphyrin (L6), [10,20-bis[2,6-di(ethoxy)phenyl]porphyrinato] zinc (II) (L7) and [5,15-dibromo-10,20,-bis[2,6-di(ethoxy)phenyl]porphyrinato] zinc (II) (L8) were prepared according to the modified literature procedures.1,2

3 4-Hexylbenzaldehyde (L1). Hexamethylenetetramine (1.65 g,

12 mmol) was added to a solution of hexylbenzene (1.82 g,

11 mmol) in trifluoroacetic acid (TFA,

10 mL) in a 50-mL round-bottom equipped with a magnetic stirbar and the mixture was heated at