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Electropolymerized Films as a Robust Molecular Platform for Volatile Memory Devices with Two Near-Infrared Outputs and Long Retention Time Bin-Bin Cui,a,b Chang-Jiang Yao,a Jiannian Yaoa and Yu-Wu Zhong*,a a
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China b
University of Chinese Academy of Sciences, Beijing 100049, China
*Email:
[email protected] http://zhongyuwu.iccas.ac.cn/
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Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013
(a)
(b) 20
(c) 10
charge-trapping peaks
30 20
0
10
0
I /A
I /A
I /A
10
-10
-10 -20
0 -10 -20
-20
-30 -1.6
(d)
-1.2
-0.8
-0.4
0.0
0.4
0.8
-1.8
E / V vs Ag/AgCl
(e)
75
-1.6
-1.4
-1.2
-1.6 -1.2 -0.8 -0.4 0.0 0.4 E / V vs Ag/AgCl
-1.0
E / V vs Ag/AgCl
(f)
60
0.8
1.2
60
scan rate (mV/s)
I / A
25 0 -25 -50 -75 0.0
0.2
0.4
0.6
0.8
E / V vs Ag/AgCl
1.0
2
40
2
R =0.9943
20
R =0.9953
20 anodic current (ipa)
anodic current (ipa)
1.2
0
cathonic current (ipc)
-20
I /A
10 20 50 100 200 400 600 800 1000 1200
40
I /A
50
0
cathonic current (ipc)
-20
-40
2
-40
2
R =0.9992
-60
R =0.9969
-60 0
200
400
600
800
1000 1200 -1
scan rate / mV s
0
200
400
600
800
scan rate / mV s
1000 1200 -1
Figure S1. (a) CV of 4(PF6) in CH3CN at a glassy carbon electrode (d = 3 mm). (b) Reductive electropolymerization of 4(PF6) (0.2 mM in CH3CN) on the glassy carbon electrode by 15 repeated cyclic potential scans at 100 mV/s between −1.00 and −1.75 V vs Ag/AgCl in 0.1 M Bu4NClO4/CH3CN. (c) CV of the polymeric film obtained in (b) at a scan rate of 100 mV/s in a clean supporting electrolyte solution. The pre-wave peaks just before the main oxidation and reduction peaks are charge-trapping peaks.1 (d) Anodic CVs of the polymeric films obtained in (b) at different scan rates from 10 to 1200 mV/s. (e,f) Linear dependence of the peak currents of the redox waves at +0.31 and +0.66 V, respectively, in (d) as a function of the scan rate. This is characteristic electrochemical behavior of redox species confined on electrode surfaces.
1
(a) Denisevich, P.; Willman, K. W.; Murray, R. W. J. Am. Chem. Soc. 1981, 103, 4727. (b) Takada, K.; Storrier, G. D.; Pariente, F.; Abruña, H. D. J. Phys. Chem. B 1998, 102, 1387.
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Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013
X-ray photoelectron spectroscopy data were obtained with an ESCALab220i-XL electron spectrometer from VG Scientific using 300W AlKα radiation. The base pressure was about 3 × 10-9 mbar. The binding energies were referenced to the C1s line at 284.8 eV from adventitious carbon. 3.00E+05
8.00E+04 C1s 7.00E+04 6.00E+04
2.00E+05 Counts / s
Counts / s
5.00E+04 4.00E+04 3.00E+04
1.00E+05 2.00E+04
Ru3d5
1.00E+04
0.00E+00
0.00E+00
1300 1200 1100 1000 900
800
700
600
500
400
300
200
100
0
Binding Energy (eV)
298
296
294
292
290
288
286
284
282
280
278
276
Binding Energy (eV)
Figure S2. XPS spectra of poly-4+/ITO film. Left plot: survey scan. Right plot: C1s and Ru3d5 peaks.
Table S1. XPS data of poly-4+/ITO film and 4(PF6) monomer as a powder. Binding energy (eV) Ru3d5 N1s O1s F1s Cl2p Si2p In3d5 C1s
280.51 399.81 532.38 685.93 207.54 102.46 444.96 284.82
Poly-4+/ITO film 0.66 5.54 12.63 -0.92 4.2 0.22 75.82
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Atomic% 4(PF6) monomer as a powder 0.24 2.00 14.5 2.01 ---80.96
Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013
Transmittance
(d)
(c) (b)
(a) 4000
3000
2000
wavenumbers / cm
1000 -1
Figure S3. FTIR spectra of (a) the monomer 4+ and (b-d) the polymeric materials after holding the potential for 1 min at 0.2 V, +0.55 V and +1.05 V vs Ag/AgCl, respectively.
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Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013
-0.20 V released, monitored at 1070 nm 100 95
T%
90 +0.55 V released, monitored at 1070 nm 85 80 75 +1.05 V released, monitored at 700 nm 70 0
20 40 60 80 100 120 140 160 180 t / min
Figure S4. Retention time measurement of poly-4+/ITO film ( = 1.7 10-9 mol/cm2, ca. 10 nm thick) at different potential stages.
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Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013
H NMR of 4(PF6) in CD3CN:
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4.0
2.51
3.45 3.43 3.41 3.39
3.5
3.0
2.5 3.20
4.5
0.70
3.85
5.0
6.01
5.36 5.33
5.66 5.62
5.5 1.79
6.0
1.85
6.54 6.53 6.52 6.40 6.37 6.35 6.32
6.5 2.00
7.0 11.62
7.5 5.03
5.09
8.0
1.83
8.11 8.09 7.86 7.83 7.76 7.66 7.57 7.55 7.54 7.23 7.06
8.5
2.34
8.50 8.48
9.0
2.24
9.5
8.99
BBC-63-1
2.00
1
ppm
Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013
MALDI-MS of 4(PF6):
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