Electrochemistry and Electrogenerated Chemiluminescence of...
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S1 Electrochemistry and Electrogenerated Chemiluminescence of Twisted Anthracene- Functionalized Bimesitylenes Jungdon Suk a , Palani Natarajan b , Jarugu Narasimha Moorthy b , and Allen J. Bard a* a Center for Electrochemistry and Department of Chemistry and biochemistry Department, The University of Texas at Austin, Austin, Texas 78712, b Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India Supporting Information 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 35 30 25 20 15 10 5 0 5 10 15 20 C urrent ( μA) Potential (V vs. Ag wire) 0.05 V/s 0.1 V/s 0.2 V/s 0.5 V/s 1 V/s 2 V/s 5 V/s 10 V/s (a) 0 1 2 3 4 5 0.00006 0.00005 0.00004 0.00003 0.00002 0.00001 0.00000 Y=1.17953E5X C urrent (A) square root of scan rate (b) 1.2 1.4 1.6 1.8 2.0 20 10 0 10 20 30 40 (c) 0.05 V/s 0.1 V/s 0.2 V/s 0.5 V/s 1 V/s 2 V/s 5 V/s 10 V/s C urrent ( μA) Potential (V vs. Ag wire) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.000000 0.000005 0.000010 0.000015 0.000020 0.000025 0.000030 0.000035 Current (A) square root of scan rate Y=1.0452E5X (d) Figure S1. (a) Oxidation CV of 0.5 mM AB1 in 3:1 Bz: MeCN at various scan rates (b) Oxidation peak current versus the square root of the scan rate (v 1/2 ) (c) Reduction CV of 0.5 mM
Transcript of Electrochemistry and Electrogenerated Chemiluminescence of...
S1
Electrochemistry and Electrogenerated Chemiluminescence of Twisted Anthracene-
Functionalized Bimesitylenes
Jungdon Suka, Palani Natarajanb, Jarugu Narasimha Moorthyb, and Allen J. Barda*
a Center for Electrochemistry and Department of Chemistry and biochemistry Department, The
University of Texas at Austin, Austin, Texas 78712,
bDepartment of Chemistry, Indian Institute of Technology, Kanpur 208 016, India
Supporting Information
1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐35
-‐30
-‐25
-‐20
-‐15
-‐10
-‐5
0
5
10
15
20
Cur
rent
(µA)
P otential (V vs . Ag wire)
0 .05 V /s 0 .1 V /s 0 .2 V /s 0 .5 V /s 1 V /s 2 V /s 5 V /s 10 V /s
(a)
0 1 2 3 4 5-‐0.00006
-‐0.00005
-‐0.00004
-‐0.00003
-‐0.00002
-‐0.00001
0.00000
Y =-‐1.17953E -‐5X
Current (A
)
s quare root of s c an rate
(b)
-‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0-‐20
-‐10
0
10
20
30
40
(c )
0 .05 V /s 0 .1 V /s 0 .2 V /s 0 .5 V /s 1 V /s 2 V /s 5 V /s 10 V /s
Cur
rent
(µA)
P otential (V vs . Ag wire) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
0.000000
0.000005
0.000010
0.000015
0.000020
0.000025
0.000030
0.000035
Curren
t (A
)
s quare root o f s c an rate
Y =1.0452E -‐5X
(d)
Figure S1. (a) Oxidation CV of 0.5 mM AB1 in 3:1 Bz: MeCN at various scan rates (b)
Oxidation peak current versus the square root of the scan rate (v1/2) (c) Reduction CV of 0.5 mM
S2
AB1 in 3:1 Bz: MeCN at various scan rates (d) Reduction peak current versus the square root of
the scan rate (v1/2)
1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8
-‐80
-‐60
-‐40
-‐20
0
20
40
60
P otential vs . Ag w ire (V )
0 .05 V /s 0 .1 V /s 0 .2 V /s 0 .5 V /s 1 V /s 5 V /s 10 V /s 20 V /s
Cur
rent
(A)
(a)
0 1 2 3 4 5
-‐0.00008
-‐0.00006
-‐0.00004
-‐0.00002
0.00000
Y = -‐1.92201E -‐5X
s quare root o f s c an rate
Current (A
)
(b )
-‐0.8 -‐1.0 -‐1.2 -‐1.4 -‐1.6 -‐1.8
-‐40
-‐20
0
20
40
60
80 0 .05 V /s 0 .1 V /s 0 .2 V /s 0 .5 V /s 1 V /s 5 V /s 10 V /s 20 V /s
Cur
rent
(A)
P otential vs . Ag w ire (V )
(c )
0 1 2 3 4 50.00000
0.00002
0.00004
0.00006
0.00008(d )
Current (A
)
s quare root o f s c an rate
Y =1.78289E -‐5X
Figure S2. (a) Oxidation CV of 0.5 mM AB3 in 3:1 Bz: MeCN at various scan rates (b)
Oxidation peak current versus the square root of the scan rate (v1/2) (c) Reduction CV of 0.5 mM
AB3 in 3:1 Bz: MeCN at various scan rates (d) Reduction peak current versus the square root of
the scan rate (v1/2)
S3
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6-‐6
-‐4
-‐2
0
2
4
P otential (V vs . S C E )
Cur
rent
(µA)
50 mV/s
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐8
-‐6
-‐4
-‐2
0
2
4
6100 mV/s
Cur
rent
(µA)
P otential (V vs . S C E )
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6-‐12
-‐10
-‐8
-‐6
-‐4
-‐2
0
2
4
6
8200 mV/s
Cur
rent
(µA)
P otential (V vs . S C E )
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐15
-‐10
-‐5
0
5
10 500 mV/s
Cur
rent
(µA)
P otential (V vs . S C E )
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐25
-‐20
-‐15
-‐10
-‐5
0
5
10
15 1 V/s
Cur
rent
(µA)
P otential (V vs . S C E )
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐30
-‐20
-‐10
0
10
20 2 V/s
Cur
rent
(µA)
P otential (V vs . S C E )
1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐40
-‐20
0
20
405 V/s
Cur
rent
(µA)
P otential (V vs . S C E )1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6
-‐60
-‐40
-‐20
0
20
40 10 V/s
Cur
rent
(µA)
P otential (V vs . S C E )
S4
Figure S3. Experimental (solid line) and simulated (dot-dashed line) cyclic voltammograms of
0.5 mM AB3 oxidation with scan rate from 50 mV/s to 10 V/s. Simulation mechanism is four,
one electron oxidation and corrected for resistance (2470 Ω) and capacitance (700 nF): E°1,ox =
1.05 V, E°2,ox = 1.09 V, E°3,ox = 1.10 V, E°4,ox = 1.13 V vs. SCE, k°> 104 cm/s, α= 0.5.
-‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0
-‐8
-‐4
0
4
8
12 200 mV/s
Curren
t (µA
)
P otential (V vs . S C E ) -‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0
-‐15
-‐10
-‐5
0
5
10
15
20500 mV/s
Cur
rent
(µA)
P otential (V vs . S C E )
-‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0
-‐15
-‐10
-‐5
0
5
10
15
20
251 V/s
Curren
t (µA
)
P otential (V vs . S C E ) -‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0
-‐20
-‐10
0
10
20
30 2 V/s
Cur
rent
(µA)
P otential (V vs . S C E )
-‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0
-‐40
-‐20
0
20
40
60 5 V/s
Curren
t (µA
)
P otential (V vs . S C E ) -‐1.2 -‐1.4 -‐1.6 -‐1.8 -‐2.0
-‐40
-‐20
0
20
40
60 10 V/s
Cur
rent
(µA)
P otential (V vs . S C E ) Figure S4. Experimental (solid line) and simulated (dot-dashed line) cyclic voltammograms of
S5
0.5 mM AB3 reduction with scan rate from 50 mV/s to 10 V/s. Simulation mechanism is four,
one electron reduction and corrected for resistance (2470 Ω) and capacitance (700 nF): E°1,red = -
1.735 V, E°2,red = - 1.755 V, E°3,red = - 1.785 V, E°4,red = - 1.8 V vs. SCE, k°> 104 cm/s, α= 0.5.
2.0 1.5 1.0 0.5 0.0 -‐0.5 -‐1.0 -‐1.5 -‐2.0
-‐10
-‐5
0
5
10
Cur
rent
(µA)
P otential (V vs . Ag wire)
Figure S5. Cyclic voltammogram of 0.5 mM AB3 in 3:1 benzene: MeCN with 0.1 M TBAPF6
before (red line) and after ECL experiment (after 1st ECL experiment with 3 min integration:
blue line and after 2nd ECL experiment with 3 min integration: green line). WE: Pt disk, CE: Pt
coil, RE: Ag wire as a QRE. Scan rate was 0.5 V/s.
