Fig.S1
Linear sweep voltammograms of compound 2b at different scan rates. Curves a−h are obtained at
50, 100, 150, 200, 250, 300, 350 and 400 mV/s, respectively. The inset graph is the plot of the
dependence of peak current on the scan rate.
Table S1
Electron-transfer number (n) for compound 2b during oxidation reaction with
different scan rates
ν/ (V·s-1)
I×10-6 /A
Q×10-6 /C
n
0.05
0.8381
1.629
1.05
0.1
1.025
1.141
0.92
0.15
1.137
0.8296
0.94
0.2
1.224
0.6228
1.01
0.25
1.386
0.5368
1.06
0.3
1.515
0.4834
1.07
0.35
1.620
0.4514
1.05
0.4645
0.97
0.4
1.757
*Q: the quantity of charge consumed during the oxidation process.
2a
Fig.S2
2b
Optimized geometry of compounds 2a and 2b
Fig.S3
Comparison between the experimental (a) and calculated (b) UV−Vis absorption spectra
of compound 2b
Table S2
Main experimental and calculated optical transitions for compound 2b
Orbital Excitations
Transition
Character
Oscillation Strength
Calcd λ/nm
Exptl λ/nm
HOMO → LUMO
ICT
πDit/Flu/Py → π*Py
0.3959
408
426
HOMO-1 → LUMO
ICT
πFlu/Py → π*Py
0.2729
381
406
HOMO → LUMO+1
ICT
πDit/Flu/Py → π*Dit/Flu/Py
0.1710
358
HOMO-1 → LUMO+1
HOMO → LUMO+5
HOMO → LUMO+6
HOMO → LUMO+8
ICT
ICT
πFlu/Py → π*Dit/Flu/Py
πDit/Flu/Py → π*Dit/Flu
0.6468
0.0815
328
295
327
289
ICT
πDit/Flu/Py → π*Dit/Flu
0.6566
271
268
HOMO-5 → LUMO+1
ICT
πFlu → π*Dit/Flu/Py
0.1885
240
229
*Dit =1,3-dithiole, Flu = fluorine, Py = pyridine
Table S3
Compound
2a
2b
Orbital energy and electron density distribution for compounds 2a and 2b
Orbital
Energy (eV)
Composition (%)
Dit
Flu
Py
LUMO+8
-0.432
18.57
57.02
24.41
LUMO+3
-1.276
47.24
37.36
15.40
LUMO+2
-1.371
15.18
55.96
28.8
LUMO+1
-1.713
40.18
32.61
27.20
LUMO
-2.253
18.21
20.02
61.77
HOMO
-5.607
41.68
36.43
21.89
HOMO-1
-6.108
2.10
65.74
32.16
HOMO-2
-6.831
93.34
4.63
2.03
HOMO-3
-6.847
53.66
36.70
9.64
HOMO-4
LUMO+8
-7.278
-0.404
12.16
58.42
29.42
24.26
65.79
9.95
LUMO+6
-0.930
64.98
27.84
7.18
LUMO+5
-0.940
33.87
53.19
12.94
LUMO+1
-1.604
26.34
41.41
32.25
LUMO
-2.131
13.53
16.82
69.64
HOMO
-5.589
34.13
35.24
30.63
HOMO-1
-5.972
1.41
58.04
40.55
HOMO-5
-7.242
14.21
72.21
13.59
Fig.S4 Molecular orbital energy diagrams and graphical representation for frontier molecular
orbitals of compound 2b