Supporting Information (SI) for
1,4-Diiodobenzene with –COO-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidine1-oxyl-4-yl) substituents at 2,5-positions: synthesis and use as a monomer for new
-conjugated polymers having nitoxyl radicals in side chains
By Takayuki Iijima, Masahiro Abe, Take-aki Koizumi, Atsushi Fukaya, Kyohei Usami,
Kenichiro Kami, and Takakazu Yamamoto
1
(C=O)
Transmittance
Monomer-1
1715
(C-H)
(C≡CH)
2105
(C≡C-H)
Monomer-1' 3210
(-C≡C)
2204
Polymer-3
4000
3500
3000
2500
2000
1500
Wavenumber / cm
1000
-1
Figure S1a. IR spectra of Monomer-1, Monomer-1', and Polymer-3.
2
500
Transmittance
4000 3500
(C-H)
(C=O)
3000 2500 2000 1500 1000
500
Wavenumber / cm-1
Figure S1b. IR spectrum of (top) Polymer-1 and (bottom) Polymer-2. The IR spectrum
of Polymer-1 shows peaks due to CO2 in air at about 2350 cm-1.
3
Monomer-1
Monomer-1'
Polymer-3 in CHCl3
Polymer-3 film
419
323
Absorbance
1
327
396
0
300
400
500
600
Wavelength / nm
Wavelength/nm
Figure S2. UV-vis spectra of Monomer-1 (green), Monomer-1' (blue), Polymer-3 in
chloroform (black), and Polymer-3 in cast film (red). Annealing the Polymer-3 film at
100 ºC for 1 h under N2 showed no observable change.
4
Figure S3. ESR spectra of (solid line) Monomer-1 and (dashed line) PTMA.
Figure S4. ESR spectra of Polymer-2.
5
Table S1. Crystallographic data and details of the structure refinements for Monomer-1.
Monomer-1
Chemical formula
C26H36I2N2O6
Formula weight
726.39
Crystal system
tetragonal
Space group
P42/n (No. 86)
a, Å
13.9179(5)
c, Å
V, Å
14.6048(8)
3
2829.1(3)
Z
μ,
4
cm-1
22.652
F(000)
Dcalcd, g
1440.00
cm-3
1.705
Crystal size, mm
0.20 x 0.20 x 0.20
No. of reflns
17501
No. of reflns used
3097
No. of variables
180
R (I > 2(I))
0.0631
R (All reflections)
0.0641
RW (All reflections)
0.1989
GOF
0.984
R1 = ||Fo|-|Fc||/|Fo| for I > 2(I) data, Rw = [ w(|Fo|-|Fc|)2/wFo2]1/2.
6