Supporting Information
Design, synthesis, and characterization of TPA-Thiophene based amide or imine
functionalized molecule for potential optoelectronics devices
Prashant K. Sarswat,a,* Amarchand Sathyapalan,a Yakun Zhu,a and Michael L. Freea
Figure A:
thiophene
DFT simulated and experimental IR spectrum of tris-4-iminophenyl-methyl-
Figure B: DFT simulated VCD spectrum of tris-4-iminophenyl-methyl-thiophene
Figure C: DFT simulated Raman spectrum of tris-4-iminophenyl-methyl-thiophene
Raman spectrum of methyl-thiophene- aldehyde
Counts
Raman spectroscopy of methyl-thiophene- aldehyde was carried out by using R 3000 QE
portable Raman spectrometer (made by Raman Systems) a 785 nm laser with a power of
~ 140mW was used for excitation. The Raman spectrometer provides wavelength
stability (less than 1cm-1 drift for over a 12 hour period). A Raman spectrum is shown in
Figure.
200
700
1200
1700
wavenumber(1/cm)
Figure D: Raman spectrum of methyl-thiophene aldehyde.
Raman spectroscopy of thiophene carboxylic acid
A Raman spectrum and peak position closely matches with Raman spectra of 2-thiophene
carboxylic acid. Major peak at 1412 and 1352 cm-1 provides additional confirmation.
Counts
Ref: Chemical Physics Letters, Volume 374, Issues 3–4, 11 June 2003, Pages 341–347
0
500
1000
1500
Wave number (1/cm)
Figure E: Raman spectrum of thiophene carboxylic acid.
2000
Raman spectroscopy of tris-4-amidophenyl- thiophene
Counts (arb. unit)
In Raman spectrum peaks corresponding to wave number 1409, 1360, and 1083 cm-1 can
be seen which corresponds to thiophene unit. (Ref: Chemistry Letters Vol.2, (1973)
1091-1096). Sharp peak at ~ 1169 cm-1 corresponds to TPA unit. (Ref: Journal of
Molecular Structure 692, Issues 1–3, 2004, 81–90). This shift suggests C–N bond
stretches with associated large C–C bonding stretching. Peak at ~ 1263, 1492, 1533,
1631, and 1696 cm-1 can be assigned to amide linkage. C-N stretching causes some shifts
in peak position.
200
400
600
800
1000
1200
1400
1600
wave number (1/cm)
Figure F: Raman spectrum of tris-4-amidophenyl- thiophene.
1800
FTIR Characterization
Figure G: FTIR spectrum of tris-4-iminophenyl methyl thiophene
The FTIR spectrum was recorded using pallets prepared from homogeneous mixture of
KBr-T4IPMT. A Bio-Rad FTS 6000 Spectrometer equipped with Bio-Rad WIN-IR PRO
software is used for sample characterization. The reported C=N stretching from 1616 cm 1
was slightly shifted due to the presence of D-A star type molecular core and thiophene.
The presence of prominent peak at 1608 cm-1 clearly indicates the formation of C=N with
some external stretching because of the presence of the thiophene moiety and triphenyl
amine core. The peaks at 1467 cm-1, 1465 cm-1, 1315 cm-1 account for (ν CN) confirms
the imine formation. The position and intensities of the peaks might be slightly shifted
due the presence of D-A molecule inside the system similar like chelation effect. The
sharp band at 837 cm-1 (ν C- S-C) indicates the presence of thiophene inside the system.
The 798.8-520 cm-1 accounts the stretching of thiophene as well as N (ν C-S and ν C-N).
NMR and Mass spectroscopy
1
H NMR and 13C NMR spectra were recorded on a Bruker AV500 spectrometer in
DMSO.
1
H NMR (500MHz, DMSO): δ 7.01 (s,6H) , 7.11-7.2 (J=8.7 Hz, 6H), 7.36-7.38 (d, J=
3.6, 3H) , 7.4 (1H), 8.61-8.63 (3H), 8.68 (1H) 2.54 (s, 9H), 3.31 (s, 3H)
13
C NMR (500MHz, DMSO): δ 152.90, 146.32, 145.80, 145.69, 141. 35, 134.30, 127.46,
124.94, 123. 13, 40.19, 16.27
Mass calculated for C36H30N4S3 is 614.84; found 614.2
Fig. H(a) NMR Characterization
Fig. H(b) NMR Characterization
Fig. H(c) NMR Characterization
Fig. H(d) NMR Characterization
Fig. H(e) NMR Characterization
Fig. J: Results: Mass spectroscopy
Orbital Structure
Figure I(a): HOMO-1 Orbital structure of tris-4-iminophenyl-ethyl-thiophene
Figure I(b): LUMO+1 Orbital structure of tris-4-iminophenyl-ethyl-thiophene
Figure I(c) Optimized structure of tris-4-amidophenyl –thiophene
Figure I (d) HOMO-1 orbital structure of tris-4-amidophenyl –thiophene
Figure I(e): LUMO+1 orbital structure of tris-4-amidophenyl –thiophene
Figure I(f): HOMO-1 orbital structure of tris-4-iminophenyl-propyl-thiophene
Figure I(g) LUMO+1 orbital structure of tris-4-iminophenyl-propyl-thiophene