Hydrogen-bonded perylene/terthiophene-materials: Synthesis and spectroscopic properties

Article abstract of DOI:10.1016/j.tet.2011.10.096

The synthesis of layered donor/acceptor-materials based on perylenes (1a-c) and ter(thiophen)es (2a, 2b), ordered by hydrogen bonding moieties is reported. Based on the successful (selective) chlorination of 3,4:9,10-perylene tetracarboxylic dianhydride (3) to obtain a perylene derivative with only four chlorine atoms, subsequent functionalization with different hydrogen-bonding moieties is achieved via the azide/alkyne click reaction as proven by extensive ESI-TOF measurements. The perylene- (1a-c) and terthiophene- (2a, 2b) compounds are useful as acceptor and donor parts, respectively, in organic solar cells as proven via UV-vis and fluorescence measurements. Charge transfer between donor and acceptor parts (2a/1b) was determined as 41% via fluorescence resonance energy transfer (FRET), proving the association of the two components via the attached hydrogen bonding moieties. These measurements indicate that the mixture 2a/1b displays large potential for use as a layered ordered material with controlled spacings for organic solar cells based on a thereby facilitated charge-transfer.

Full text of DOI:10.1016/j.tet.2011.10.096

Hydrogen-Bonded Perylene/Terthiophene-Materials: Synthesis and
Spectroscopic Properties
Ali Shaygan Niaa , Claudia Endersa , and Wolfgang H. Bindera
aMartin-Luther University Halle-Wittenberg, Institute of Chemistry, Chair of Macromolecular Chemistry,
von Danckelmannplatz 4, D-06120 Halle (Saale), Germany, e-mail: wolfgang.binder@chemie.uni-
halle.de
Contents
S1-Chlorination reaction of compound 3 .................................................................................................... S2
S2-Characterization of compound 5............................................................................................................ S4
S3-Characterization of compound 1a.......................................................................................................... S5
S4-Characterization of compound 1b.......................................................................................................... S5
S5-Characterization of compound 1c.......................................................................................................... S7
S6-Characterization of compound 2a.......................................................................................................... S8
S7-Characterization of compound 2b.......................................................................................................... S9
 Corresponding author. Tel.: +49-345-55-25930; fax: +49-345-55-25892; e-mail: wolfgang.binder@chemie.uni-halle.de
S1

S1- Chlorination reaction of compound 3
Figure S1. Chlorination reaction of 3 in different reaction times
The product of the chlorination reaction was purified by soxhlet extraction with dichloromethane as
solvent, however the poor solubility of this product (4) did not allow characterization with NMR
spectroscopy or mass spectrometry.
Figure S2. Left: ESI-TOF-MS spectrum of 1a (starting material 3 was chlorinated for 20 hours) Right :
a) (M = C46H32Cl4N12O8, [M+H]+), b) (M = C46H32Cl4N12O8, [M+Na]+), c) (M = C46H31Cl5N12O8,
[M+H]+), d) (M = C46H31Cl5N12O8, [M+Na]+), e) (M = C46H29Cl5N12O8, [M+K]+), f) (M =
C46H28Cl6N12O8, [M+K]+)
S2

Therefore the definition of the number of the chlorine atoms was only possible after reaction to a
soluble product like 1a, b, c or elemental analysis of the insoluble product (4). A first try for this reaction
was done according to the literature1 in 20 hours at 70°C in chlorosulfonic acid and iodine. For
investigations of the attached number of chlorines further steps of the reaction were conducted by reaction
of 4 with 3-azidopropylamine in toluene under reflux to yield 5 and subsequent transformation of 5 via
the azide /alkyne- “click”- reaction to yield the soluble product 1a. The resulting product was
1
characterized by H-NMR spectroscopy and ESI-TOF- mass spectrometry. The ESI-TOF-MS spectrum
indicated a mixture of products substituted with 4-, 5- and 6- chlorine atoms as indicated by six main
peaks (see Figure S2). The peak at 1023.12 Da was simulated for the product with 4 chlorines as proton
adduct ([C46H32Cl4N12O8+H]+); the peak at 1045.07 Da was simulated again for 4 chlorine atoms as
sodium adduct ([C46H32Cl4N12O8+Na]+). Two peaks at 1057.05 Da and 1079.03 Da were simulated for the
product with five substituted chlorines as proton ([C46H31Cl5N12O8+H]+) and sodium adduct
([C46H31Cl5N12O8+Na]+). Finally, the peak at 1093.12 Da was simulated for five substituted chlorine as a
biradical species ([C46H29Cl5N12O8+K]+), the peak at 1127.08 Da was simulated with six chlorine atoms as
a biradical species. ([C46H28Cl6N12O8+K]+).
Therefore it was decided to decrease the reaction time of the chlorination by reacting for 10 hours. This
time, before continuing the other steps of the reaction, the number of the chlorine atoms was investigated
by elemental analysis and was shown that the product contained approximately 4 chlorine atoms
(Measured: 26.84-26.73%, Calculated: 26.75). Again, this product was treated with 3-azidopropylamine
and subsequently transformed to 1a via the azide/alkyne click reaction.
ESI-TOF-MS showed that it still contained some product with five chlorine atoms. The mass spectrum
(Figure S3) showed two main peaks at 1045.11 Da which was simulated for the product with four chlorine
atoms as sodium adduct ( [C46H32Cl4N12O8+Na]+) and 1093.16 Da was simulated for five substituted
chlorine as a biradical species ([C46H29Cl5N12O8+K]+). This result showed that elemental analysis is not an
exact measurement for determination of the number of chlorine atoms
Figure S3. a) ESI-TOF-MS spectrum of compound 1a b) measured and simulated isotopic pattern of 1a
1) (M = C46H32Cl4N12O8, [M+Na]+) 2) (M = C46H32Cl4N12O8, [M+k-2H]+)
S3

Thus the reaction time of the chlorination was decreased to 5 hours and the elemental analysis of
chlorinated product 4 showed that it was a mixture of products with 4- and 3- chlorine atoms at bay region
of perylene. (Elemental analysis : Measured: 23.4-23.93%, Calculated: 26.75%). However, it was
possible to separate these two products by column chromatography after attaching the azide moiety at the
imide position. The elemental analysis of product 5 after purification showed that it contained four
chlorine atoms (Measured :20.30% , Calculated: 20.42%). Furthermore the ESI-TOF-MS analysis of the
products after the click reaction 1a,b,c showed that they had been accomplished a clean substitution with
four chlorine atoms.
S2- Characterization of compound 5
a)
b)
Figure S4. a) 1H and b) 13C NMR spectrum of compound 5 in CDCl3
S4

S3-Characterization of compound 1a
a)
b)
b)
c)
Figure S5. a) 1H-NMR spectrum in DMSO-d6 of compound 1a b) HPLC chromatogram of 1a at the
detecting UV wavelength of 520 nm c) measured (top) and simulated (bottom) isotopic pattern as proton
adduct (M = C46H32Cl4N12O8, [M+H]+) and potassium adduct (M = C46H32Cl4N12O8, [M+K]+)
S5

S4-Characterization of compound 1b
a)
b)
c)
-The UV chromatogram showed a tailing
effect which is related to the hydrogen-
bonding interaction of triazine moiety of 1b
with the column material
Figure S6. Spectroscopic properties of 1b a) 1H-NMR b) 13C-NMR spectrum in DMSO-d6 c) HPLC
chromatogram of 1b at the detecting UV wavelength of 520 nm
S6

S5-Characterization of compound 1c
a)
b)
c)
Figure S7. Spectroscopic properties of 1c a) 1H-NMR b) 13C-NMR in DMSO-d6 c) HPLC chromatogram
of 1c at the detecting UV wavelength of 520 nm
S7

S6-Characterization of compound 2a
a)
b)
c)
Figure S8. Spectroscopic properties of 2a a) 1H-NMR b) 13C-NMR in DMSO-d6 c) HPLC
chromatogram of 2a at the detecting UV wavelength of 400 nm
S8

S7-Characterization of compound 2b
a)
b)
Figure S9. a) 1H-NMR spectrum of 2b in DMSO-d6 b) HPLC chromatogram of 2b at detecting UV
wavelength of 300 nm
(1)
Baggerman, J.; Jagesar, D. C.; Vallée, R. A. L.; Hofkens, J.; De Schryver, F. C.; Schelhase, F.;
Vögtle, F.; Brouwer, A. M. Chem. Eur. J. 2007, 13, 1291-1299.
S9