Rational synthesis and comparative investigation on a series of fluorinated aryl substituted diketopyrrolopyrrole

Article abstract of DOI:10.1016/j.tet.2016.12.021

We novelly designed and synthesized a set of fluorinated diphenyl-diketopyrrolopyrrole (DPP) compounds by varying the position and amount of fluorine atom, and to the best of our knowledge, it is the first time a difluoromethyl group and perfluoroalkyl ch

Full text of DOI:10.1016/j.tet.2016.12.021

Accepted Manuscript
Rational synthesis and comparative investigation on a series of fluorinated aryl
substituted diketopyrrolopyrrole
Jie Xu, Shaoze Zhang, Shengying Wu, Shiming Bi, Xinjin Li, Yunxiang Lu, Limin
Wang
PII:
S0040-4020(16)31289-3
10.1016/j.tet.2016.12.021
TET 28313
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 October 2016
Revised Date: 9 December 2016
Accepted Date: 12 December 2016
Please cite this article as: Xu J, Zhang S, Wu S, Bi S, Li X, Lu Y, Wang L, Rational synthesis and
comparative investigation on a series of fluorinated aryl substituted diketopyrrolopyrrole, Tetrahedron
(2017), doi: 10.1016/j.tet.2016.12.021.
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series of fluorinated aryl substituted
diketopyrrolopyrrole
Jie Xu a , Shaoze Zhang c , Shengying Wu a , Shiming Bi a , Xinjin Li a , Yunxiang Lu c , Limin Wang a, b,
aShanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, Meilong Road, 130, Shanghai 200237,
China
bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, The Chinese Academy of Sciences, 345 Lingling Road,
Shanghai 200032, China
cKey Laboratory for Advanced Materials and Department of Chemistry, East China University of Science and Technology, Shanghai 200237, China
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Tetrahedron
journal homepage: www.elsevier.com
Rational synthesis and comparative investigation on a series of fluorinated aryl
substituted diketopyrrolopyrrole
Jie Xu a , Shaoze Zhang c , Shengying Wu a , Shiming Bi a , Xinjin Li a , Yunxiang Lu c Limin Wanga, b,
,
a Shanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, Meilong Road, 130, Shanghai 200237, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, The Chinese Academy of Sciences, 345 Lingling Road, Shanghai
200032, China
c Key Laboratory for Advanced Materials and Department of Chemistry, East China University of Science and Technology, Shanghai 200237, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
We novelly designed and synthesized a set of fluorinated diphenyl-diketopyrrolopyrrole (DPP)
compounds by varying the position and amount of fluorine atom, and to the best of our
knowledge, it is the first time a difluoromethyl group and perfluoroalkyl chains had been
introduced into the DPP unit in good yields. We investigate the optical/electrochemical
properties of all the compounds. Density functional theory (DFT) calculations were applied to
explore orbital energy value of these compounds. The results demonstrated that the
perfluorocarbon chains substituted DPPs with larger red-shift in both absorption and emission
spectra and narrower bandgap.
Available online
Keywords:
Fluorinated diketopyrrolopyrrole
Difluoromethyl
2009 Elsevier Ltd. All rights reserved
.
Perfluoroalkyl
Cyclic voltammetry
DFT calculations
———
Corresponding author. Tel./ fax: +86 21 64253881; e-mail: wanglimin@ecust.edu.cn (L.Wang)

2
Tetrahedron
1. Introduction
similar reaction of IDPP with perfluorobutyl or perfluorohexyl
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iodide in the prescence of DMF using activated copper.14
Fluorination of conjugated organic molecules for
2.2. Optical properties of targeted compounds
optoelectronic applications has attracted increasingly research
interest over the years.1The introduction of fluorine atom could
lead excited state switching2 and hyper- or hypochromic effects
(i.e. in-/decrease of absorbance), as well as significant batho-
(red) or hypsochromic (blue) shifts of the optical spectra to the
whole molecules.3,4 Furthermore, due to fluorine with the highest
electronegativity (EN), C-F bond could break the symmetry of
the molecular orbitals (MOs) and lower the highest occupied and
lowest unoccupied molecular orbitals (HOMO and LUMO).5,6
These fluorinated compounds could achieve higher open circuit
voltages in organic solar cells,7 promote tuning of p-type towards
Fig. 1 shows the absorption spectra of nine targeted DPP
derivatives in DCM (0.1 mM). The maximum absorption bands
of HDPP, pFDPP, CH3DPP, mFDPP, CF2HDPP, 2mFDPP,
CF3DPP, Rf4CDPP and Rf6CDPP were 463, 463, 467, 470,
472, 474, 475, 479, 480 nm, respectively. Among the fluorinated
DPPs, the increasing electro-withdrawing ability of substituent
on aryl ring resulted in a gradual red-shift of the absorption
maxima. Surprisingly, the maximum absorption band of pFDPP
was equal to HDPP, but slightly blue-shifted compared to the
compound mFDPP, which indicates that para-substituted
fluorine atoms affected weakly the absorption spectra.
Interestingly, the maximum absorption of CF3DPP and 2mFDPP
are slightly red-shifted compared to CF2HDPP and mFDPP
respectively due to the difference of the amounts of fluorine
atoms. Moreover, the maximum absorption of Rf4CDPP and
Rf6CDPP are red-shifted by 16 nm, 17 nm relative to that of
HDPP due to the electron-withdraw properties of two
perfluoroalkyl chains substituents.
n-type semiconductors.8 Consequently,
a
more detailed
investigation on the impact of fluorine on the structure-property
relationship is vital. 9
Diketopyrrolopyrrole (DPP) unit has a large planar π surface,
exhibits strong π-π interactions and an electron-deficiency.10
Furthermore, DPP derivatives have advantageous optical
properties, such as strong absorption and emission in visible
region, high photostability and large Stokes shift.11 But
fluorination of DPP-based compounds are rarely reported.12
Herein, we originally varied the level of fluorination and position
of substitution, and constructed seven DPP-based fluorinated
compounds (pFDPP, mFDPP, 2mFDPP, CF2HDPP, CF3DPP,
Rf4CDPP and Rf6CDPP, as shown in scheme 1, “p” and “m”
refer to the fluorine atoms oriented para- and meta- to the DPP
core, “Rf” refer to perfluoro) to compared with two non-
fluorinated compounds (HDPP and CH3DPP) in the
optical/electrochemical properties. To the best of our knowledge,
it is the first time a difluoromethyl group and perfluoroalkyl
chains had been introduced into the DPP unit in good yields.
Besides, the electron-withdrawing, optical and electrochemical
properties of these DPP derivatives was systematically studied.
The fluorescence spectra of DPP derivatives in DCM (0.1
mM) were shown in Fig.2. All of them emitted intense
fluorescence and the maximum bands ranged from 524 nm to 550
nm. In accordance with the absorption spectra, the maximum
emission of mFDPP, CF2HDPP, 2mFDPP and CF3DPP show
the relatively redshifted by 7, 12, 12, 14 nm compared to HDPP.
However the maximum emission of pFDPP is blue-shifted by 3
nm to HDPP due to the repulsion between the neighboring
fluorine atoms, causing larger steric hindrance, reducing the
planarity of the molecule and affecting the conjugation 15. The
maximum emission of CH3DPP is red-shifted by 3 nm compared
to HDPP due to the hyperconjugated effects with the DPP core.
Though the length of a perfluorocarbon chain is increased, the
maximum emission of Rf6CDPP is equal to Rf4CDPP of 550
nm, which may be attributed to the fact that the fluorine atoms on
perfluorocarbon
Scheme 1. The chemical structures of fluorinated and non-fluorinated
diphenyl-DPP compounds.
2. Results and discussion
2.1. Design and synthesis
Fig 1. Absorption spectra of all targeted compounds in DCM.
The seven targeted compounds IDPP~2mFDPP (1-1~1-7)
were designed and synthesized according to the synthetic route
shown in Scheme 2. Intermediate DPP dye (2) was prepared
according to the published literature. 11 According to the synthetic
route shown in Scheme 3, compound CF2HDPP was obtained by
the reaction of IDPP with (difluoromethyl)-trimethylsilane
(TMSCF2H) which is according to the relevant literature.13
Compounds Rf4CDPP and Rf6CDPP were obtained by the

To enhance the understanding of the impact of solvents on
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DPP systems by inspecting the properties of UV-vis absorption
and fluorescence emission. In the solution of methanol, both
absorption and emission of DPP derivatives have a subtle blue-
shift compared to DCM for methanol is a stronger polar solvent
where electrostatic effects are dominant.16 Furthermore, during
the experimental process, DPP derivatives have poor solubility in
methanol due to weak polar properties of themselves. For
example, the maximum absorption and emission of pFDPP (459
nm and 520 nm) in methanol exhibited blue-shifted compared to
in DCM (463 nm and 524 nm), respectively. However, both
maximum absorption and emission of all compounds have a red-
shifted in the solution of toluene. The maximum absorption and
emission of Rf6CDPP (489 nm and 556 nm) in toluene exhibited
red-shifted compared to DCM (480 nm and 550 nm),
respectively. The detailed absorption and emission spectra data of
DPP derivatives in solvents were shown in Table 2.
Fig 2. Emission spectra of all targeted compounds in DCM.
Table 1
Table 2
The absorption and emission spectra data of DPP derivatives in
dichloromethane.
The maximum absorption and emission spectra data of DPP derivatives in
different solvents
Molecule
a
ε(10ꢃ)
(ꢄꢅꢆꢇꢈꢅꢆ
ꢀꢉꢊ
Stokes
b
MeOH
ꢀꢁꢂ
CH3CN
ꢀꢁꢂ
acetone
ꢀꢁꢂ
THF
ꢀꢁꢂ
DMF
ꢀꢁꢂ
toluene
ꢀꢁꢂ
molecule
ꢀ
ꢁꢂ(nm)
ꢋꢌ
shift (nm)
)
(nm)
/ꢀꢉꢊꢍnm /ꢀꢉꢊ ꢍnm /ꢀꢉꢊꢍnm /ꢀꢉꢊꢍnm /ꢀꢉꢊꢍnm /ꢀꢉꢊꢍnm
pFDPP
HDPP
459/520
459/523
462/526
462/530
462/529
466/537
467/540
469/544
470/544
462/522
461/526
466/527
467/532
464/533
470/540
470/542
474/548
476/548
465/522
464/526
469/527
468/533
468/533
472/540
474/544
477/549
477/548
469/526
469/529
472/535
473/535
473/535
480/543
480/546
485/551
484/552
466/527
466/530
470/531
472/537
470/537
476/544
476/548
480/554
480/555
472/529
472/533
476/534
477/540
477/540
484/548
482/550
488/556
489/556
pFDPP
HDPP
463
463
467
470
472
474
475
479
480
1.54
1.66
1.85
1.02
1.14
1.87
1.44
1.88
1.71
524
527
530
534
539
539
544
550
550
0.58
0.56
0.55
0.78
0.63
0.76
0.59
0.46
0.48
61
64
63
64
67
65
69
71
70
CH3DPP
mFDPP
CH3DPP
mFDPP
CF2HDPP
2mFDPP
CF3DPP
Rf4CDPP
Rf6CDPP
CF2HDPP
2mFDPP
CF3DPP
Rf4CDPP
Rf6CDPP
a The excitation wavelength were the max absorption wavelength.
2.4. Electrochemical properties of targeted compounds
b Fluorescent quantum yields were determined in reference to rhodamine 6G
Cyclic voltammetry (CV) method was carried out to
investigate the electrochemical behavior of DPP derivatives with
a three-electrode system in which platinum button was used as
working electrode, platinum wire as counter electrode and
saturated calomel electrode (SCE) as reference electrode.
Ferrocene/ferrocenium (Fc/Fct) was employed as an external
(ꢋꢌ= 0.89, in CH2Cl2).
reference and 0.1
M tetrabutylammonium perchlorate as
supporting electrolyte in dichloromethane solution. The oxidation
potentials (ꢎꢆ ꢏ ) of nine targeted compounds (pF~Rf6CDPP)
⁄
were measured to be 1.36, 1.35, 1.27, 1.44, 1.45, 1.48, 1.49, 1.50
and 1.55 V versus normal hydrogen electrode (NHE) which are
higher than that of Fc/Fct (1.19 V vs. NHE) redox electrolyte
(Fig. 4). The oxidation potential of fluorinated DPPs are higher
than that of non-fluorinated DPP (HDPP), which is ascribed to
the electron-withdrawing ability of fluorine atoms. In this regard,
the oxidation potential of pFDPP and mFDPP are 10 mV and
190mV higher than HDPP, and the oxidation potentials of
CF3DPP (1.49 V) and 2mFDPP (1.48 V) are higher than
CF2HDPP (1.45 V) and
Fig 3. Typical fluorescence photograph of fluorinated DPP derivatives in
DCM. (from left to right: pFDPP, 2mFDPP, Rf6CDPP; the fluorescence was
excited at 365 nm)
chain edge of compound Rf6CDPP are too distant to influence
the electron cloud of DPP core. Also compounds Rf4CDPP and
Rf6CDPP show a relatively larger stokes shift (Rf4CDPP: 71 nm
and Rf6CDPP: 70 nm).
The electron withdrawing effect of pFDPP is similar with
HDPP, and tiny weaker than CH3DPP. Moreover, pFDPP has
little influence on the absorption spectra, while fluorine meta-
substitution (mFDPP) makes absorption red-shifted. Gradually
augment in both absorption and emission had been observed in
the fluorinated compounds (CF2HDPP, CF3DPP, Rf4CDPP and
Rf6CDPP) which accompanied with an increase in fluorine
atoms. The detailed absorption and emission spectra data of DPP
derivatives in DCM were shown in Table 1. In addition, Fig. 3
showed the fluorescence and typical color images of DPP
derivatives, which were excited at 365 nm.
2.3. Optical properties of targeted compounds in different
solvents
Fig 4. Cyclic voltammograms (oxidation curve) of DPP derivatives and
ferrocene using o.1 M tertbutylammonium hexafluorophosphate (TBAPF6) as

4
Tetrahedron
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electrolyte in DCM with platinum button working electrodes, a platinum
wire counter electrode, and an SCE reference electrode.
Table 3
Electrochemical properties of DPP derivatives
HOMOa
(V)
ꢀꢐꢑꢒꢓꢔ
(nm)
507
509
512
514
518
520
522
526
526
ꢎꢕꢅꢕ
LUMOd
(V)
b
c
Molecule
(eV)
2.45
2.44
2.42
2.41
2.39
2.38
2.37
2.36
2.36
pFDPP
HDPP
1.36
1.35
1.27
1.44
1.45
1.48
1.49
1.50
1.55
-1.09
-1.09
-1.15
-0.97
-0.94
-0.9
CH3DPP
mFDPP
CF2HDPP
2mFDPP
CF3DPP
Rf4CDPP
Rf6CDPP
-0.88
-0.86
-0.81
Fig. 5. Frontier MO energies (in eV against the vacuum level)
As shown in Fig. 5, the HOMO orbitals of DPP compounds
are mainly located on the diketopyrrolopyrrole accepter part.
Meanwhile, according to the frontier MO energies calculations,
the HOMO values of fluorinated DPPs are lower than non-
fluorinated DPP (HDPP), and the same as LUMO values.
However the methyl substituted DPP (CH3DPP) shows a little
higher LUMO/HOMO value than HDPP due to the methyl being
hyperconjugated with DPP core. During the nine DPP
derivatives, the LUMO/HOMO values of Rf4CDPP and
Rf6CDPP are lower than any other DPPs which is corresponding
to the experimental results.
a HOMO was measured in DCM with 0.1 M tetrabutylammonium perchlorate
(TBAP) as a supporting electrolyte (calibrated with ferrocene/ferrocenium
(Fc/Fc+) as an external reference and converted to a normal hydrogen
electrode (NHE) by addition of 0.69 V).
b ꢀꢐꢑꢒꢓꢔ is the onset absorption wavelength.
c E0-0 was estimated from the absorption thresholds from the absorption
spectra of dyes in solution.
d LUMO was estimated by subtracting E0-0 from HOMO; vs. NHE.
mFDPP (1.44 V), respectively, which shows fluorinated DPP
compounds with different amounts of fluorine atoms and
different decoration positions could affect the HOMO values in
varying degree. The zero-zero transition energies (ꢎꢕꢅꢕ) of DPP
derivatives (pF~Rf6CDPP) were determined to be 2.45, 2.44,
2.42, 2.41, 2.39, 2.38, 2.37, 2.36 and 2.36 eV, respectively,
which are estimated from the absorption thresholds of
compounds in dichloromethane. The LUMO levels of DPP
compounds (pF~Rf6CDPP) were from ꢎꢖꢗꢘꢗ − ꢎꢕꢅꢕ , are
−1.09, −1.09, −1.15, −0.97, −0.94, −0.9, −0.88, −0.86 and
−0.81 V versus NHE, respectively. These results indicate that the
stronger electron-withdrawing abilities of fluorinated DPP
compounds, the lower MO orbital values. The detailed
electrochemical data is shown in Table 3.
3. Conclusions
In summary, seven fluorinated DPPs and two non-fluorinated
DPPs had been successfully designed and synthesized. All of
them exhibit strong fluorescence in DCM solution, and most
fluorinated DPP derivatives showed a various red-shifted in both
absorption and emission spectrum except pFDPP with a tiny
blue-shifted in emission spectrum. Moreover, the absorption and
fluorescence emission spectrum of targeted DPPs in six various
solvents had been measured to explore the solvent impact on
DPP compounds, and both maximum absorption and emission of
all compounds have a red-shifted in the solution of toluene
compared to any other solvents. Additionally, the electrochemical
properties and electron distributions of DPP derivatives had been
respectively investigated by CV method and DFT calculations,
two perfluoroalkyl chains substituted DPPs had narrower
bandgap than other DPP derivatives. Through the systematic
comparison, the results indicated that perfluoroalkyl chains
substituted DPPs with larger Stokes shift and narrower bandgap
compared to non-fluorinated DPPs. And it makes them promising
candidates for the design of new organic electronic materials.
Besides, we offer new methods to introduce a difluoromethyl
group and perfluoroalkyl chains into the DPP unit in good yields.
2.5. DFT calculations
To gain insight into the molecular structure and electron
distributions, we employed density functional theory (DFT)
calculations to optimize the geometries of the targeted molecules.
The geometries of all the complexes under study were fully
optimized by means of the B3LYP/6-31+G* methods.17,18 No
symmetry or geometry constraint was imposed during the
optimizations. Frequency calculations were performed at the
same theoretical levels to corroborate that all the structures are
factual minima on the potential energy surface. Then, the
molecular orbital analyses of the complexes were undertaken
with Multiwfn program,19 and the contour surfaces of the highest
occupied molecular orbitals (HOMOs) and lowest unoccupied
molecular orbitals (LUMOs) were visualized using the VMD
package.20 All of these calculations were carried out with the
Gaussian 09 suite of programs.21
4. Experimental Section
4.1. General information
N, N-dimethylformamide (DMF) was refluxed with calcium
hydride and distilled before use. All others chemicals were
purchased from commercial sources and used without further
purification. Reactions were monitored by TLC. Flash
chromatography separations were carried out using silica gel
1
(200-300 mesh). H NMR, 13C NMR and 19F NMR spectra were
collected on a Bruker Avance DPS-300 spectrometer using
CDCl3 as solvent and tetra-methylsilane as an internal reference,
respectively. Mass spectrometry was performed by Bruker Biflex
III MALDI-TOF (both positive and negative ion reflector mode).
Absorption spectra were measured on a Thermo UV-Vis
spectrophotometer. Fluorescence spectra were measured on a
Thermo Fluorescence spectrophotometer. Both excitation and
emission slit widths were 2.5 nm. The cyclic voltammo-grams of

DPP-based derivatives were obtained using a Versastat II
electrochemical workstation.
109.9, 98.1, 41.7, 31.5, 19.9, 13.6; HRMS (TOF-ESI): m/z
ACCEPTED MANUSCRIPT
[M+H]+ calcd for C26H27N2O2I2: 653.0162; found: 653.0176.
4.2. Typical procedure for DPP dye
4.3.2 2,5-dibutyl-3,6-diphenyl-2,5-dihydropyrrolo[3,4-c]pyrrole-
1,4-dione (1-2/HDPP). Yellow solid (522 mg, 87%). mp 118-119
°C. 1H NMR (400 MHz, CDCl3): δ ppm 7.81 (m, 4H), 7.52
(m,6H), 3.76 (t, J = 7.6 Hz, 4H), 1.58 (m, 4H), 1.26 (m, 4H), 0.84
(t, J = 7.6 Hz, 3H); 13C NMR (100MHz, CDCl3): δ ppm 162.7,
148.5, 131.1, 128.9, 128.7, 128.3, 109.7, 41.7, 31.5, 19.9, 13.6.
HRMS (TOF-ESI): m/z [M+Na]+ calcd for C26H28N2O2Na:
423.2048; found: 423.2045.
A mixture of sodium (2.30 g, 100 mmol), t-amyl alcohol (50
mL) and catalytic amount of FeCl3 were added into a three-
necked flask under air. After being stirred vigorously at 100 °C
for 1 h, the mixture was cooled to 50 °C, 3 (40 mmol) was added.
Then the mixture was heated to 100 °C, diisopropyl succinate
(4.00 g, 40 mmol) in t-amyl alcohol (20 mL) was added dropwise
over 2 h. Subsequently, the resulting suspension was kept for 3 h
at 120oC, and cooled to room temperature. Glacial acetic acid
was slowly added till pH was 7.0, followed by methanol and
water (1:2, v:v, 100 mL) added, the mixture was heated under
4.3.3 2,5-dibutyl-3,6-di-p-tolyl-2,5-dihydropyrrolo[3,4-c]pyrrole-
1,4-dione (1-3/ CH3DPP). Yellow solid (436 mg, 68%). mp 132-
1
133 °C. H NMR (400 MHz, CDCl3): δ ppm 7.72 (d, J = 8.0 Hz,
4H), 7.32 (d, J = 8.0 Hz, 4H), 3.76 (t, J = 7.6 Hz, 4H), 2.43 (s,
6H), 1.58 (m, 4H), 1.26 (m, 4H), 0.84 (t, J = 7.6 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ ppm 162.8, 148.4, 141.6, 129.6,
128.7, 125.5, 109.4, 41.7, 31.5, 21.7, 20.0, 13.6; HRMS (TOF-
ESI): m/z [M+Na]+ calcd for C28H32N2O2Na: 451.2361; found:
451.2356.
reflux for
2 h. After cooling filtration and dried, the
corresponding product was obtained. The product (2) was used
without further purification.
4.2.1 3,6-bis(4-iodophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-
1,4-dione (2-1/2-I). Bluish-red solid (4.1 g, 38%).
4.2.2 3,6-di-p-tolyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione
(2-3/2-CH3). Bluish-red solid (3.4 g, 36%).
4.3.4 2,5-dibutyl-3,6-bis(4-(trifluoromethyl)phenyl)-2,5-dihydro-
pyrrolo[3,4-c]pyrrole-1,4-dione (1-4/CF3DPP). Yellow solid
1
(407 mg, 76%). mp 251-253 °C. H NMR (400 MHz, CDCl3): δ
4.2.3 3,6-bis(4-(trifluoromethyl)phenyl)-2,5-dihydro-pyrrolo[3,4-
ppm 7.92 (d, J = 8.4Hz, 4H), 7.80 (d, J = 8.4Hz, 4H), 3.75 (t, J =
7.6 Hz, 4H), 1.57 (m, 4H), 1.26 (m, 4H), 0.85 (t, J = 7.6 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ ppm 162.3, 147.4, 132.7 (q, J =
32.8 Hz), 131.3, 129.0, 125.9 (q, J = 3.6 Hz), 123.6 (q, J = 271.0
Hz), 110.6, 41.7, 31.6, 19.9, 13.5; 19F NMR (376MHz, CDCl3): δ
ppm -63.1 (s, 6F); HRMS (TOF-ESI): m/z [M+Na]+ calcd for
C28H27N2O2F6: 537.1977; found: 537.1967.
c]pyrrole-1,4-dione (2-4/2-CF3). Red-black solid (4.4 g, 51%).
4.2.4 3,6-bis(4-fluorophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-
1,4-dione (2-5/2-pF). Red solid (3.9 g, 60%).
4.2.5 3,6-bis(3-fluorophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-
1,4-dione (2-6/2-mF). Red solid (5.7 g, 87%).
4.2.6 3,6-bis(3-fluorophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-
1,4-dione (2-7/2-2mF). Red solid (5.3 g, 83%).
4.3.5 2,5-dibutyl-3,6-bis(4-fluorophenyl)-2,5-dihydropyrrolo[3,4-
c]pyrrole-1,4-dione (1-5/pFDPP). Yellow solid (379 mg, 58%).
1
mp 168-169 °C. H NMR (400 MHz, CDCl3): δ ppm 7.82 (m,
4H), 7.21 (t ,J = 4.8Hz, 6H), 3.74 (t, J = 7.6 Hz, 4H), 1.56 (m,
4H), 1.26 (m, 4H), 0.85 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ ppm 163.5 (d, J = 252.1 Hz), 162.6, 147.4, 131.0 (d, J
= 8.7 Hz), 124.3(d, J = 3.6 Hz), 116.2(d, J = 21.9 Hz), 109.6,
41.6, 31.5, 19.9, 13.6; 19F NMR(376MHz, CDCl3): δ ppm -
107.2(m, 2F); HRMS (TOF-ESI): m/z [M+H]+ calcd for
C26H27N2O2F2: 437.2041; found: 437.2045.
4.3.6
2,5-dibutyl-3,6-bis(3-fluorophenyl)-2,5-dihydropyrrolo-
[3,4-c]pyrrole-1,4-dione (1-6/mFDPP). Yellow solid (529 mg,
1
81%). mp 138-140 °C. H NMR (400 MHz, CDCl3): δ ppm 7.59
(m, 2H), 7.50 (m, 4H), 7.20 (m, 2H), 3.74 (t, J = 7.6 Hz, 4H),
1.54 (m, 4H), 1.25 (m, 4H), 0.85 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ ppm 162.7 (d, J = 246.3 Hz), 162.3, 147.3,
130.6 (d, J = 8.2 Hz), 129.9 (d, J = 8.1 Hz), 124.5 (d, J = 3.0 Hz),
118.2 (d, J = 21.1 Hz), 115.5 (d, J = 23.4Hz), 110.1, 41.6, 31.5,
19.9, 13.6; 19F NMR (376 MHz, CDCl3): δ ppm -111.0 (m, 2F);
HRMS (TOF-ESI): m/z [M+H]+ calcd for C26H27N2O2F2:
437.2041; found: 437.2039.
Scheme 2. The synthetic routes of compounds IDPP~2mFDPP (1-1~1-7).
4.3. Typical procedure for compounds (1-1~1-7)
The mixture of 2 (1 mmol), K2CO3 (690 mg, 5 mmol) and
30mL DMF were added into a schlenk tube under N2. After being
stirred vigorously at 100 °C for 0.5 h, the mixture was cooled to
50 °C, the 1-iodobutane (736 mg, 4 mmol) was added. Then the
mixture was heated to 100 °C for 3 h. Then the reactant was
poured into 400 mL deionized water. The precipitate was filtered
and washed with water, then dried overnight in a vacuum
4.3.7
2,5-dibutyl-3,6-bis(3,5-difluorophenyl)-2,5-dihydro-
pyrrolo[3,4-c]pyrrole-1,4-dione (1-7/2mFDPP). Yellow solid
1
desiccator. The residue was purified by
a
column
(524 mg, 74%). mp 139-141 °C. H NMR (400 MHz, CDCl3): δ
ppm 7.36 (m, 4H), 6.97 (tt, J1 = 8.6 Hz, J2 = 2.4 Hz, 2H), 7.20
(m, 2H), 3.74 (t, J = 7.6 Hz, 4H), 1.54 (m, 4H), 1.26 (m, 4H),
0.86 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ ppm
163.2 (d, J = 249.2 Hz), 163.0 (d, J = 249.0 Hz), 161.9, 146.4 (t,
J = 2.9 Hz), 130.6 (t, J = 10.0 Hz), 111.8 (d, J = 27.3 Hz), 111.7
(d, J = 11.4 Hz), 110.5, 106.8 (t, J = 25.0 Hz), 41.7, 31.5, 19.9,
13.5; 19F NMR (376 MHz, CDCl3): δ ppm -107.2(t, J = 7.5 Hz,
4F); HRMS (TOF-ESI): m/z [M+H]+ calcd for C26H25N2O2F4:
473.1852; found: 473.1852.
chromatography on silica gel with eluent (petroleum
ether/dichloromethane = 1:2, v/v) to yield the corresponding
product (1).
4.3.1 2,5-dibutyl-3,6-bis(4-iodophenyl)-2,5-dihydro-pyrrolo[3,4-
c]pyrrole-1,4-dione (1-1/IDPP). Yellow solid (534 mg, 82%).
1
mp 228-229 °C. H NMR (400 MHz, CDCl3): δ ppm 7.87 (d, J =
8.4 Hz, 4H), 7.53 (d, J = 8.4 Hz, 4H), 3.73 (t, J = 7.6 Hz, 4H),
1.55 (m, 4H), 1.25 (m, 4H), 0.85 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ ppm 162.5, 147.6, 138.2, 130.0, 127.5,

6
Tetrahedron
chromatography on silica gel with petroleum ether and
ACCEPTED MANUSCRIPT
dichloromethane (5:1, v/v) as eluent to give a yellow solid (127
1
mg, 61%). mp 142-145 °C. H NMR(400 MHz, CDCl3): δ ppm
7.97 (d, J = 8.4Hz, 4H), 7.77 (d, J = 8.4 Hz, 4H), 3.76 (t, J = 7.6
Hz, 4H), 1.57 (m,4H), 1.27 (m, 4H),0.85 (t, J = 7.6 Hz, 6H); 13C
NMR (100 MHz, CDCl3): δ ppm 162.2, 147.3, 131.5, 131.2 (t, J
= 22.4 Hz), 128.9, 127.5 (t, J = 6.3 Hz), 121.7 (m), 118.5 (m),
115.7, 112.8 (m), 110.7; 19F NMR (376 MHz, CDCl3): δ ppm -
125.5 (m, 2F), -122.5 (m, 2F), -111.3 (t, J = 11.3 Hz, 2F), -80.9
(t, J = 9.4 Hz, 3F); HRMS (TOF-ESI): m/z [M+H]+ calcd for
C34H27N2O2F18: 837.1785; found: 837.1781.
4.6. Synthesis of compound 2,5-dibutyl-3,6-bis(4-(perfluoro-
hexyl)phenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione
(Rf6CDPP)
The synthetic method of compound Rf6CDPP was similar to
that of compound Rf4CDPP, with perfluorohexyl iodide
replacing perfluorobutyl iodide. The compound was purified by a
Scheme 3. The synthetic route of compounds (CF2HDPP, Rf4CDPP,
o
column
chromatography
using
eluent
(petroleum
Rf6CDPP) (i) CF3CF2CF2CF2I or CF3CF2CF2CF2CF2CF2I/Cu, DMF, 125 C;
ether/dichloromethane = 5:1, v/v) to afford a yellow solid (150
(ii) TMSCF2H, CuCl, Phen, t-BuOK, DMF, r.t., 10h
1
mg, 58%). mp 139-140 °C. H NMR(400 MHz, CDCl3): δ ppm
4.4. Synthesis of compound 2,5-dibutyl-3,6-bis(4-(difluoro-
methyl)phenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione
(CF2HDPP)
7.88 (d, J = 8.4Hz, 4H), 7.68 (d, J = 8.4 Hz, 4H), 3.68 (t, J = 7.6
Hz, 4H), 1.48 (m,4H), 1.19 (m, 4H), 0.76 (t, J = 7.6 Hz, 6H); 13
C
NMR (100 MHz, CDCl3): δ ppm 162.3, 147.3, 131.5, 131.3 (t, J
= 26.4 Hz), 128.9, 127.5 (t, J = 6.5 Hz), 121.5 (t, J = 243.0 Hz),
118.6 (m), 115.5 (m), 113.3 (m), 110.9 (m), 110.7, 108.1 (m),
41.7, 31.6, 19.9, 13.6; 19F NMR (376 MHz, CDCl3): δ ppm -
126.1 (m, 2F), -122.8 (m, 2F), -121.6 (m, 4F), -111.1 (t, J = 15.1
Hz, 2F), -80.8 (t, J = 9.4 Hz, 3F); HRMS (TOF-ESI): m/z
[M+H]+ calcd for C34H27N2O2F26: 1037.1657; found: 1037.1658.
To a Shchlenk tube equipped with a magnetic stir bar were
added CuCl (118 mg, 1.2 mmol) and t-BuOK (268 mg, 2.4
mmol) were added under N2 atmosphere. DMF (3.0 mL) was
added to the tube. After stirring for 5 minutes, HCF2SiMe3 (298
mg, 2.4 mmol) was added to the mixture. The resulting mixture
was stirred for 15 minutes and then 1,10-phenanthroline (216 mg,
1.2 mmol) dissolved in DMF (2.0 mL) was added. After stirring
for another 10 min, 2,5-dibutyl-3,6-bis(4-iodophenyl)-2,5-
dihydropyrrolo-[3,4-c]pyrrole-1,4-dione (IDPP) (326 mg, 0.5
mmol) was dispersed in DMF (2.5 mL) and added to the mixture
under N2 atmosphere. The reaction mixture was kept at r.t. for 9
hours and then diluted with diethyl ether, washed with water and
brine, dried over sodium sulfate, and concentrated. The crude
products were purified by column chromatography on silica gel
to give the corresponding products. The compound was purified
Acknowledgements
This research was financially supported by the National
Natural
Science Foundation of China (21272069, 20672035) and the
Fundamental Research Funds for the Central Universities and
Key
Laboratory of Organofluorine Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences.
by
a
column chromatography using eluent (petroleum
Supplementary data
ether/dichloromethane = 2:1, v/v) to afford an orange solid (145
mg, 54%). mp 145-146 °C. H NMR(400 MHz, CDCl3): δ ppm
1
Supplementary data (copies of the 1H, 13C and 19F NMR
spectra of all DPP derivatives) associated with this article can be
found in the online version.
7.89(d, J = 8.4Hz, 4H), 7.67(d, J = 8.4 Hz, 4H), 6.72(t, J = 56.2
Hz,2H),3.75(t, J = 7.6 Hz, 4H), 1.55(m,4H),1.25(m,4H),0.85(t, J
= 7.6 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ ppm 162.4, 147.7,
136.7 (t, J = 22.4 Hz), 130.4, 129.0, 126.2 (t, J = 6.2 Hz), 113.9
(t, J = 238.3 Hz), 110.4, 41.7, 31.6, 19.9, 13.6; 19F NMR (376
MHz, CDCl3): δ ppm -112.1 (d, J = 56.4 Hz, 4F); HRMS (TOF-
ESI): m/z [M+Na]+ calcd for C28H28N2O2F4Na: 523.1985; found:
523.1976.
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