T-shaped push-pull chromophores: First modification of the indan-1,3-dione-fused benzene ring by cross-coupling reactions

Article abstract of DOI:10.1055/s-0033-1339664

A series of eight novel T-shaped chromophores with indan-1,3-dione central acceptor moiety and peripheral N,N-dimethylamino and thiophene donors were synthesized. 4,7-Diiodoindan-1,3-dione was prepared in a straightforward manner from phthalanhydride. Its modification with donors was accomplished by Knoevenagel, Suzuki-Miyaura, and Sonogashira reactions. Target push-pull chromophores were further investigated by X-ray analysis, UV/Vis spectra, and theoretical calculations. Georg Thieme Verlag Stuttgart, New York.

Full text of DOI:10.1055/s-0033-1339664

3044▌
PAPER
paper
T-Shaped Push–Pull Chromophores: First Modification of the Indan-1,3-
dione-Fused Benzene Ring by Cross-Coupling Reactions
T-Shaped Push–Pull Chromophores
Parmeshwar Solanke,a Filip Bureš,*a Olřich Pytela,a Jiří Kulhánek,a Zdeňka Padělkováb
a
Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice, 53210,
Czech Republic
Fax +420(46)6037068; E-mail: filip.bures@upce.cz
b
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice,
53210, Czech Republic
Received: 04.07.2013; Accepted after revision: 01.08.2013
in a new series of indan-1,3-dione-derived push–pull sys-
Abstract: A series of eight novel T-shaped chromophores with in-
tems 1–8 (Figure 1). Indan-1,3-dione is a well known
dan-1,3-dione central acceptor moiety and peripheral N,N-dimeth-
diketone, which has widely been used as terminal accep-
ylamino and thiophene donors were synthesized. 4,7-Diiodoindan-
1,3-dione was prepared in a straightforward manner from phthalan-
tor moiety in D-π-A chromophores.4 The main reasons of
hydride. Its modification with donors was accomplished by Kno- its popularity and wide use can be attributed to i) the pres-
evenagel, Suzuki–Miyaura, and Sonogashira reactions. Target
push–pull chromophores were further investigated by X-ray analy-
sis, UV/Vis spectra, and theoretical calculations.
ence of reactive methylene and thus resulting possible
modification via Knoevenagel condensation and ii) the
relatively strong electron-withdrawing character, which
Key words: chromophores, cross-coupling, conjugation, UV/Vis
spectroscopy, theoretical calculations
can be further enhanced by replacement of one or both
oxo groups by dicyanovinyl moieties.5 Indan-1,3-dione-
derived push–pull chromophores recently found applica-
tions as active organic layers in DSSC, OLED, and OPVC
devices,6–8 molecular glasses with NLO properties,9 chro-
moionophores for anion sensing and recognition,10 as well
as in biological sciences.11
Extended and functionalized organic aromatics can be
considered as modern, tunable, and active substances for
materials chemistry.1 The presence of delocalized clouds
of π-electrons determines their unique properties such as
reactivity towards electrophiles, color, spectral properties,
π–π interactions, crystallinity, polarizability, chemical,
and thermal stability as well as their typical smell.
linear
T-shaped
D
π-linker
π-linker
D
An attachment of an electron donor (D) and an electron
acceptor (A) to a π-conjugated molecule renders them an
even more interesting class of compounds, the so-called
push–pull chromophores. In these molecules, D–A inter-
action through the π-systems causes molecule polariza-
tion and D-π-A system constitute a dipole. This direct
interaction or intramolecular charge-transfer (ICT), which
can be expressed by limiting resonance structures (aro-
matic vs quinoid arrangement), is primarily responsible
for the linear as well as nonlinear optical (NLO) proper-
ties of organic D-π-A chromophores.1 Organic push–pull
molecules attract considerable attention due to their pro-
spective and manifold applications in organic-light emit-
ting diodes (OLEDs), organic-photovoltaic cells
(OPVCs), dye-sensitizing solar cells (DSSCs), organic
field effect transistors (OFETs), optical memories, etc.2
We have recently developed a variety of (hetero)organic
push–pull chromophores featuring various donors, accep-
tors, π-systems, and arrangements (linear, Y-shaped, X-
shaped, etc.).3 Hence, as a part of our ongoing research on
NLO-active chromophores (NLOphores), we report here-
O
O
O
O
D = electron donor
D
D
1–8
Figure 1 Linear versus T-shaped arrangement of indan-1,3-dione-
derived push–pull chromophores
In contrast to common linear indan-1,3-dione based
charge-transfer chromophores known to date,4–12 the new
series of compounds 1–8 possess T-shaped (D-π)3–A ar-
rangement with indan-1,3-dione central acceptor, one
N,N-dimethylamino-substituted π-linker at C2, and two
peripheral donors at C4 and C7. Whereas the substituents
at C2 can conveniently be introduced via Knoevenagel
condensation, indan-1,3-diones disubstituted at C4 and
C7 are scarce. Only methyl- and methoxy-substituted in-
dan-1,3-diones are known to date.11a,13 To the best of our
knowledge, no synthetic attempts were made to modify
indan-1,3-dione acceptor moiety on the fused benzene
ring. Hence, we report herein our synthetic strategy to tar-
SYNTHESIS 2013, 45, 3044–3051
Advanced online publication: 29.08.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0033-1339664; Art ID: SS-2013-Z0458-OP
© Georg Thieme Verlag Stuttgart · New York

PAPER
T-Shaped Push–Pull Chromophores
3045
get push–pull chromophores 1–8, their full spectral char- in 46% yield. The conversion of 9 to 4,7-diioiodoindan-
acterization, and further evaluation of the ICT by X-ray 1,3-dione 10 was accomplished by reaction with ethyl
analysis, UV/Vis spectra, and calculations.
acetoacetate and subsequent decarboxylation11a in 50%
yield. The regioselective outcome of the aforementioned
iodination, molecular structures, and spatial arrangements
of 9 and 10 were also confirmed by X-ray analysis as can
be seen from the ORTEP views in Figure 2. Al2O3-cata-
lyzed Knoevenagel condensation of 10 with 4-(N,N-di-
methylamino)-substituted benzaldehyde and cinnam-
aldehyde afforded indan-1,3-dione derivatives 11 and 12
in good yield of 80 and 77%, respectively.
The obvious retrosynthetic strategy leading to chromo-
phores 1–8 involves preparation of dihaloindan-1,3-dione
and its subsequent Knoevenagel and cross-coupling reac-
tions with appropriately donor-substituted π-linkers. Sev-
eral mono- or polyhalogenated indan-1,3-dione
derivatives are known,14 but none of them has halogens
appended to the C4 and C7. Considering the fact that in-
dan-1,3-diones can conveniently be synthesized from
phthalanhydrides,11a it was desirable to start from this 4,7-Diiodoindan-1,3-dione derivatives 11 and 12 were
readily available and inexpensive starting material. How- further treated with 4-(N,N-dimethylamino)phenylboron-
ever, phthalanhydride iodinations reported to date gave ic acid pinacol ester,19 4-ethynyl-N,N-dimethylaniline,
generally poor regioselectivities or polyiodinated prod- thiophen-2-ylboronic acid, and 2-ethynylthiophene20 in
ucts.15 Hence, we have attempted the iodination using terms of two-fold Suzuki–Miyaura and Sonogashira
modified Leznoff’s protocol originally developed for the cross-coupling reactions to afford target T-shaped chro-
iodination of phthalimide.16 In contrast to 4,5-regioselec- mophores 1–8 in the indicated yields (Scheme 1).
tivity on phthalimide, a similar reaction on phthalanhy-
dride afforded smoothly the desired product 9 with iodo
Monocrystals suitable for X-ray analysis of compounds 1,
9, and 10 were prepared by slow diffusion of hexane into
substituents at C3 and C6 (Scheme 1). Thus, the iodin-
their CH2Cl2 solutions. Whereas the crystal structures of
ation of phthalanhydride using I2 in 25% oleum showed
compounds 9 and 10 confirm the regioselective outcome
of phthalanhydride iodination, the X-ray analysis of target
the same regioselectivity as its recently published
bromination17 and afforded 3,6-diiodophthalanhydride 9
O
n
I
I
1. MeCOCH2COOEt
Et3N, Ac2O, 25 °C
I
2. HCl–H2O, 80 °C
O
O
N
I
I
I
I2/oleum (25%), 70 °C
46%
Me
Me
Al2O3/CH2Cl2
50%
O
O
O
O
O
O
n
O
O
10
9
Me
11, n = 0, 80 %
12, n = 1, 77 %
N
Me
Me
Me
Me
Me
Me
Me
N
N
N
N
Me
Me
O
O
O
O
Me
Me
N
B(pin)
S
n
n
B(OH)2
Me
Me
3, n = 0, 47%
4, n = 1, 75%
1, n = 0, 82%
2, n = 1, 60%
N
N
[PdCl2(PPh3)2], Na2CO3
THF–H2O, 60 °C
Me
Me
11 or 12
or
S
S
S
S
Me
N
Me
O
O
O
O
S
[PdCl2(PPh3)2], CuI
THF, Et3N, 60 °C
n
n
Me
Me
7, n = 0, 32%
8, n = 1, 54%
5, n = 0, 30%
6, n = 1, 75%
N
N
Me
Me
Scheme 1 Synthesis of target T-shaped chromophores 1–8
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 3044–3051

3046
P. Solanke et al.
PAPER
torsion angles of 25–35° were usually observed.3d,e Strong
out of plain deviations of the DMA rings in 1 are most
likely caused by a repulsion of the indan-1,3-dione oxy-
gen atoms and DMA ortho hydrogens. Therefore, both
DMA rings are twisted and slightly bent. A polarization of
NLOphore 1 can also be assessed by evaluating the quin-
oid character δr of appended DMA rings.3b Whereas both
lateral DMA ring possess δr equal to 0.031 and 0.033, the
lower DMA ring has δr = 0.041 (for benzene, δr = 0; in
fully quinoid structure such as benzoquinone, δr = 0.1).
The difference clearly reflects the planar versus out of
plane arrangements of both types of connections. Hence,
the lower DMA ring contributes to the ICT more signifi-
cantly.
All target compounds 1–8 are highly colored solids. Their
optical properties were studied by UV/Vis absorption
spectroscopy as shown in Figure 3, Table 1, and the Sup-
porting Information. The spectra were measured in di-
chloromethane at a concentration of 1 × 10–5 M and are
dominated by intensive CT-peaks appearing within the
range of 486–570 nm (2.55–2.18 eV) with molar absorp-
tion coefficients ε = 31.9–87.9 × 103 M·cm–1.
The positions of the longest-wavelength absorption max-
ima (λmax) are obviously dependent on the π-system
length, terminal acceptor used (DMA vs thienyl) and
chromophore overall planarity. The influence of the π-
system length and planarity can be demonstrated on chro-
mophores 1–4 in which the π-spacer was systematically
extended by olefinic and acetylenic subunits. This exten-
sion shifted the λmax by 60 nm. Chromophore 4, which
possesses the longest π-system with one additional double
bond (cinnamaldehyde moiety at C2) and two acetylenic
subunit separating lateral DMA donors, showed the most
bathochromically shifted CT-band at 564 nm. On the con-
trary, chromophore 1 without additional olefinic and acet-
ylenic units showed significant out of plain twist (see the
Figure 2 Crystal structures of compounds 9 (R = 0.03), 10
(R = 0.02) and 1 (R = 0.08); vibrational ellipsoids of the ORTEP plots
are shown at the 50% probability level (150 K), molecules of solvents
(CH2Cl2) were omitted for clarity.18
chromophore 1 can be used to determine the extent of the
ICT (Figure 2). The indandione moiety with appended 4-
(N,N-dimethylamino)benzylidene substituent can be con-
sidered as a fully planar π-system. However, both N,N-di-
methylanilino rings (DMA) at C4 and C7 are twisted out
of the main chromophore plain with average torsion an-
gles 43° and 46°. For direct DMA to benzene connections,
Table 1 Measured and Calculated (MOPAC2012) Properties of Chromophores 1–8
Product λmax
[nm (eV)]a
ε
Mp
EHOMO
(eV)b
ELUMO
(eV)b
ΔE
(eV)b
μ
(D)c
β
γ
(mol–1dm3cm–1]a (°C)
(10–29 esu)d (10–29 esu)e
1
2
3
4
5
6
7
8
486 (2.55)
530 (2.34)
503 (2.46)
546 (2.27)
495 (2.51)
554 (2.23)
510 (2.43)
570 (2.18)
53600
50100
87900
31900
70500
43100
55400
41700
280–283
–7.89
–7.90
–7.81
–7.83
–8.27
–8.16
–8.40
–8.17
–0.70
–1.01
–0.94
–1.12
–1.06
–1.24
–1.41
–1.45
–7.19
–6.89
–6.87
–6.71
–7.21
–6.92
–6.99
–6.72
3.79
4.46
4.86
5.30
3.98
4.96
3.86
4.99
1.70
4.11
1.63
3.92
295
527
265–267
>400
867
>400
1110
253–255
241–243
222–224
185–187
173.9
205071
341715
778606
842837
278.5
293.9
443.5
a Position (λmax) and molar absorption coefficient (ε) of the longest-wavelength absorption maxima (measured in CH2Cl2, c = 1 × 10–5 M).
b Calculated energies of HOMO and LUMO and their differences ΔE (gap).
c Calculated ground state permanent dipole moment μ.
d Calculated first hyperpolarizability β.
e Calculated second hyperpolarizability γ.
Synthesis 2013, 45, 3044–3051
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T-Shaped Push–Pull Chromophores
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Figure 4 Optimized geometries and HOMO (red) and LUMO (blue)
localizations in representative chromophores 1, 4, 6, and 8
Figure 3 UV/Vis absorption spectra of chromophores 1–8 measured
in dichloromethane (c = 1 × 10–5 M)
1,3-dione and C2-appended part of the π-system. The op-
timized geometries of 1 and 4 (Figure 1) confirmed the
difference in anchoring the lateral DMA groups through
sigma or triple bonds (compare with Figure 2). The latter
connection caused planarization of the entire π-system. In
contrast to DMA, directly appended thiophene rings were
less twisted from indan-1,3-dione plain (average torsion
angles 22–28°). However, planarization of the π-system
through an additional ethynylene unit as in 7 and 8 result-
ed in extension of the LUMO over the indan-1,3-dione-
fused benzene ring.
X-ray data discussion above), which caused hypsochro-
mic shift of the CT band to 486 nm. A similar trend can be
seen in the chromophore series 5–8 with thienyl lateral
donors. However, a comparison of both series allowed
evaluation of donating nature of both moieties. A compar-
ison of λmax values across the structural analogues 1/5, 2/6,
3/7 and 4/8 revealed bathochromic shift with Δλmax 9, 24,
7, and 24 nm for thienyl-substituted chromophores 5–8.
These changes are remarkably pronounced for chromo-
phores 6 and 8 with the cinnamaldehyde moiety at C2.
Chromophore 8 with indan-1,3-dione acceptor core func-
tionalized by one 4-(N,N-dimethylamino)cinnamalde-
hyde moiety combined with two lateral thienyl donors
linked through ethynyl spacers showed the most batho-
chromically shifted CT band up to 570 nm.
The calculated HOMO/LUMO energies and their respec-
tive differences ΔE reflect the same trends as seen by the
absorption spectroscopy. Thus, the π-system extension
and molecule planarization led to lowered HOMO-
LUMO gap. The lowest ΔΕ values and highest dipole mo-
ments were calculated for planar molecules 4 (ΔΕ = –6.71
eV; μ = 5.30 D) and 8 (ΔΕ = –6.72 eV; μ = 4.99 D) featur-
ing the largest π-system.
A comparison of the longest-wavelength absorption max-
ima of target compounds 1–8 (λmax = 486–570 nm) with
diiodo-substituted molecules 11 of (λmax = 502 nm; SI)
and 12 (λmax = 562 nm; SI) clearly demonstrates, that the
lower DMA rings appended to C2 contribute more signif-
icantly to the ICT. This is in agreement with the afore-
mentioned conclusions deduced from the X-ray data.
Hence, the lateral donors appended at C4 and C7 can be
denoted as auxiliary.
The calculated first and second hyperpolarizabilities β and
γ were affected by similar structural features as the afore-
mentioned properties. The values in Table 1 clearly dem-
onstrates that, within the particular series 1–4 and 5–8,
both hyperpolarizabilities increase with the π-system ex-
tension and planarization. For instance, a simple replace-
ment of 4-(N,N-dimethylamino)benzaldehyde moiety in 1
with its cinnamaldehyde derivative as in 2 resulted in dou-
bling of their hyperpolarizabities β (1.7 vs 4.11 × 10–29
esu) and γ (295 vs 527 × 10–29 esu). However, the most
dramatic changes were caused by replacing the lateral
DMA donor groups with thiophene rings. Such relatively
small structural modification resulted in a hundred-fold
increase of the calculated first hyperpolarizabilities β! The
second hyperpolarizabilites γ increased even in three or-
ders of magnitude. Although the auxiliary electron-donat-
ing ability and high polarizability of thiophene ring are
well known,24,25 such dramatic increase is remarkable.
Electronic properties such as HOMO and LUMO ener-
gies, ground state permanent dipole moment μ and first
and second hyperpolarizabilities β and γ were calculated
and visualized for the most stable conformers using PM3
(ArgusLab),21 PM7 (MOPAC2012),22 and OPchem.23 The
acquired data are summarized in Table 1. Visualizations
of the HOMO and LUMO for representative chromo-
phores 1, 4, 6 and 8 are shown in Figure 4 (for complete
listing, see the Supporting Information).
As expected, the HOMO is generally localized on the do-
nor moieties while the LUMO is spread over the indan-
© Georg Thieme Verlag Stuttgart · New York
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P. Solanke et al.
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4,7-Diiodoindan-1,3-dione (10)
Hence, T-shaped push–pull chromophores 1–8, which can
be prepared from readily available phthalic anhydride in a
four step synthesis, proved to be very promising candi-
dates for further elaboration and application as active lay-
ers in optoelectronic devices.
Into a solution of 3,6-diiodophthalanhydride 9 (4.0 g, 10.0 mmol) in
Ac2O (10 mL) and Et3N (5.5 mL) was added ethyl acetoacetate
(1.52 mL, 12.0 mmol) and the reaction mixture was stirred at 25 °C
for 24 h. Crushed ice (20 g) and 35% aq HCl (10 mL) were added
with stirring and the precipitate was collected by filtration. The re-
sulting solid was treated with hot (70–80 °C) 10% aq HCl (900 mL)
to assure complete decarboxylation. The title compound 10 was ob-
tained as a light-yellow solid (2.0 g, 50%); mp 180–183 °C; Rf = 0.4
(CH2Cl2–hexane, 2:1).
Reagents and solvents were reagent-grade and were purchased from
Penta, Aldrich, and Acros and used as received. Column chroma-
tography was carried out with silica gel 60 (particle size 0.040–
0.063 mm, 230–400 mesh; Merck) and commercially available sol-
vents. TLC was conducted on aluminum sheets coated with silica
gel 60 F254 obtained from Merck, with visualization by UV lamp
(254 or 360 nm). Melting points were measured on a Büchi B-540
melting point apparatus in open capillaries and are uncorrected. 1H
and 13C NMR spectra were recorded in CDCl3 at 400 MHz and 100
MHz, respectively, with a Bruker Avance 400 instruments at 25 °C.
Chemical shifts are reported in ppm relative to the signal of Me4Si.
The residual solvent signal in the 1H and 13C NMR spectra was used
as an internal reference (CDCl3: 7.25 and 77.23 ppm). Coupling
constants (J) are given in Hz. Standard abbreviations are used for in-
dicating signal multiplicities. Quaternary carbons of compound 11
were not observed due to its sparing solubility in deuterated sol-
vents. EI-MS spectra were measured on a GC/MS configuration
comprised of an Agilent Technologies – 6890N gas chromatograph
(HP-5MS column, length 30 m, I.D. 0.25 mm, film 0.25 μm)
equipped with a 5973 Network MS detector (EI 70 eV, mass range
33−550 Da). High-resolution MALDI MS spectra were measured
on a MALDI mass spectrometer LTQ Orbitrap XL (Thermo Fisher
Scientific, Bremen, Germany) equipped with nitrogen UV laser
(337 nm, 60 Hz). The LTQ Orbitrap instrument was operated in
positive-ion mode over a normal mass range (m/z 50–1500) with the
following setting of tuning parameters: resolution 100,000 at
m/z = 400, laser energy 17 mJ, number of laser shots 5, respectively.
The survey crystal positioning system (survey CPS) was set for the
random choice of shot position by automatic crystal recognition.
The isolation width Δm/z 4, normalized collision energy 25%, acti-
vation Q value 0.250, activation time 30 ms and helium as the col-
lision gas were used for CID experiments in LTQ linear ion trap.
The used matrix was 2,5-dihydroxybenzoic acid (DHB). Mass spec-
tra were averaged over the whole MS record (30 s) for all measured
samples. IR spectra were recorded as neat using HATR adapter on
a PerkinElmer FTIR Spectrum BX spectrometer. UV/Vis spectra
were recorded on a HP LE2201 spectrophotometer in CH2Cl2
(c = 1 × 10–5 M). Elemental analyses were performed on an EA
1108 Fisons instrument.
IR (HATR): 3647, 3006, 1732, 1502, 1184, 1134, 1087, 909, 764
cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.33 (s, 2 H, CH2), 7.88 (s, 2 H,
2 × CH).
13C NMR (100 MHz, CDCl3): δ = 44.8, 89.0, 143.8, 147.7, 193.7.
MS (EI, 70 eV): m/z (%) = 398 (100, [M]+), 370 (10), 342 (8), 229
(20), 215 (14), 201 (23), 74 (19).
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C9H5I2O2:
398.8373; found: 398.8371.
Knoevenagel Condensation Reactions of 1,3-Dione 10; General
Procedure
4,7-Diiodoindan-1,3-dione (10; 3.98 g, 10.0 mmol) and 4-(N,N-di-
methylamino)benzaldehyde (1.57 g, 10.5 mmol) or 4-(N,N-dimeth-
ylamino)cinnamaldehyde (1.84 g, 10.5 mmol) were dissolved in
CH2Cl2 (20 mL). Al2O3 (5.1 g, 50.0 mmol, activity II–III) was add-
ed and the reaction mixture was stirred at 25 °C for 3 h. Al2O3 was
filtered off, the solvent was evaporated in vacuo, and the crude
product was purified by column chromatography (SiO2; CH2Cl2–
hexane, 1:1).
2-[4-(N,N-Dimethylamino)benzylidene]-4,7-diiodoindan-1,3-di-
one (11)
The title compound was prepared from 4-(N,N-dimethylami-
no)benzaldehyde following the general procedure (4.2 g, 80%); or-
ange solid; mp 228–230 °C; Rf = 0.5 (CH2Cl2–hexane, 2:1).
IR (HATR): 3627, 3009, 1716, 1494, 1386, 1184, 1135, 1087, 907,
789 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.17 [s, 6 H, N(CH3)2], 6.74 (d,
J = 9.6 Hz, 2 H, 2 × CH), 7.73–7.78 (m, 2 H, 2 × CH), 7.82 (s, 1 H,
CH=), 8.54 (br s, 1 H, CH), 8.57 (br s, 1H, CH).
13C NMR (100 MHz, CDCl3): δ = 40.4, 88.3, 88.4, 111.8, 122.3,
139.0, 146.0, 146.5, 149.7 (signals of six Cq are missing).
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C18H14I2NO2:
529.9108; found: 529.9106.
3,6-Diiodophthalanhydride (9)
UV/Vis (CH2Cl2): λmax (log ε) = 502 (4.80), 279 (4.04), 229 nm
(4.33).
Into a solution of phthalic anhydride (14.80 g, 100.0 mmol) in fum-
ing H2SO4 (60 mL, 25%) was added I2 (50.8 g, 200.0 mmol) and the
reaction mixture was stirred at 70 °C for 24 h. The mixture was
poured over crushed ice (400 g), the precipitate was collected by fil-
tration and washed with H2O (2 × 100 mL), 2% aq Na2CO3 (1 × 100
mL), sat. aq Na2S2O3 (1 × 100 mL), and H2O (1 × 100 mL) and
dried on air. The crude product was extracted with CH2Cl2 (3 × 200
mL), the combined organic extracts were dried (Na2SO4), and evap-
orated to afford the title compound 9 as an off-white solid (18.4 g,
46%); mp 229–233 °C; Rf = 0.7 (CH2Cl2–hexane, 2:1).
2-{(2E)-3-[4-(N,N-Dimethylamino)phenyl]prop-2-en-1-yli-
dene}-4,7-diiodoindan-1,3-dione (12)
The title compound was prepared from 4-(N,N-dimethylamino)cin-
namaldehyde following the general procedure (4.3 g, 77%); dark
metallic solid; mp 277–281 °C; Rf = 0.5 (CH2Cl2–hexane, 2:1).
IR (HATR): 3625, 2918, 1732, 1506, 1384, 1210, 1185, 1136, 1087,
907, 812, 624 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.12 [s, 6 H, N(CH3)2], 6.67 (d,
J = 8.8 Hz, 2 H, 2 × CH), 7.38 (d, J = 14.8 Hz, 1 H, CH=), 7.61 (d,
J = 8.8 Hz, 2 H, 2 × CH), 7.68 (d, J = 12.0 Hz, 1 H, CH=), 7.74 (s,
1 H, CH), 7.75 (s, 1 H, CH), 8.31 (dd, J1 = 14.8 Hz, J2 = 12.0 Hz, 1
H, CH=).
IR (HATR): 3627, 2998, 1716, 1501, 1393, 1213, 1186, 1135, 905,
836, 743 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.91 (s, 2 H, 2 × CH).
13C NMR (100 MHz, CDCl3): δ = 91.3, 134.3, 147.45, 159.7.
MS (EI, 70 eV): m/z (%) = 400 (100, [M]+), 356 (45), 229 (49), 201
(54), 127 (11), 74 (44).
13C NMR (100 MHz, CDCl3): δ = 40.4, 88.1, 88.5, 112.1, 119.7,
121.9, 123.8, 132.3, 142.0, 146.2, 146.3, 149.0, 153.3, 156.2, 157.7,
187.8, 190.0.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C20H16I2NO2:
555.9265; found: 555.9257.
Synthesis 2013, 45, 3044–3051
© Georg Thieme Verlag Stuttgart · New York

PAPER
T-Shaped Push–Pull Chromophores
3049
UV/Vis (CH2Cl2): λmax (log ε) = 562 (4.80), 338 (4.03), 232 nm
(4.36).
2-[4-(N,N-Dimethylamino)benzylidene]-4,7-bis(thiophen-2-
yl)indan-1,3-dione (5)
The title compound was prepared from 11 and thiophen-2-ylboronic
acid following the general procedure (66 mg, 30%); dark red solid;
mp 253–255 °C; Rf = 0.2 (CH2Cl2–hexane, 1:1).
Suzuki–Miyaura Reactions of 11 and 12; General Procedure
Diiodo derivatives 11 (265 mg, 0.5 mmol) or 12 (278 mg, 0.5 mmol)
and 4-(N,N-dimethylamino)phenylboronic acid pinacol ester (272
mg, 1.1 mmol) or thiophen-2-ylboronic acid (141 mg, 1.1 mmol)
were dissolved in a mixture of THF–H2O (20 mL, 4:1). Argon was
bubbled through the solution for 15 min whereupon [PdCl2(PPh3)2]
(18 mg, 0.025 mmol) and Na2CO3 (159 mg, 1.5 mmol) were added
and the reaction mixture was stirred at 60 °C for 3 h. The reaction
mixture was diluted with H2O (50 mL) and extracted with CH2Cl2
(2 × 50 mL). The combined organic extracts were dried (Na2SO4),
the solvents were evaporated in vacuo, and the crude product was
purified by column chromatography (SiO2; indicated solvent sys-
tem).
IR (HATR): 3295, 2905, 1653, 1532, 1382, 1320, 1247, 1158, 1105,
1034, 989, 699 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.11 [s, 6 H, N(CH3)2], 6.68 (d,
J = 9.2 Hz, 2 H, 2 × CH), 7.15–7.19 (m, 2 Hthiophene), 7.46 (t, J = 5.0
Hz, 2 Hthiophene), 7.56 (d, J = 4.0 Hz, 1 Hthiophene), 7.67 (d, J = 4.0 Hz,
1 Hthiophene), 7.67–7.74 (m, 3 H, 2 × CH + CH=), 8.46 (s, 1 H, CH),
8.48 (s, 1 H, CH).
13C NMR (100 MHz, CDCl3): δ = 40.3, 111.6, 122.3, 123.0, 127.0,
127.2, 127.5, 127.6, 129.3, 129.7, 132.2, 132.3, 136.1, 136.6, 137.0,
138.5, 138.8, 139.0, 139.1, 147.9, 154.2, 188.7, 190.4.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C26H20NO2S2:
442.0930; found: 442.0930.
2-[4-(N,N-Dimethylamino)benzylidene]-4,7-bis[4-(N,N-dimeth-
ylamino)phenyl]indan-1,3-dione (1)
The title compound was prepared from 11 and 4-(N,N-dimethylami-
no)phenylboronic acid pinacol ester following the general proce-
dure (211 mg, 82%); orange solid; mp 280–283 °C; Rf = 0.1
(CH2Cl2–hexane, 2:1).
UV/Vis (CH2Cl2): λmax (log ε) = 242 (4.46), 286 (4.40), 364 (3.88),
495 nm (4.85).
Anal. Calcd for C26H19NO2S2: C, 70.72; H, 4.34; N, 3.17. Found: C,
70.59; H, 4.29; N, 3.13.
IR (HATR): 3115, 2920, 1658, 1548, 1516, 1340, 1170, 1108, 1018,
812, 624 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.03 [s, 6 H, N(CH3)2], 3.05 [s, 6
H, N(CH3)2], 3.08 [s, 6 H, N(CH3)2], 6.65 (d, J = 8.8 Hz, 2 H,
2 × CH), 6.83 (d, J = 8.8 Hz, 4 H, 4 × CH), 7.49–7.59 (m, 6 H,
6 × CH), 7.69 (s, 1 H, CH=), 8.45 (s, 1 H, CH), 8.47 (s, 1 H, CH).
13C NMR (100 MHz, CDCl3): δ = 40.2, 40.6, 40.7, 111.4, 111.8,
122.4, 124.3, 125.8, 126.1, 130.7, 135.9, 136.4, 136.7, 138.0, 138.5,
139.2, 146.5, 150.3, 150.5, 153.7, 189.5, 191.1.
2-{(2E)-3-[4-(N,N-Dimethylamino)phenyl]prop-2-en-1-yli-
dene}-4,7-bis(thiophen-2-yl)indan-1,3-dione (6)
The title compound was prepared from 12 and thiophen-2-ylboronic
acid following the general procedure (175 mg, 75%); dark brown
solid; mp 241–243 °C; Rf = 0.2 (CH2Cl2–hexane, 1:1).
IR (HATR): 3610, 2929, 1741, 1542, 1369, 1180, 964, 676 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.05 [s, 6 H, N(CH3)2], 6.63 (d,
J = 9.0 Hz, 2 H, 2 × CH), 7.15–7.20 (m, 2 Hthiophene), 7.24 (d,
J = 15.0 Hz, 1 H, CH=), 7.45–7.48 (m, 2 Hthiophene), 7.54–7.58 (m, 4
H, 2 × CH + thiophene + CH=), 7.66–7.74 (m, 3 H, thiophene +
CH + CH), 8.22 (dd, J1 = 15.0 Hz, J2 = 12.3 Hz, 1 H, CH=).
13C NMR (100 MHz, CDCl3): δ = 40.3, 112.0, 119.8, 124.0, 124.2,
127.1, 127.3, 127.5, 127.6, 129.3, 129.7, 131.7, 132.1, 132.5, 136.3,
136.9, 137.2, 138.7, 138.8, 138.9, 147.0, 152.7, 154.3, 189.5, 190.1.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C34H34N3O2:
516.2646; found: 516.2642.
UV/Vis (CH2Cl2): λmax (log ε) = 256 (4.46), 307 (4.38), 486 nm
(4.73).
Anal. Calcd for C34H33N3O2: C, 79.19; H, 6.45; N, 8.15. Found: C,
79.12; H, 6.49; N, 8.20.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C28H22NO2S2:
468.1086; found: 468.1088.
2-{(2E)-3-[4-(N,N-Dimethylamino)phenyl]prop-2-en-1-yli-
dene}-4,7-bis[4-(N,N-dimethylamino)phenyl]indan-1,3-dione
(2)
The title compound was prepared from 12 and 4-(N,N-dimethylami-
no)phenylboronic acid pinacol ester following the general proce-
dure (163 mg, 60%); dark metallic solid; mp 265–267 °C; Rf = 0.1
(CH2Cl2–hexane, 2:1).
UV/Vis (CH2Cl2): λmax (log ε) = 245 (4.45), 295 (4.36), 554 nm
(4.63).
Anal. Calcd for C28H21NO2S2: C, 71.92; H, 4.53; N, 3.00. Found: C,
72.22; H, 4.48; N, 3.04.
Sonogashira Reactions of 11 and 12; General Procedure
Diiodo derivatives 11 (265 mg, 0.5 mmol) or 12 (278 mg, 0.5 mmol)
and 4-ethynyl-N,N-dimethylaniline (160 mg, 1.1 mmol) or 2-ethyn-
ylthiophene (119 mg, 1.1 mmol) were dissolved in a mixture of
THF–Et3N (20 mL, 4:1). Argon was bubbled through the solution
for 15 min whereupon [PdCl2(PPh3)2] (18 mg, 0.025 mmol) and CuI
(10 mg, 0.05 mmol) were added and the reaction mixture was stirred
at 60 °C for 3 h. The reaction mixture was diluted with H2O (50 mL)
and extracted with CH2Cl2 (2 × 50 mL). The combined organic ex-
tracts were dried (Na2SO4), the solvents were evaporated in vacuo,
and the crude product was purified by column chromatography
(SiO2; indicated solvent system).
IR (HATR): 3318, 2904, 1642, 1537, 1419, 1313, 1156, 1101, 1019,
810 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.03 [s, 12 H, 2 × N(CH3)2], 3.05
[s, 6 H, N(CH3)2], 6.62 (d, J = 8.4 Hz, 2 H, 2 × CH), 6.83 (t, J = 9.2
Hz, 4 H, 4 × CH), 7.18 (d, J = 14.8 Hz, 1 H, CH=), 7.45–7.59 (m, 9
H, 6 × CH + 2 × CH + CH=), 8.24 (dd, J1 = 14.8 Hz, J2 = 12.4 Hz,
1 H, CH=).
13C NMR (100 MHz, CDCl3): δ = 40.3, 40.6, 40.7, 111.8, 111.9,
120.0, 124.1, 125.5, 125.6, 125.8, 130.7, 130.7, 131.2, 136.1, 136.6,
137.1, 138.5, 139.2, 139.4, 145.5, 150.4, 150.5, 152.3, 152.6, 190.3,
190.8.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C36H36N3O2:
542.2802; found: 542.2791.
2-[4-(N,N-Dimethylamino)benzylidene]-4,7-bis{[4-(N,N-di-
methylamino)phenyl]ethynyl}indan-1,3-dione (3)
The title compound was prepared from 11 and 4-ethynyl-N,N-di-
methylaniline following the general procedure (132 mg, 47%); dark
metallic solid; mp >400 °C; Rf = 0.2 (CH2Cl2–hexane, 2:1).
UV/Vis (CH2Cl2): λmax (log ε) = 253 (4.52), 320 (4.47), 530 nm
(4.70).
Anal. Calcd for C36H35N3O2: C, 79.82; H, 6.51; N, 7.76. Found: C,
79.59; H, 6.47; N, 7.68.
IR (HATR): 3346, 2884, 1697, 1540, 1362, 1338, 1310, 1159, 1101,
1030, 642 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.01 [s, 6 H, N(CH3)2], 3.02 [s, 6
H, N(CH3)2], 3.13 [s, 6 H, N(CH3)2], 6.66–6.75 (m, 6 H, 6 × CH),
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 3044–3051

3050
P. Solanke et al.
PAPER
7.58–7.65 (m, 6 H, 6 × CH), 7.78 (s, 1 H, CH=), 8.57 (s, 1 H, CH),
8.59 (s, 1 H, CH).
IR (HATR): 3630, 3006, 1688, 1510, 1182, 1136, 1087, 911, 813,
642 cm–1.
13C NMR (100 MHz, CDCl3): δ = 40.3, 40.3, 40.4, 86.1, 86.2, 99.1,
99.5, 109.8, 110.0, 111.6, 111.9, 112.1, 118.9, 119.0, 122.5, 123.5,
131.5, 133.8, 136.6, 137.5, 138.3, 139.0, 141.1, 147.2, 150.7, 150.8,
154.0, 188.3, 190.1.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C38H34N3O2:
564.2646; found: 564.2636.
1H NMR (400 MHz, CDCl3): δ = 3.06 [s, 6 H, N(CH3)2], 6.65 (d,
J = 9.0 Hz, 2 H, 2 × CH), 7.04–7.08 (m, 2 Hthiophene), 7.28 (d,
J = 15.0 Hz, 1 H, CH=), 7.37–7.40 (m, 2 Hthiophene), 7.46 (d, J = 4.0
Hz, 1 Hthiophene), 7.50 (d, J = 4.0 Hz, 1 Hthiophene), 7.58 (d, J = 9.0 Hz,
2 H, 2 × CH), 7.64 (d, J = 12.2 Hz, 1 H, CH=), 7.68 (s, 1 H, CH),
7.69 (s, 1 H, CH), 8.30 (dd, J1 = 15.0 Hz, J2 = 12.2 Hz, 1 H, CH=).
13C NMR (100 MHz, CDCl3): δ = 40.3, 90.7, 90.8, 90.9, 91.0,
112.0, 118.3, 118.6, 119.8, 123.0, 123.9, 127.5, 127.6, 128.9, 129.0,
131.8, 133.5, 133.6, 136.8, 137.4, 140.1, 141.3, 147.2, 152.8, 154.6,
188.6, 189.0.
UV/Vis (CH2Cl2): λmax (log ε) = 273 (4.52), 358 (4.62), 503 nm
(4.94).
Anal. Calcd for C38H33N3O2: C, 80.97; H, 5.90; N, 7.45. Found: C,
80.78; H, 5.98; N, 7.47.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C32H22NO2S2:
516.1086; found: 516.1084.
2-{(2E)-3-[4-(N,N-Dimethylamino)phenyl]prop-2-en-1-yli-
dene}-4,7-bis{[4-(N,N-dimethylamino)phenyl]ethynyl}indan-
1,3-dione (4)
The title compound was prepared from 12 and 4-ethynyl-N,N-di-
methylaniline following the general procedure (221 mg, 75%); dark
metallic solid; mp >400 °C; Rf = 0.2 (CH2Cl2–hexane, 2:1).
UV/Vis (CH2Cl2): λmax (log ε) = 246 (4.38), 334 (4.50), 420 (4.21),
570 nm (4.62).
Anal. Calcd for C32H21NO2S2: C, 74.54; H, 4.11; N, 2.72. Found: C,
74.35; H, 4.20; N, 2.71.
IR (HATR): 3732, 2924, 1716, 1522, 1362, 1338, 1227, 1156, 1055,
943, 812, 641 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.00 [s, 6 H, N(CH3)2], 3.01 [s, 6
H, N(CH3)2], 3.06 [s, 6 H, N(CH3)2], 6.65–6.67 (m, 6 H, 6 × CH),
7.26 (d, J = 15.0 Hz, 1 H, CH=), 7.57–7.64 (m, 9 H, 6 × CH +
2 × CH + CH=), 8.33 (dd, J1 = 15.0 Hz, J2 = 12.2 Hz, 1 H, CH=).
Acknowledgment
This research was supported by the Czech Science Foundation
(P106/12/0392).
13C NMR (100 MHz, CDCl3): δ = 40.3, 40.4, 40.5, 86.0, 86.1, 99.3,
99.6, 109.7, 109.8, 111.9, 112.0, 118.8, 119.1, 120.0, 124.1, 124.8,
131.5, 133.7, 136.8, 137.4, 139.7, 140.9, 146.2, 150.7, 150.8, 152.5,
153.4, 189.2, 189.6.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
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References
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C40H36N3O2:
590.2802; found: 590.2797.
(1) Materials for Nonlinear Optics: Chemical Perspectives,
ACS Symposium Series Vol. 455; Marder, S. R.; Sohn, J. E.;
Stucky, G. D., Eds.; American Chemical Society:
UV/Vis (CH2Cl2): λmax (log ε) = 279 (4.40), 361 (4.40), 546 nm
(4.50).
Washington DC, 1991, 2.
Anal. Calcd for C40H35N3O2: C, 81.47; H, 5.98; N, 7.13. Found: C,
82.05; H, 5.87; N, 7.09.
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2-[4-(N,N-Dimethylamino)benzylidene]-4,7-bis[(thiophen-2-
yl)ethynyl]indan-1,3-dione (7)
The title compound was prepared from 11 and 2-ethynylthiophene
following the general procedure (78 mg, 32%); dark metallic solid;
mp 222–224 °C; Rf = 0.1 (CH2Cl2–hexane, 1:1).
IR (HATR): 3724, 2915, 1660, 1514, 1392, 1180, 1138, 968, 693
cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.14 [s, 6 H, N(CH3)2], 6.73 (d,
J = 9.2 Hz, 2 H, 2 × CH), 7.05–7.08 (m, 2 Hthiophene), 7.39 (d, J = 5.2
Hz, 2 Hthiophene), 7.47 (d, J = 4.0 Hz, 1 Hthiophene), 7.49 (d, J = 4.0 Hz,
1 Hthiophene), 7.67–7.73 (m, 2 H, 2 × CH), 7.80 (s, 1 H, CH=), 8.55
(s, 1 H, CH), 8.57 (s, 1 H, CH).
13C NMR (100 MHz, CDCl3): δ = 40.3, 90.7, 90.9, 90.9, 91.0,
111.7, 118.4, 118.5, 122.4, 122.7, 123.0, 123.1, 127.5, 127.6, 128.8,
129.0, 133.5, 133.6, 136.6, 137.5, 138.6, 139.4, 141.5, 148.1, 154.3,
187.8, 189.6.
HR-MALDI-MS (DHB): m/z [M + H]+ calcd for C30H20NO2S2:
(4) (a) Moylan, C. R.; Twieg, R. J.; Lee, V. Y.; Swanson, S. A.;
Betterton, K. M.; Miller, R. D. J. Am. Chem. Soc. 1993, 115,
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Akiyama, S.; Nakazumi, H. Bull. Chem. Soc. Jpn. 1991, 64,
1641. (g) Gleiter, R.; Hoffmann, R.; Irngartinger, H.;
490.0930; found: 490.0925.
UV/Vis (CH2Cl2): λmax (log ε) = 292 (4.41), 320 (4.42), 405 (4.35),
510 nm (4.74).
Anal. Calcd for C30H19NO2S2: C, 73.60; H, 3.91; N, 2.86. Found: C,
73.59; H, 3.89; N, 2.79.
2-{(2E)-3-[4-(N,N-Dimethylamino)phenyl]prop-2-en-1-yli-
dene}-4,7-bis[(thiophen-2-yl)ethynyl]indan-1,3-dione (8)
The title compound was prepared from 12 and 2-ethynylthiophene
following the general procedure (139 mg, 54%); dark metallic solid;
mp 185–187 °C; Rf = 0.1 (CH2Cl2–hexane, 1:1).
Synthesis 2013, 45, 3044–3051
© Georg Thieme Verlag Stuttgart · New York

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Synthesis 2013, 45, 3044–3051