Sequence-independent synthesis of π-conjugated arylenevinylene oligomers using bifunctional thiophene monomers

Article abstract of DOI:10.1002/adfm.201101897

Sequence-independent or "click" chemistry is applied for the preparation of a series of novel and structurally similar π-conjugated oligomers. The new oligomers are prepared using Wittig-Horner chemistry from bifunctional building blocks that can be inter

Full text of DOI:10.1002/adfm.201101897

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Sequence-Independent Synthesis of π-conjugated
Arylenevinylene Oligomers using Bifunctional Thiophene
Monomers
Kammasandra Nanjunda Shivananda, Irit Cohen, Elena Borzin, Yulia Gerchikov,
Michal Firstenberg, Olga Solomeshch, Nir Tessler, and Yoav Eichen*
obstacle for the full realization of the poten-
tial embedded in organic optoelectronics
and molecular nanoelectronics.[7] Assembly
by design (i.e., engineering) of complex
structures with molecular, electronic grade
precision is expected to open new frontiers
in organic electronics by offering new fami-
lies of materials to the organic electronics
world.[8]
In nature, most chemical entities are
prepared by target-specific machinery
that is tailored to produce one material or
a very narrow set of structurally similar
compounds in a “copy exact” manner. This
approach is being utilized in most cases
where high-fidelity in synthesis is required,
as can be seen in the biosynthesis of most
small molecules. On the other hand, the
survival of the biological realm depends on
Sequence-independent or “click” chemistry is applied for the preparation of a
series of novel and structurally similar π-conjugated oligomers. The new oligo-
mers are prepared using Wittig–Horner chemistry from bifunctional building
blocks that can be interconnected to one another at any desired sequence. The
bifunctional building blocks consist of aromatic skeletons with acetal protected
aldehyde groups on one side and a phosphonic acid diethyl ester group para to
the aldehyde functionality. The first step in the arylenevinylene formation is a
Wittig–Horner coupling of a functionalized aldehyde with the methyl phospho-
nate ester ylide of a bifunctional monomer. A stepwise protection–deprotection
process is applied for the preparation of structurally similar π-conjugated oligo-
phenylene vinylenes. New di-, tri-, penta-, and hepta-phenylenevinylenes are
prepared and characterized. Selected penta-arylenevinylenes are incorporated
as the semiconductor channel in organic field-effect transistors.
versatility, therefore nature utilizes “click”-type chemistry when
dealing with producing the molecular basis of diversity, poly-
nucleic acids and proteins.[9] In this case, nature’s machinery
produces highly complex materials out of a limited number of
bifunctional building blocks. The biosynthesis of these materials
proceeds in a way that is virtually independent of the sequence
that is being prepared, much like the way LEGO bricks are
assembled to one another to form various structures.[10]
Adopting such a strategy in the preparation of organic
electronic materials is expected to allow us to build complex
π-conjugated structures and fine tune these materials in ways
that have only before been seen in nature.[11]
1. Introduction
Over the past decade π-conjugated arylene and arylenevinylene
oligomers and polymers have generated considerable attention
because of their possible applications in organic electronics such
as light-emitting diodes,[1] organic lasers,[2] fi eld-effect transis-
tors (FET),[3] sensors,[4] and photovoltaic cells.[5] Despite the con-
siderable diversity available in the structures of these materials,
most of the research is limited to very simple sequences, mostly
homo-oligomers and homo-polymers. This stems mainly from
the increasing complexity of synthesis and purification as one
moves to more complex sequences of larger building blocks.[6]
As a result, it is widely accepted that synthesis is still a major
The application of sequence-independent chemistry to the
preparation of π-conjugated electronic materials has been previ-
ously reported by several groups. Alternating Heck and Horner–
Wadsworth–Emmons (HWE) reactions were applied by Yu et al.
for the stepwise construction of oligo (p-phenylene-vinylene)s
from two different bifunctional monomers.[12] Following a sim-
ilar approach, Tour et al. prepared a large library of phenylene
vinylene derivatives.[13] A similar stepwise Wittig–Horner protec-
tion–deprotection process was utilized by Nierengarten et al.[14]
wherein the synthesis of new dumbbell-shaped di-(pyrazolino-[60]
fullerene)–oligo-phenylene vinylenes was reported. Krebs et al.[15]
has prepared oligo-phenylene vinylenes for solar cell applications
using a similar approach; Suginome[16] used a protection-depro-
tection version of the Suzuki-Miyora coupling reaction to make
Dr. K. N. Shivananda, I. Cohen, Dr. E. Borzin,
Y. Gerchikov, Dr. M. Firstenberg, Prof. Y. Eichen
Schulich Faculty of Chemistry
Technion- Israel Institute of Technology
Technion City, 32000 Haifa, Israel
E-mail: chryoav@tx.technion.ac.il
Dr. O. Solomeshch, Prof. N. Tessler
Nanoelectronics Center
Department of Electrical Engineering
Technion- Israel Institute of Technology Technion City
32000 Haifa, Israel
DOI: 10.1002/adfm.201101897
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H+ in H2O/THF
Base/THF
Base/THF
Scheme 1. Schematic illustration of the sequence-independent Wittig–Horner process using bifunctional monomers.
oligoarenes; and Bäuele et al.[17] used combinatorial parallel syn-
thesis and constructed a library of 16 and 256 tetramers as can-
didates for a liquid crystal devices. A combinatorial synthesis on
solid support was used by Bäuerle et al.[18] and Anderson et al.[19]
to make a library of oligo-thiophenes and phenylene ethynylene
pentamers respectively, both showing promising optoelectronic
properties. Young et al. and Moore et al.[20] utilized a similar
method to prepare oligomers (1,3-phenylene ethynylene) on solid
support. Recently we reported on the use of solution synthesis
of oligo π-conjugated peptides as well as the Wittig–Horner syn-
thesis of oligo-phenylene vinylenes for making and optimizing
new materials for electrical and electrooptical applications.[21]
The general protection-deprotection Wittig–Horner process
using bifunctional monomers is outlined in Scheme 1. A first
group A, bearing an aldehyde moiety, is reacted with a bifunctional
π-conjugated monomer, A1, bearing a protected aldehyde on its one
side and a diethoxy phosphoryl methyl group in the 4 position.
After the first coupling step and formation of the new double
bond, the product is deprotected to release the aldehyde group of
the di-arylenevinylenes for a subsequent step. This sequence may
be repeated with the deprotected product of the preceding step as
the starting material for subsequent reaction, using any bifunc-
tional monomer, An, to construct an oligo-phenylenevinylene
of any desired sequence. Additionally, at any stage, the depro-
tected oligomer can be coupled with a bifunctional aromatic/
nonaromatic system, X, bearing two diethoxy phosphoryl methyl
groups, producing symmetrical oligo-phenylenevinylenes.
Here, we apply the Wittig–Horner sequence-independent
double-bond formation to the preparation of structurally controlled
functional oligomers using two new bifunctional thiophene mono-
mers. By fabricating field-effect transistors of these oligomers, we
demonstrate the potential inherent to this approach.
2. Results and Discussions
2.1. Materials
2.1.1. Mono Aldehydes
5-Hexylthiophene-2-carbaldehyde, 1; 3,3-dibutyl-3,4-dihydro-2H-
thieno [3,4-b][1,4] dioxepine-6-carbaldehyde, 2;[22] 7-(2-ethylheptyl)-
2,3-dihydrothieno [3,4-b][1,4]dioxine-5-carbaldehyde, 3;[23] 9-hexyl
-9H-carbazole -3-carbaldehyde, 4;[24] 4-diphenylamino-benzalde-
hyde, 5;[25] 4-(dibutylamino) benzaldehyde, 6; and 3,4,5-trimeth-
oxybenzaldehyde, 7, were used as the starting groups for the
unidirectional process.
N
6
N
4
O
O
O
N
O
O
O
S
S
O
H
O
H
H
O
H
H
O
S
O
H
O
H
O
O
1
2
3
5
7
iv
i
ii
iii
v
I-
10
11
12
13
14
8
Scheme 2. Preparation of bifunctional monomer 8: i) POCl3/DMF, –10 °C to room temperature, quantitative yield; ii) 2,2-dimethyl-propane-1,3-diol,
p-toluenesulfonic acid, refluxing toluene, quantitative yield; iii) dimethylimminium chloride, 1:1 dichloromethane:CH3CN, 80 °C to r.t, quantitative yield;
iv) CH3I, 1:1 CHCl3:Et2O, quantitative yield; and v) P(OCH2CH3)3, refluxing DMF, quantitative yield.
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dichloromethane to yield the N,N-dime-
thyl aminomethyl thiophene derivative 13,
which was subsequently treated with methyl
iodide to yield the ammonium salt 14. Reac-
tion between 14 and triethyl phosphite in
dry DMF afforded bifunctional monomer
8. The same approach was applied to syn-
thesis of bifunctional monomer 9 starting
from 3,4-dimethoxythiophene, 15, instead
of 3,3-dibutyl-2,4-dihydrothieno[3,4-b][1,4]
dioxepine, 16. Both bifunctional mono-
mers consist of a π-conjugated backbone
bearing two functional groups, a diethoxy
phosphoryl methyl group and an acetal pro-
tected aldehyde, rendering them suitable
for recurrent Wittig–Horner reactions.
i
ii
iii
iv
15
v
16
17
18
19
vi
I-
20
9
Scheme 3. Preparation of bifunctional monomer 9: i) 2,2-dibutylpropane-1,3-diol, p-tolue-
nesulfonic acid, refluxing toluene, 80% yield; ii) POCl3/DMF, –10 °C to r.t, quantitative yield;
iii) 2,2-dimethyl-propane-1,3-diol, p-toluenesulfonic acid, refluxing toluene, quantitative yield; iv)
dimethylimminium chloride, CH3CN, 80 °C to r.t, quantitative yield; v) CH3I, 1:1 CHCl3:Et2O,
quantitative yield; and vi) P(OCH2CH3)3, refluxing DMF, quantitative yield.
2.1.3. Di-arylenevinylenes
Nine di-arylenevinylenes were prepared by
coupling bifunctional monomers 8 and 9
with aldehydes 1–7. All nine coupling reac-
tions were performed using the same conditions: t-BuO−K+,
THF, 1 h at –10 °C, under inert atmosphere (Scheme 4 and 5).
The NMR spectra of the crude mixture suggests the formation
of E-21–E-29 (E isomers) proceeds to completion without the
formation of by-products. In a subsequent step, the di-aryle-
nevinylenes were deprotected to release their aldehyde moiety
and prepare them for the next Wittig–Horner reaction. All nine
protected aldehydes, E-21–E-29, were deprotected using the
same conditions in a mixture of tetrahydrofuran (THF, 10 mL)
2.1.2. Bifunctional Monomers
Bifunctional monomers 8 and 9 were prepared according to
Scheme 2 and 3 respectively. 3,4-ethylenedioxy thiophene
(EDOT), 10, was reacted with POCl3 and dimethlyformamide
(DMF) to obtain EDOT-aldehyde 11 by Vilsmeier reaction.[26] The
aldehyde group of 11 was then protected with 2,2-dimethyl-1,3-
propandiol under acidic conditions to afford the acetal-protected
EDOT, 12. 12 was reacted with dimethyl imminium chloride in
E-24 (E-33)
E-25 (E-34)
5
4
6
7
8
3
E-23 (E-32)
2
E-26 (E-35)
1
E-22 (E-31)
E-27 (E-36)
E-21 (E-30)
Scheme 4. The synthesis of di-arylenevinylenes E-21 to E-27 and E-30 to E-36 using the bifunctional monomer 7-(diethoxy phosphoryl methyl)-5-(5,5-
dimethyl-1,3-dioxan-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine, 8, and monoaldehydes 1–7. In brackets: the number of the respective deprotected di-
arylenevinylene aldehydes. Reaction conditions: Coupling: potassium t-butoxide (t-BuOK), THF, 1 h at –10 °C; Deprotection: THF, 1:10 HCl in H2O.
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5
1
E-29 (E-38)
9
E-28 (E-37)
Scheme 5. The synthesis of di-arylenevinylenes E-28 and E-29 and E37 and E-38 using the bifunctional 8-(diethoxy phosphoryl methyl)-6-(5,5-dimethyl-
1,3-dioxan-2-yl)-3,3-dimethyl-2,4-dihydrothieno[3,4-b][1,4] dioxepine monomer, 9, and monoaldehydes 1 and 5. In brackets: the number of the respec-
tive deprotected di-arylenevinylene aldehydes. Reaction conditions: Coupling: t-BuO−K+, THF, 1 h at –10 °C; Deprotection: THF, 1:10 HCl in H2O.
and 1:10 HCl in H2O (10 mL). The solution was stirred for 1 h
at room temperature, yielding the nine aldehydes, E-30–E-38,
respectively.
2.1.5. Penta-arylenevinylenes
Penta-arylenevinylenes were prepared by coupling depro-
tected di-arylenevinylene aldehydes E-30–E-38 with
bifunctional diethoxy phosphoryl methyl 1,4-bis(diethoxy
phosphoryl methyl)-2,5-bis(2-ethylhexoxy)benzene, 43[27]
(Scheme 7 and 8). All the reactions were performed by
using the following conditions: 43 (1 eq.) was dissolved in
dry THF under inert atmosphere at –10 °C, followed by the
addition of t-BuO−K+ (4 eq.) to the solution, turning its color
deep red. The respective deprotected aldehyde (2.1 eq.) was
added to the solution and the mixture was stirred for 30 min
at –10 °C. NMR spectra of the crude reaction mixtures of
E,E,E,E-44–E,E,E,E-52 shows quantitative conversion of the
respective starting materials.
2.1.4. Tri-arylenevinylenes
Protected tri-arylenevinylenes E,E-39 and E,E-40 were prepared
by coupling bifunctional monomer 8 with deprotected di-aryle-
nevinylene aldehydes, E-31 and E-36, under the same conditions
that were used for the preparation of the protected di-arylenevi-
nylene (Scheme 6). NMR spectra of the crude reaction mixtures
shows that the reactions proceed to completion. Deprotected tri-
arylenevinylenes E,E-41 and E,E-42 were obtained by using the
conditions used for the deprotection of the di-arylenevinylenes.
2.1.6. Hepta-arylenevinylenes
O
O
O
P
Hepta-arylenevinylenes were prepared by coupling deprotected
tri-arylenevinylene aldehydes E,E-41 and E,E-42 with bifunc-
tional diethoxy phosphoryl methyl-1,4-bis(diethoxy phosphoryl
methyl)-2,5-bis(2-ethylhexoxy)benzene, 43[27] (Scheme 9). The
reactions were performed using the same conditions used for
the preparation of the protected di- and tri-arylenevinylenes
O
O
P
O
O
O
43
8
E,E-39 (E,E-41)
E-31
8
E-36
E,E-40 (E,E-42)
Scheme 6. The synthesis of tri-arylenevinylenes E,E-39 and E,E-40 and E,E-41 and E,E-42 using the bifunctional 7-(diethoxy phosphoryl methyl)-5-(5,5-
dimethyl-1,3-dioxan-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine monomer 8 and di-arylenevinylene aldehydes E-31 and E-36. In brackets: the number of the
respective deprotected tri-arylenevinylene aldehydes. Reaction conditions: Coupling: t-BuOK, THF, 1 hr at –10 °C; Deprotection: THF, 1:10 HCl in H2O.
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43
43
43
43
2.1X E-30
E,E,E,E-44
2.1X E-31
2.1X E-32
2.1X E-33
E,E,E,E-45
E,E,E,E-46
E,E,E,E-47
43
2.1X E-34
E,E,E,E-48
Scheme 7. The synthesis of penta-arylenevinylenes E,E,E,E44 to E,E,E,E-48 using the bifunctional diethoxy phosphoryl methyl 1,4-bis(diethoxy phosphoryl
methyl)-2,5-bis(2-ethylhexoxy) benzene monomer, 43, and di-arylenevinylene aldehydes E-31 to E-34. Reaction conditions: t-BuOK, THF, 30 min at –10 °C.
with the exception that, similar to the case of the preparation
of penta-arylenevinylenes, the aldehyde was added to the reac-
tion mixture in a 2.1:1 excess with respect to the phosphonate.
Here, as well, NMR spectra of the crude reaction mixtures of
E,E,E,E,E,E-53–E,E,E,E,E,E-54 clearly show that the reactions
proceeded to completion.
different oligomers were deduced from the absorption edge in
their absorption spectra, and from their cyclic voltammograms.
Table 1 depicts the resulting highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO)
values and the optical properties of the different oligomers.
Figure 2 depicts the energy of the absorption band-edge as a
function of the inverse number of double bonds in the two
oligomer series E-22, E-31, E,E,E,E-45, E,E,E,E,E,E-53 and
E-27, E-36, E,E,E,E-50, E,E,E,E,E,E-54. Linear dependencies are
observed in both cases. It is clearly seen that regardless of the
increasing number of units in arylenevinylenes, the difference
between two similar oligomers is negligible.
2.2. Optical and Electrical Characterization
of the New Oligomers
The absorption and emission spectral data of protected di-
arylenevinylenes E-21–E-27 and deprotected di-arylenevinylenes
E-30–E-36, penta-arylenevinylenes E,E,E,E-44–E,E,E,E-52, and
hepta-arylenevinylenes E,E,E,E,E,E-53 and E,E,E,E,E,E-54 are
shown in Figure 1. The electronic and optical properties of the
different penta-arylenevinylenes and hepta-arylenevinylenes are
presented in Table 1, as well as the absorption and emission
maxima of E,E,E,E-44–E,E,E,E-54. The electronic levels of the
2.3. Organic Field-Effect Transistors
Organic field-effect transistors (OFETs)[28,29] were fabricated in
a bottom-contact configuration[30] by spin-coating an 80 nm
thick film of penta-arylenevinylenes atop an OFET structure
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43
43
43
2.1X E-35
2.1X E-36
E,E,E,E-49
E,E,E,E-50
2.1X E-37
E,E,E,E-51
43
2.1X E-38
E,E,E,E-52
Scheme 8. The synthesis of penta-arylenevinylenes E,E,E,E-49 to E,E,E,E-52 using the bifunctional diethoxy phosphoryl methyl 1,4-bis(diethoxy phos-
phoryl methyl)-2,5-bis(2-ethylhexoxy) benzene monomer, 43, and di-arylenevinylene aldehydes E-35 to E-38. Reaction conditions: t-BuOK, THF, 30 min
at –10 °C.
using a previously described procedure.[31] Penta-arylenevinylenes
E,E,E,E-44–E,E,E,E-52 function as the hole conducting channel
in the p-type FET, which is switched on at negative gate-source
voltages.
value for VT and Equation (1), the mobility in the linear regime
(VDS = –4 V, VGS = –11 V, IDS = 6.49 μA) for E,E,E,E-50 was
calculated to be about μ = 1 × 10−3 cm2 V−1 s−1 . Mobility values
for E,E,E,E-44 to E,E,E,E-49 were calculated in the same manner
and found to be 2 to 5 orders of magnitude lower, a difference
we largely attribute to film morphology properties.
Figure 3i depicts the transfer characteristics, i.e., the drain-
sourcecurrents(IDS ),ofanOFETcontainingpenta-arylenevinylene
E,E,E,E-50 as the semiconducting channel, as a function of gate-
source voltage (VG) for several drain-source voltages (VDS = from
–2 to –10 V). Figure 3ii depicts the IDS in the OFET as a function
of VDS for different VG values (VG = from 0 to –20 V). By exam-
ining Figure 3i,ii, one can see that the transistor characteristics
are not ideal, as there is the presence of some contact resistance
(slight diode effect in Figure 3ii). Nevertheless, as a material char-
acterization, one can still extract the charge (holes) mobility of
E,E,E,E-50 from the transfer curves, either in the linear or satura-
tion regime:
3. Conclusion
A stepwise, protection–deprotection, Wittig–Horner sequence
independent methodology was applied for the preparation of
a series of structurally similar π-conjugated di-, tri-, penta-, and
hepta-arylenevinylene oligomers using two new bifunctional mon-
omers, 8 and 9. The synthesis procedures consist of only two dif-
ferent high-yield and general steps of deprotection of the aldehyde
and subsequent double-bond formation. The new optical and elec-
trochemical properties of the new oligomers were characterized,
demonstrating the ability to fine-tune and optimize the optical
properties as well as the HOMO and LUMO band positions.
The potential embedded in using such a sequence-independent
approach is also demonstrated in applying selected penta-aryle-
nevinylenes as the semiconductor channel in OFETs. The results
clearly indicate that fine-tuning the structure of the oligomer one
can improve the transistor properties and hole mobility by sev-
eral orders of magnitude. Efforts are currently directed towards
a better understanding of the structure–hole-mobility correlation
⎧
I
DS
⎪
ꢀ
ꢁ
Linear regime
2
⎨
V
W
L
DS
C
(V −V )V −
DS
2
ins
GS
T
µ =
I
⎪
⎩
DS SAT
Saturation regime
W
L
2
(1)
C
[V −V ]
ins
g
T
Where μ is the mobility, W = 10 mm and L = 4 μm are, respec-
tively, the effective length and separation of the electrodes, and
capacity of the insulation layer Cins = 40 nF cm−2 . By extrapo-
lating the current to zero in the linear regime, we may deduce a
threshold voltage (VT) value of approximately –5.8 V. Using this
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43
43
2.1X E,E-41
E,E,E,E,E,E-53
E,E,E,E,E,E-54
2.1X E,E-42
Scheme 9. The synthesis of hepta-arylenevinylenes E,E,E,E,E,E-53 and E,E,E,E,E,E-54 using the bifunctional diethoxy phosphoryl methyl 1,4-bis(diethoxy
phosphoryl methyl)-2,5-bis(2-ethylhexoxy) benzene monomer, 43, and tri-arylenevinylene aldehydes E,E-41 to E,E-42. Reaction conditions: t-BuO−K+,
THF, 30 min at –10 °C.
CDCl3, δppm): 101.4, 97.3, 79.5, 66.6, 66.4, 24.7, 23.6; MS (TOF LD+)
with the aim of establishing a general approach to high tailoring
high-mobility organic semiconductors.
m/z: 257.46 [M+H]+; mp = 134 °C.
(2,3-Dihydro-5-(5,5-dimethyl-1,3-dioxan-2-yl)thieno[3,4-b][1,4]
dioxin-
7-yl)-N,N-dimethylmethanamine, 13: A solution of dimethylimminium
chloride (0.54 g, 5.85 mmol) in acetonitrile (10 mL) was added slowly,
at room temperature and under an inert atmosphere, to a solution of
12 (1 g, 3.9 mmol) in dichloromethane (20 mL). A white precipitate
formed, and then the solution was refluxed for 1 h and cooled to room
temperature. Et3N (10 mL) was added to the solution and the mixture
was stirred for an additional 30 min at room temperature. The product
was extracted from the reaction mixture with DCM, dried over anhydrous
Na2SO4, and the solvent was removed under reduced pressure. The
crude product was subsequently used as-is for the next step.
4. Experimental Section
Apparatus: NMR spectra were recorded on Bruker-AM-300 and
Bruker-AM-500 spectrometers. Mass spectra were recorded using
matrix-assisted laser desorption ionization (MALDI) micro MX
(MICROMASS) MS Technologies. Waters LCT Premier electrospray
ionization (ESI) flow 0.2 mL min−1 acetonitrile:H2O (50:50). Melting
points were recorded on a DSC (differential scanning calorimetry)
machine. Absorption and emission spectra were recorded on a UV-1601,
UV-visible spectrometer (Shimadzu) and a Fluorolog (Jobin Yvon)
luminescence spectrometer respectively. All optical measurements were
performed in analytical grade solvents. Cyclic voltammograms were
recorder by using a PGSTAT12 (Autolab) system. The three electrode
electrochemical cell included an Ag/AgNO3 (10−2 M in acetonitrile)
reference electrode, a Pt (diameter Φ = 3 mm) working electrode and a
Pt counter electrode.
Solution processing and all film/devices are made in a nitrogen
glove-box (LABMASTER 130, M. Braun, GmbH, Germany) integrated with
a thermal evaporator. The substrates of the FET devices were prepared
using photolithography. All current–voltage characteristics of FETs were
recorded using a 4155B semiconductor parameter analyzer (Agilent).
Materials: All starting materials and solvents described in the
manuscript were purchased from Sigma-Aldrich and Fluka. Solvents
and starting materials were used as received unless noted. Anhydrous
solvents were obtained using standard methods.
1H NMR (300 MHz, CDCl3, δppm): 6.51 (s, 1H), 5.61 (s, 1H), 4.17 (m,
4H), 3,72 (d, 2H), 3.64 (d, 2H), 2.25 (s, 6H), 1.12 (s, 3H), 0.70 (s, 3H);
13C NMR (75 MHz, CDCl3,
δppm): 101.4, 97.3, 79.5, 55.2, 66.6, 66.4, 42.3,
24.7, 23.6; MS (TOF LD+) m/z: 314.1 [M+H]+.
[7-(5,5-Dimethyl-[1,3]dioxan-2-yl)-2,3-dihydro-thieno[3,4-b][1,4]dioxin-
5-ylmethyl]-trimethyl-iodine-amine, 14: An excess of methyl iodide was
added to a solution of 13 (330 mg, 0.83 mmol) in a mixture of CHCl3 (10
mL) and Et2O (15 mL). After stirring the mixture for 12 h in the dark, the
precipitate was filtered and washed with Et2O, yielding 14 in the form of
white crystals (quant).
1H NMR (300 MHz, CDCl3, δppm): 6.51 (s, 1H), 5.61 (s, 1H), 4.17 (m,
4H), 3.57 (d, 2H), 3.45 (d, 2H), 2.25 (s, 9H), 1.12 (s, 3H), 0.70 (s, 3H);
13C NMR (75 MHz, CDCl3,
δppm): 101.4, 97.3, 79.5, 55.2, 66.6, 66.4, 42.3,
24.7, 23.6; MS (TOF LD+) m/z: 456.1 [M+H]+; mp > 250 °C.
Diethyl(2,3-dihydro-5-(5,5-dimethyl-1,3-dioxan-2-yl)thieno[3,4-b][1,4]
dioxin-7-yl)methylphosphonate, 8: A solution of 14 in dry DMF (15 mL)
and triethyl phosphite (10 mL) was stirred overnight at 150 °C under
an inert atmosphere, and then cooled to room temperature. An excess
of DMF and triethyl phosphite were removed under reduced pressure
and water was added to the mixture. The crude product was extracted
with Et2O and dried over anhydrous Na2SO4. The solvent was removed
under reduced pressure and the crude product was washed with hexane
in order to remove traces of triethyl phosphite. The product was purified
by column chromatography (alumina; 100% DCM) yielding 8 in the form
of a yellowish oil (quant).
5-hexylthiophene-2-carbaldehyde, 1,[26] 3,3-dibutyl-3,4-dihydro-2H-
thieno[3,4-b][1,4]di-oxepine-6-carbaldehyde, 2,[22] 7-(2-ethylheptyl)-2,3-
dihydrothieno [3,4-b][1,4]dioxine-5-carbaldehyde, 3,[26] 9-hexyl-9H-
carbazole-3-carbaldehyde,4,[26] 4-diphenylamino-benzal dehyde, 5,[26]
4-(dibutylamino)benzaldehyde, 6, and 3,4,5-trimethoxybenzaldehyde,
7, were used as the first monomers for the unidirectional process.
2,3-Dihydro-thieno[3,4-b][1,4]dioxine-5-carbaldehyde,
11[26]
and
3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4] dioxepine, 16,[32] were
prepared according to a reported procedures.
5-(5,5-Dimethyl-[1,3]dioxin-2-yl)-2,3-dihydro-thieno[3,4-b][1,4]dioxine,
12: A solution of 2,2-dimethyl-1,3-propandiol (1.2 g, 11 mmol), 11 (1 g,
5.8 mmol) and a catalytic amount of p-toluenesulfonic acid in toluene
(50 mL) was refluxed for 1 h at 110 °C. The reaction mixture was then
cooled to room temperature, washed with brine, and extracted with
dichloromethane. The organic phase was dried over anhydrous Na2SO4
and the solvent was removed under reduced pressure. The crude product
was purified by column chromatography (alumina; 30% dichloromethane
in hexane) yielding 12 in the form of a white solid (quant).
1H NMR (300 MHz, CDCl3, δppm): 5.58 (s, 1H), 4.13 (s, 4H), 4.03 (m,
4H), 3.64 (d, 2H), 3.51 (d, 2H), 3.15 (s, 1H), 3.08 (s, 1H), 1.23 (t, 6H),
1.19 (s, 3H), 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 138.4, 138.1,
112.1, 106.8, 95.1, 76.7, 64.6, 62.3, 29.8, 24.7, 21.2, 16.1; MS (TOF LD+)
m/z: 407.2 [M+H]+.
3,3-Dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine-6-carbaldehyde,
17: POCl3 (1.76 mL, 18 mmol) was added dropwise to the stirred
suspension of 16, (2 mL, 18 mmol) in DMF (15 mL) at –10 °C under
nitrogen atmosphere. The mixture was stirred for an additional 2 h at
room temperature, then poured into ice and neutralized. The product
was extracted with dichloromethane, dried over anhydrous Na2SO4 and
1H NMR (300 MHz, CDCl3, δppm): 6.55 (s, 1H), 5.60 (s, 1H), 4.17
(m, 4H), 3.57 (s, 4H), 1.12 (s, 3H), 0.70 (s, 3H); 13C NMR (125 MHz,
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b
E-21
E-22
E-24
E-25
E-26
E-27
E-21
E-22
E-24
E-25
E-26
E-27
a
1.0
0.8
0.6
0.4
0.2
0.0
1.0
0.8
0.6
0.4
0.2
0.0
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
Energy (eV)
Energy (eV)
E,E-30
E,E-31
E,E-33
E,E-34
E,E-35
E,E-36
c
E,E-30
E,E-31
E,E-33
E,E-34
E,E-35
E,E-36
d
1.0
0.8
0.6
0.4
0.2
0.0
1.0
0.8
0.6
0.4
0.2
0.0
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
Energy (eV)
Energy (eV)
E,E,E,E-44
E,E,E,E-45
E,E,E,E-46
E,E,E,E-47
E,E,E,E-48
E,E,E,E-49
E,E,E,E-50
E,E,E,E-51
E,E,E,E-52
E,E,E,E-53
E,E,E,E-54
E,E,E,E-44
E,E,E,E-45
E,E,E,E-46
E,E,E,E-47
E,E,E,E-48
E,E,E,E-49
E,E,E,E-50
E,E,E,E-51
E,E,E,E-52
E,E,E,E,E,E-53
E,E,E,E,E,E-54
f
e
1.0
1.0
0.8
0.6
0.4
0.2
0.0
0.8
0.6
0.4
0.2
0.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
Energy (eV)
Energy (eV)
Figure 1. a) Normalized absorption spectra of protected di-arylenevinylene E-21–E-27. b) Normalized emission spectra of protected di-arylenevi-
nylene E-21–E-27. c) Normalized absorption spectra of deprotected diarylenevinylene E-30–E-36. d) Normalized emission spectrum of deprotected
diarylenevinylene E-30–E-36. e) Normalized absorption spectra of penta-arylenevinylene E,E,E,E-44–E,E,E,E-52 and hepta-arylenevinylene E,E,E,E,E,E-
53–E,E,E,E,E,E-54. f) Normalized emission spectra of penta-arylenevinylene E,E,E,E-44–E,E,E,E-52 and hepta-arylenevinylene E,E,E,E,E,E-53–
E,E,E,E,E,E-54.
the solvent was removed under reduced pressure, obtaining 17 in the
form of brown oil (quant).
chromatography (alumina; 30% dichloromethane in hexane), yielding
18 as brown oil (quant.).
1H NMR (300 MHz, CDCl3, δppm): 9.84 (s, 1H), 6.01(s, 1H), 3.85(s,
1H NMR (300 MHz, CDCl3, δppm): 6.15 (s, 1H), 5.60 (s, 1H), 3.88 (s,
4H), 3.57 (d, 2H), 3.45 (d, 2H), 1.12 (s, 3H), 1.29(m, 12H), 0. 19 (t, 6H),
4H), 1.29(m, 12H), 0.19 (t, 6H); 13C NMR (75 MHz, CDCl3,
δppm) 180.0,
151.27, 140.98, 115.07, 105.21, 77.32, 34.13, 31.23, 26.7, 23.41, 14.31;
0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 149.97, 140.98, 115.07,
MS (TOF LD+) m/z: 297 [M+H]+.
105.21, 99.01, 77.32, 34.13, 31.23, 30.09, 26.7, 23.41, 14.31; MS (TOF
3,3-Dibutyl-6-(5,5-dimethyl-1,3-dioxan-2-yl)-3,4-dihydro-2H-
thieno[3,4-b][1,4] dioxpine, 18: 2,2-methyl-1,3-propanediol (1.2 g,
11 mmol) and catalytic quantity of p-toluenesulfonic acid were added
to a solution of 17 (2.37 g, 8 mmol) in toluene (50 mL). The reaction
mixture was heated to reflux for 1 day then the solvent was removed
under reduced pressure. The crude product was purified using column
LD+) m/z: 383.22 [M+H]+.
1-(3,3-Dibutyl-8-(5,5-dimethyl-1,3-dioxan-2-yl)-3,4-dihydro-2H-
thieno[3,4-b][1,4] dioxepin-6-yl)-N,N-dimethylmethanamine, 19: A solution
of dimethylimminium chloride (0.36 g, 3.9 mmol) in acetonitrile (10 mL)
was added slowly, to a solution of 18 (1 g, 2.6 mmol) in dichloromethane
(20 mL) at room temperature and under an inert atmosphere. A white
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T a b le 1 . Electronic and optical properties of the different penta-arylenevinylenes and hepta-arylenevinylenes.
Material
HOMO Theoreticala)
[eV]
LUMO Theoreticala)
[eV]
HOMO
[eV]
LUMO
[eV]
Absorption
(edge) [eV]
Absorption
(max) [eV]
Emission
(max) [eV]
E,E,E,E-44
E,E,E,E-45
E,E,E,E-46
E,E,E,E-47
E,E,E,E-48
E,E,E,E-49
E,E,E,E-50
E,E,E,E-51
E,E,E,E-52
E,E,E,E,E,E-53
E,E,E,E,E,E-54
4.16
4.27
4.35
4.24
4.30
3.97
4.30
4.35
4.27
4.13
4.10
2.01
2.12
2.09
2.04
2.09
1.80
2.15
2.18
2.07
2.28
2.23
4.45
4.58
4.19
4.48
4.11
4.33
4.53
4.59
5.17
4.49
5.01
2.19
2.30
3.15
2.10
1.91
3.07
2.31
2.35
3.1
2.14
2.16
2.12
2.15
2.18
2.22
2.23
2.21
2.21
2.00
2.00
2.42
2.10
2.19
2.07
2.20
2.14
2.25
2.20
2.25
2.19
2.02
1.99
2.47
2.42
2.45
2.50
2.54
2.52
2.53
2.57
2.89
3.07
2.25
2.26
a)Density functional theory (DFT) calculation B3LYP 6-31G.
precipitate formed, and then the solution was refluxed for an additional
1 h and cooled to room temperature. Et3N (10 mL) were added to the
solution and stirred for an additional 30 min at room temperature. The
product was extracted from the reaction mixture with DCM, dried over
Na2SO4, and the solvent was removed under reduced pressure. The
crude product was subsequently used as-is for the next step.
Diethyl(3,3-dibutyl-8-(5,5-dimethyl-1,3-dioxan-2-yl)-3,4-dihydro-2H-
thieno[3,4-b][1,4] dioxepin-6-yl) methylphosphonate, 9: A solution of 20
in triethyl phosphite (10 mL) was stirred overnight at 150 °C under an
inert atmosphere, and then cooled to room temperature. An excess of
DMF and triethyl phosphite were removed under reduced pressure and
water was added to the mixture. The crude product was extracted with
Et2O and dried over anhydrous Na2SO4. The solvent was removed under
reduced pressure and the crude product was washed with hexane in
order to remove traces of triethyl phosphite. The product was purified by
column chromatography (alumina; 100% DCM) yielding 9 in the form of
a yellowish oil (quant).
1H NMR (300 MHz, CDCl3, δppm): 6.15 (s, 1H), 3.88 (s, 4H), 3.57 (d,
2H), 3.45 (d, 2H), 2.25 (s, 6H), 1.12 (s, 3H), 1.29(m, 12H), 0. 19 (t, 6H),
0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 149.97, 140.98, 115.07,
105.21, 99.01, 77.32, 51.98, 44.59, 34.13, 31.23, 30.09, 26.7, 23.41, 14.31;
MS (TOF LD+) m/z: 440.27 [M+H]+.
1-(3,3-Dibutyl-8-(5,5-dimethyl-1,3-dioxan-2-yl)-3,4-dihydro-2H-
thieno[3,4-b][1,4]dioxepin-6-yl)-N,N,N-trimethyl-methanamineiodiode, 20:
Excess of methyl iodide was added to a solution of 19 (330 mg, 0.75
mmol) in a mixture CHCl3 (10 mL) and Et2O (15 mL). After stirring the
mixture for 12 h in the dark, the precipitate was filtered and washed with
Et2O, yielding 20 in the form of white crystals (quant).
1H NMR (300 MHz, CDCl3, δppm): 5.58 (s, 1H), 4.13 (s, 4H), 4.03
(m, 4H), 3.64 (d, 2H), 3.51 (d, 2H), 3.15 (s, 1H), 3.08 (s, 1H), 1.23 (t,
6H), 1.19 (s, 3H), 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 149.97,
140.98, 115.07, 105.21,99.01, 77.32, 60.01, 34.13, 31.23,30.09, 26.7,
23.41, 16.98, 14.39, 14.08; MS (TOF LD+) m/z: 533.25 [M+H]+.
General Procedure for Preparation of Acetal Protected Di- and Tri-
arylenevinylenes: All nine acetal protected di-arylenevinylenes as well as
the two acetal protected tri-arylenevinylenes were prepared by coupling
between the respective aldehydes and acetal protected bifunctional
monomers 8 and 9. All the reactions were performed using the same
conditions: 1.1 eq. of the bifunctional monomer were dissolved in dry
THF (15 mL) in a two necked flask and the reaction mixture cooled to
–10 °C, under nitrogen atmosphere. 2 eq. of t-BuOK were then added
to the solution turning its color into deep red. 1 eq. of a solution of
the respective aldehyde in dry THF was added at –10 °C to the deep
red solution and the resulting mixture was stirred at room temperature
for 1 h. The solvent was removed under reduced pressure and water
was added to the mixture. The product was extracted with DCM and
the organic layer was dried over anhydrous Na2SO4. The solvent
was removed under reduced pressure and the crude was purified by
column chromatography (alumina; 30% DCM in hexane) E-21–E-29 and
E,E-39–E,E-40.
1H NMR (300 MHz, CDCl3, δppm): 6.15 (s, 1H), 3.88 (s, 4H), 3.57 (d,
2H), 3.45 (d, 2H), 2.25 (s, 9H), 1.12 (s, 3H), 1.29(m, 12H), 0.19 (t, 6H),
0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 149.97, 140.98, 115.07,
105.21, 99.01, 77.32, 55.98, 51.59, 34.13, 31.23, 30.09, 26.7, 23.41, 14.31;
MS (TOF LD+) m/z: 582.71 [M+H]+.
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
The NMR spectra of the reaction mixtures showed that materials
E-21–E-29 and E,E-39–E,E-40 (all in >90% of the E isomer) were obtained
as the sole products and the reactions proceeded to completion.
5-(2-Ethylhexyl)-2,3-dihydro-7-((E)-2-(2,3-dihydro-5-(5,5-dimethyl-1,3-
dioxan-2-yl)thieno[3,4-b][1,4]dioxin-7-yl)vinyl)thieno[3,4-b][1,4]dioxine, E-21:
Yield: 95%. 1H NMR (300 MHz, CDCl3, δppm): 6.89 (d, 1H), 6.74 (d, 1H),
5.64 (s, 1H), 4.19 (s, 8H), 3.69 (d, 2H), 3.60 (d, 2H), 2.54 (d, 2H), 1.53 (s,
1H), 1.25 (q, 11H), 0.85 (t, 6H). 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
0.00 0.03 0.06 0.09 0.12 0.15 0.18 0.21
1/NDB
δ
ppm): 138.98, 138.70, 138.27, 137.44, 117.50, 116.54, 115.82, 114.08
Figure 2. Energy of the absorption band edge as a function of 1/NDB (1/
(number of double bonds)) of E-27, E-36, E,E,E,E-50, and E,E,E,E,E,E-54
113.15, 110.73, 95.26, 64.81, 53.35, 40.44, 32.30, 31.82, 30.03, 29.74, 29.59,
29.26, 28.68, 25.51, 22.94, 22.74, 22.59, 21.69, 14.07, 14.04, 10.72; HRMS
(ESI) m/z: [M+H]+ calcd for C28H38O6S2, 535.2109; found, 535.2178.
…
᭿
(•,−) and E-22, E-31, E,E,E,E-45, and E,E,E,E,E,E-53 ( , ).
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-6.E-06
-1.E-05
-1.E-05
-8.E-06
-6.E-06
-4.E-06
-2.E-06
0.E+00
ii
i
-5.E-06
-4.E-06
-3.E-06
-2.E-06
-1.E-06
0.E+00
(e)
(e)
(d)
(d)
(c)
(c)
(b)
(a)
(b)
(a)
0
-5
-10 -15 -20 -25 -30
VGS [V]
0
-5 -10 -15 -20 -25 -30
VDS[V]
Figure 3. Electronic characterization of penta-arylenevinylene (E,E,E,E-50). i) Drain-source current as a function of the gate-source voltage (VGS), for
various values of the drain voltage (VDS). a) –2 V; b) –4 V; c) –6 V; d) –8 V; e) –10 V. ii) Drain-source current as a function of VDS, for various values of
VGS. a) 0 V; b) –5 V; c) –10 V; d) –15 V; e) –20 V.
3,3-Dibutyl-3,4-dihydro-6-((E)-2-(2,3-dihydro-5-(5,5-dimethyl-1,3-
5-((E)-2-(5-Hexylthiophen-2-yl)vinyl)-2,3-dihydro-7-(5,5-dimethyl-1,3-
dioxan-2-yl)thieno[3,4-b][1,4]dioxine, E-27: Yield: 90%. 1H NMR (300
MHz, CDCl3, δppm): 6.97 (d, 1H), 6.83 (d, 1H), 6.78 (d, 1H), 6.63 (d,
1H), 5.69 (s, 1H), 4.23 (s, 4H), 3.73 (d, 2H), 3.64 (d,2H), 2.77 (t, 2H),
1.68 (t, 2H), 1.39 (m 6H), 1.29 (s, 3H), 0.90 (t, 3H), 0.70 (s, 3H); 13C
dioxan-2-yl)thieno[3,4-b][1,4]dioxin-7-yl)vinyl)-2H-thieno[3,4-b][1,4]
1
dioxepine, E-22: Yield: 94%. H NMR (300 MHz, CDCl3, δppm): 6.97 (d,
1H), 6.83 (d, 1H), 6.78 (d, 1H), 6.63 (d, 1H), 5.69 (s, 1H), 4.23 (s, 4H),
3.73 (d, 2H), 3.64 (d, 2H), 2.77 (t, 2H), 1.68 (t, 2H), 1.39 (m, 6H), 1.29
(s, 3H), 0.90 (t, 3H), 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δ
ppm):
NMR (75 MHz, CDCl3, δppm): 145,05, 140.42, 138.99, 137.99, 125.61,
145.05, 140.42, 138.99, 137.99, 125.61, 124.50, 120.39, 116.66, 116.35,
111.43, 95.21, 64.79, 31.49, 31.40, 30.01, 3.00, 28.65, 22.76, 22.49,
21.70, 14.03; HRMS (ESI) m/z: [M+H]+ calcd for C24H32O4S2, 549.2266;
found, 549.2798.
124.50, 120.39, 116.66, 116.35, 111.43, 95.21, 64.79, 31.49, 31.40, 30.01,
3.00, 28.65, 22.76, 22.49, 21.70, 14.03; HRMS (ESI) m/z: [M+H]+ calcd
for C24H32O4S2, 449.1742; found, 449.1798.
3,3-Dibutyl-6-((E)-2-(5-hexylthiophen-2-yl)vinyl)-3,4-dihydro-8-(5,5-
dimethyl-1,3-dioxan-2-yl)-2H-thieno[3,4-b][1,4]dioxepine, E-28: Yield: 90%.
1H NMR (300 MHz, CDCl3, δppm): 7.57 (d, 2H), 7.31 (t, 4H), 7.17 (s,
1H), 7.10 (s, 1H), 7.06 (m, 6H), 6.95 (d, 2H), 4.33 (d, 2H), 4.32 (d, 2H),
3.60 (s, 4H), 1.21(m, 12H), 1.15 (s, 3H), 0.72 (s, 9H); 13C NMR (75
5-(3,4,5-Trimethoxystyryl)-2,3-dihydro-7-(5,5-dimethyl-1,3-dioxan-2-yl)
thieno[3,4-b] [1,4]dioxine, E-23: Yield: 90%. 1H NMR (300 MHz, CDCl3,
δ
ppm): 7.32 (d, 2H), 6.95 (d, 1H), 6.60 (d, 1H), 6.58 (d, 2H), 5.70 (s,
1H), 4.20 (s, 4H), 3.72 (d, 2H), 3.64 (d, 2H), 3.27 (t, 4H), 1.57 (q,
4H), 1.31 (t, 3H), 0.97 (t, 6H), 0.77 (s, 3H); 13C NMR (75 MHz, CDCl3,
MHz, CDCl3, δppm): 149.3, 149.1, 141.2, 139.2, 137.8, 133.7, 133.4, 131.1,
δ
ppm): 147.52, 139.09, 137.06, 127.39, 127.02, 124.35, 118.08, 122.94,
129.7, 129.1, 128.4, 128.3, 128.2, 126.3, 125.4, 124.8, 119.2, 113.8, 97.2,
79.5, 77.79,.31.49, 31.40, 30.01, 28.65, 24.7, 23.6, 22.76, 22.49, 21.70,
14.03; HRMS (ESI) m/z: [M+H]+ calcd for C41H49O4S2, 652.3382, found,
652.3289.
111.57, 110.15, 95.36, 64.88, 64.64, 50.68, 30.05, 29.42, 22.83, 21.73,
20.28 14.00; HRMS (ESI) m/z: [M+H]+ calcd for C30H43NO4S, 486.2599;
found, 486.3019.
4-((E)-2-(2,3-Dihydro-5-(5,5-dimethyl-1,3-dioxan-2-yl)thieno[3,4-b][1,4]
dioxin-7-yl) inyl)-N,N-diphenylbenzenamine, E-24: Yield: 92%. 1H NMR
(300 MHz, CDCl3, δppm): 7.57 (d, 2H), 7.31 (t, 4H), 7.17 (s, 1H), 7.10
(s, 1H), 7.06 (m, 6H), 6.95 (d, 2H), 4.33 (d, 2H), 4.32 (d, 2H), 3.60 (s,
4H), 1.15 (s, 3H), 0.72 (s, 3H), 13C NMR (75 MHz, CDCl3, <δppm): 149.3,
149.1, 141.2, 139.2, 137.8, 133.7, 133.4, 131.1, 129.7, 129.1, 128.4, 128.3,
128.2, 126.3, 125.4, 124.8, 119.2, 113.8, 97.2, 79.5, 66.5, 32.0, 24.7, 23.6;
MS (TOF LD+) m/z: 526.19 [M+H]+.
N-(4-((E)-2-(3,3-Dibutyl-3,4-dihydro-6-(5,5-dimethyl-1,3-dioxan-2-yl)-
2H-thieno[3,4-b][1,4]dioxepin-8-yl)vinyl)phenyl)-N-phenylbenzenamine,
E-29: Yield 92%. 1H NMR (300 MHz, CDCl3, δppm): 6.98 (d, 1H), 6.93
(d, 1H), 6.78 (d, 1H), 6.63 (d, 1H), 5.69 (s, 1H), 4.23 (s, 4H), 3.73 (d,
2H), 3.64 (d,2H), 2.77 (t, 2H), 1.68 (t, 2H), 1.39 (m 6H), 1.29 (s, 7H),
0.90 (t, 11H), 0.70 (s, 9H); 13C NMR (75 MHz, CDCl3,
δppm): 149,05,
145.42, 139.98, 138.09, 126.51, 124.98, 121.39, 117.36, 116.75, 111.43,
95.21, 77.79, 77.4, 31.49, 31.40, 30.01, 3.00, 28.65, 22.76, 22.49, 21.70,
14.03; HRMS (ESI) m/z: [M+H]+ calcd for C33H50O4S2, 575.3150; found,
575.3298.
9-Hexyl-3-((E)-2-(2,3-dihydro-5-(5,5-dimethyl-1,3-dioxan-2-yl)
thieno[3,4-b][1,4]dioxin-7-yl)vinyl)-9H-carbazole, E-25: Yield: 95%. 1H
NMR (300 MHz, CDCl3, δppm): 8.13 (d, 2H), 7.57 (d, 1H), 7.54 (m, 4H),
7.12 (d, 1H), 7.11 (d, 1H), 5.69 (s, 1H), 4.26 (s, 4H), 4.20 (d, 2H), 3,72
(d, 2H), 3.64 (d, 2H), 1.83 (m, 2H), 1.42 (q, 8H), 1.29 (s, 3H), 0.85 (t,
6-[(E)-2-[5-[(E)-2-[5-(5,5-Dimethyl-1,3-dioxan-2-yl)-2,3-
dihydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]-2,3-dihydrothieno[3,4-b][1,4]
dioxin-7-yl]vinyl]-3,3-dibutyl-2,4-dihydrothieno [3,4-b][1,4]dioxepine, E,E-
39: Yield: 90%. 1H NMR (300 MHz, CDCl3, δppm): 6.97(d, 2H), 6.63
(s, 2H), 6.01(s, 1H), 5.63 (s, 1H), 4.21 (t, 18H), 3.87 (s, 2H), 3.81 (s,
2H), 3.69 (d, 2H), 3.61 (d,2H), 1.33 (t, 12H), 1.25 (t, 3H), 0.93 (t, 6H).
3H). 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 140.70, 139.97,
139.04, 137.58, 128.35, 127.71, 124.16, 123.05, 122.74, 118.82, 118.13,
117.68, 115.17, 110.86, 108.72, 95.33, 64.81, 53.35, 44.44, 31.50, 31.47,
30.08, 26.85, 22.57, 22.45, 22.30; HRMS (ESI) m/z: [M+H]+ calcd for
C33H41NO4S, 532.2443; found, 532.2524.
0.75 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 147.98, 146.82, 138.95
137.82, 128.01, 120.99, 120.01, 114.02, 114.12, 104.11, 65.78, 64.43,
44.23, 43.89, 32.43, 31.98, 29.76, 29.01, 24.78, 23.39, 22.58, 21.71,
14.03, 13.93; HRMS (ESI) m/z: [M+H]+ calcd for C37H46O8S3, 715.2354;
found, 715.9531.
N,N-Dibutyl-4-((E)-2-(2,3-dihydro-5-(5,5-dimethyl-1,3-dioxan-2-yl)
thieno[3,4-b][1,4]dioxin-7-yl)vinyl)benzenamine, E-26: Yield: 90%. 1H NMR
(300 MHz, CDCl3, δppm): 7.02(d, 1H), 6.78 (d, 1H), 6.63 (d, 2H), 5.67(s,
1H), 4.24 (s, 4H), 3.85 (d, 9H), 3.70 (d, 2H), 3.62 (d, 2H), 1.26 (s, 3H).
5-(5,5-Dimethyl-1,3-dioxan-2-yl)-7-[(E)-2-[7-[(E)-2-(5-hexyl-2-thienyl)
vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl]vinyl]-2,3-dihydrothieno[3,4-b]
[1,4]dioxine, E,E-40: Yield: 90%. 1H NMR (300 MHz, CDCl3, δppm): 7.01
(d, 1H), 6.91 (d, 1H), 6.78 (d, 2H), 6.63 (d, 2H), 5.69 (s, 1H), 4.23 (t,
8H), 3.73 (d, 2H), 3.64 (d, 2H), 2.77 (t, 2H), 1.68 (t, 2H), 1.39 (m, 6H),
0.72 (s, 3H); 13C NMR (75 MHz, CDCl3,
δppm): 153.19, 138.97, 138.27,
137.48, 132.93, 126.33, 117.28, 116.57, 111.91, 102.98, 95.09, 64.74,
64.67, 55.89, 29.99 22.70, 21.63; HRMS (ESI) m/z: [M+H]+ calcd for
C23H28O7S, 449.1555; found, 449.1650.
©
1498 wileyonlinelibrary.com
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Funct. Mater. 2012, 22, 1489–1501

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1.29 (s, 3H), 0.90 (t, 3H), 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
δ
ppm):
13C NMR (75 MHz, CDCl3,
δ
ppm): 179.11, 148.12, 147.38, 139.39 138.15,
146,91, 141.39, 139.86, 138.09, 126.76, 124.50, 120.39, 116.66, 116.35,
111.43, 95.21, 64.79, 31.49, 31.40, 30.01, 3.00, 28.65, 22.76, 22.49, 21.70,
14.03; HRMS (ESI) m/z: [M+H]+ calcd for C32H38O6S3, 615.1830; found,
615.8456.
128,15, 127.95, 125.25, 124.94, 115.38, 114.91, 65.26, 64.44, 31.44,
31.30, 30.37, 28.62, 22.45, 13.98; HRMS (ESI) m/z: [M+H]+ calcd for
C19H22O3S2, 363.1010; found, 363.1074.
8-(4-(Diphenylamino)styryl)-3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]
General Procedure for Deprotection of Acetal Protected Di- and Tri-
arylenevinylenes: Acetal protected di- and tri-arylenevinylenes (E-21–E-29
and E,E-39–E,E-40) were dissolved in a mixture of THF (10 mL) and
1:1 37% aqueous HCl and water (10 mL) and stirred for 1 h at room
temperature. The solution was then neutralized and the product extracted
with DCM. The organic phase was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The products E-30–E-38 and
E,E-41–E,E-42 were purified using column chromatography (silica, 50%
DCM in hexane). The NMR spectra of the reaction mixtures showed that
materials E-30–E-38 and E,E-41–E,E-42 (all in >95% of the E isomer)
were obtained as the sole products and the reactions proceeded to
completion.
dioxepine-6-carbaldehyde, E-37: Yield: 95%. 1H NMR (300 MHz, CDCl3,
δ
ppm): 9.91(s, 1H), 7.57 (d, 2H), 7.31 (t, 4H), 7.17 (s, 1H), 7.10 (s, 1H),
7.06 (m, 6H), 6.95 (d, 2H), 4.33 (d, 2H), 4.32 (d, 2H), 1.21(m, 12H),1.15
(s, 3H), 0.72 (s, 9H); 13C NMR (75 MHz, CDCl3,
ppm): 179.01, 148.93,
δ
147.01, 142.02, 138.82, 136.08, 132.97, 132.04, 130.01, 128.17, 127.1,
126.4, 126.03, 125.2, 125.03, 124.94, 124.08, 118.2, 113.8, 97.2, 79.5,
77.79,.31.49, 31.40, 30.01, 28.65, 24.7, 23.6, 22.49, 21.70, 14.03; HRMS
(ESI) m/z: [M+H]+ calcd for C36H39NO3S2, 566.2650; found, 566.2689.
3,3-Dibutyl-8-((E)-2-(5-hexylthiophen-2-yl)vinyl)-3,4-dihydro-2H-
thieno[3,4-b][1,4]dioxepine-6-carbaldehydecarbaldehyde, E-38: Yield: 95%.
1H NMR (300 MHz, CDCl3, δppm): 9.86 (s, 1H), 6.98 (d, 1H), 6.93 (d,
1H), 6.78 (d, 1H), 6.63 (d, 1H), 5.69 (s, 1H), 4.23 (s, 4H), 2.77 (t, 2H),
1.68 (t, 2H), 1.39 (m, 6H), 1.29 (s, 7H), 0.90 (t, 11H), 0.70 (s, 9H); 13C
7-((E)-2-(5-(2-Ethylhexyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)-
2,3-di hydrothieno[3,4-b][1,4]dioxine-5-carbaldehyde, E-30: Yield: 95%. 1H
NMR (300 MHz, CDCl3, δppm): 9.84 (s, 1H), 7.15 (d, 1H), 6.73 (d, 1H),
4.32 (s, 8H), 2.55 (d, 2H), 1.53 (s, 1H), 1.25 (q, 8H), 0.85 (m, 6H); 13C
NMR (75 MHz, CDCl3, δppm): 178.98, 148,05, 143.92, 140.18, 139.10,
129.95, 127.38, 122.39, 118.96, 117.63, 111.93, 96.21, 77.4, 31.09, 30.01,
3.00, 28.65, 24.96, 23.79, 21.89, 14.13; HRMS (ESI) m/z: [M+H]+ calcd
for C28H40O3S2, 489.2418; found, 489.2349.
NMR (75 MHz, CDCl3, δppm): 178.93, 140.47, 138.46, 137.58, 129.39,
121.56, 118.87, 114.40, 113.09, 112.59, 65.27, 64.41, 40.42, 32.31, 29.91,
28.66, 25.53, 22.91, 14.04, 10.70; HRMS (ESI) m/z: [M+H]+ calcd for
C23H28O5S2, 449.1378; found, 449.1456.
7-[(E)-2-[7-[(E)-2-(3,3-Dibutyl-2,4-dihydrothieno[3,4-b][1,4]dioxepin-6-yl)
vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl]vinyl]-2,3-dihydrothieno[3,4-b]
[1,4]dioxine-5-carbaldehyde, E,E-41: Yield: 95%. 1H NMR (300 MHz, CDCl3,
7-((E)-2-(3,3-Dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)
vinyl)-2,3-dihydrothieno3,4-b][1,4]dioxine-5-carbaldehyde, E-31: Yield: 95%.
1H NMR (300 MHz, CDCl3, δppm): 9.78 (s, 1H), 7.17 (d, 1H), 6.76 (d,
1H), 6.31 (s, 1H), 5.58 (s, 1H), 4.13 (s, 4H), 3.88 (s, 2H), 3.79 (s, 2H),
δ
ppm): 9.81 (s, 1H), 7.19 (d, 1H), 6.80 (d, 1H), 6.39 (s, 1H), 5.58 (s, 1H),
4.13 (s, 8H), 3.88 (s, 2H), 3.79 (s, 2H), 1.33 (t, 12H), 0.88 (m, 6H); 13C
NMR (75 MHz, CDCl3, ppm): 179.31, 148.42, 147.18, 139.59 138.12,
δ
128.42, 121.59, 120.43, 114.81, 114.07, 104.02, 65.27, 64.43, 43.53, 43.51,
31.80, 31.45, 29.58, 29.54, 29.24, 24.88, 23.40, 22.58, 14.03, 13.93; HRMS
(ESI) m/z: [M+H]+ calcd for C32H36O7S3, 629.1623; found, 628.8243.
7-[(E)-2-[7-[(E)-2-(5-Hexyl-2-thienyl)vinyl]-2,3-dihydrothieno[3,4-b][1,4]
dioxin-5-yl]vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carbaldehyde, E,E-
42: Yield: 95%. 1H NMR (300 MHz, CDCl3, δppm): 9.79 (s, 1H), 7.43
(d, 1H), 6.81 (d, 1H), 6.73 (s, 1H), 6.64 (s, 1H), 4.13 (s, 8H), 2.71 (t,
2H), 1.65 (t, 2H), 1.29 (m, 6H), 0.70 (s, 3H); 13C NMR (75 MHz, CDCl3,
1.33 (t, 12H), 0.88 (m, 6H);13C NMR (75 MHz, CDCl3,
δppm): 179.31,
148.42, 147.18, 139.59 138.12, 128.42, 121.59, 120.43, 114.81, 114.07,
104.02, 65.27, 64.43, 43.53, 43.51, 31.80, 31.45, 29.58, 29.54, 29.24,
24.88, 23.40, 22.58, 14.03, 13.93; HRMS (ESI) m/z: [M+H]+ calcd for
C24H30O5S2, 463.1534; found, 463.1636.
7-(4-(Dibutylamino)styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-
carbaldehyde, E-32: Yield: 95%. 1H NMR (300 MHz, CDCl3, δppm): 9.82 (s,
1H), 7.32 (d, 2H), 6.95 (d, 1H), 6.60 (d, 1H), 6.58 (d, 2H), 5.70 (s, 1H),
4.20 (s, 4H), 3.72 (d, 2H), 3.64 (d, 2H), 3.27 (t, 4H), 1.57 (q, 4H), 1.35
δ
ppm): 180.01, 149.01, 148.32, 140.13, 138.95, 128,79, 128.25, 125.84,
125.04, 116.18, 114.91, 65.26, 64.44, 31.44, 31.30, 30.37, 28.62, 22.45,
13.98; HRMS (ESI) m/z: [M + H]+ calcd for C27H28O5S3,529.1098; found,
529.7641.
(t, 4H), 0.94 (t, 6H); 13C NMR (75 MHz, CDCl3,
δppm): 178.85, 148.42,
137.09, 132.06, 130.39, 128.34, 123.05, 113.90, 111.81, 111.38, 110.15,
95.36, 64.88, 64.64, 29.33, 20.21, 13.89; HRMS (ESI) m/z: [M+H]+ calcd
for C29H43NO3S, 399.1868; found, 399.5462; mp = 112 ºC.
General Procedure for the Preparation of Penta- and Hepta-
arylenevinylenes: t-BuOK (4 eq.) was added to a solution of bifunctional
monomer 43[27] (1 eq.) in dry THF under nitrogen atmosphere and at
–10°C, turning the solution deep red. 2.1 eq. of the respective deprotected
aldehyde (E-30–E-38 and E,E-41–E,E-42) were then added to the solution
and the resulting mixture was stirred at room temperature for 1 h. The
solvent was removed under reduced pressure, and then water and DCM
were added to the crude. The organic phase was separated, dried over
anhydrous Na2SO4 and concentrated under reduced pressure. The
products (E,E,E,E-44–E,E,E,E-52 and E,E,E,E,E-53–E,E,E,E,E-54) were
purified by column chromatography (alumina, 0–30% DCM in hexane).
The NMR spectra of the reaction mixtures showed that materials
E,E,E,E-44–E,E,E,E-52 and E,E,E,E,E-53–E,E,E,E,E-54 (all in >80% of the E
isomer) were obtained as the sole products.
7-(4-(Diphenylamino)styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-
carbaldehyde, E-33: Yield: 98%. 1H NMR (300 MHz, CDCl3, δppm): 9.87
(s, 1H), 7.80 (d, 2H), 7.3 (t, 4H), 7.25 (s, 1H), 7.16 (s, 1H), 7.07 (m,
6H), 6.90 (d, 2H), 4.47 (d, 2H); 13C NMR (75 MHz, CDCl3,
δppm): 181.4,
149.5, 149.2, 140.0, 139.6, 132.8, 132.2, 131.1, 131.0, 129.3, 129.0,
128.4, 127.8, 126.4, 125.1, 125.0, 117.3, 66.9, 66.4; MS (TOF LD+) m/z:
C27H21NO3S, 440.12 [M+H]+.
7-((E)-2-(9-Hexyl-9H-carbazol-6-yl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]
dioxine-5-carbaldehyde, E-34: Yield: 96%. 1H NMR (300 MHz, CDCl3,
δ
ppm): 9.89 (s, 1H), 8.13 (d, 2H), 7.57 (d, 1H), 7.54 (m, 4H), 7.12 (d,
1H), 7.11 (d, 1H), 5.69 (s, 1H), 4.26 (s, 4H), 4.20 (t, 2H), 1.83 (m, 2H),
1.42 (q, 8H), 0.83 (t, 3H); 13C NMR (75 MHz, CDCl3,
ppm): 178.97,
δ
148.92, 140.70,140.65, 140.57, 137.87, 132.81, 129.27, 127.16, 125.90,
123.07, 122.80, 122.61, 119.17, 114.40, 114.29, 108.90, 64.81, 53.35,
42.97, 31.46, 31.45, 30.79, 28.82, 26.81, 22.49, 13.96; HRMS (ESI) m/z:
[M+H]+ calcd for C27H27NO3S, 446.1711; found, 446.1791.
5-((1E)-2-(5-((1E)-2-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-
((E)-2-(5-(2-ethylhexyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)
vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)
vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)-7-(2-ethylhexyl)-2,3-
dihydrothieno[3,4-b][1,4]dioxine, E,E,E,E-44: Yield: 89%. 1H NMR (300
MHz, CDCl3, δppm): 7.19 (d, 2H), 7.14 (d, 2H), 6.97 (d, 2H), 6.87 (d,
4H), 4.27 (s, 8H), 3.91 (d, 4H), 3.84 (d, 4H), 2.51 (d, 4H), 1.85 (t, 2H),
1.54 (t, 4H), 1.39 (m, 32H), 0.80 (m, 24H); 13C NMR (75 MHz, CDCl3,
7-(3,4,5-Trimethoxystyryl)-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-
1
carbaldehyde, E-35: Yield: 95%. H NMR (300 MHz, CDCl3, δppm): 9.87 (s,
1H), 7.02 (s, 2H), 6.78 (d, 1H), 6.58 (d, 1H), 4.24 (s, 4H). 3.89 (d, 9H); 13
C
NMR (75 MHz, CDCl3, δppm): 179.36, 153.19, 148.76, 138.67, 138.60, 131.93,
131.59, 127.97, 116.67, 115.37, 103.86, 64.74, 64.67, 60.94, 56.13; HRMS
(ESI) m/z: [M + H]+ calcd for C18H18O6S, 363.0824; found, 363.0798.
7-((E)-2-(5-Hexylthiophen-2-yl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]
dioxine-5-carbaldehyde, E-36: Yield: 96%. 1H NMR (300 MHz, CDCl3,
δppm): 150.95, 139.18, 138.60, 138.59, 138.31, 132.32, 130.78, 128.69,
126.31, 116.09, 115.97, 115.93, 113.62, 71.55, 68.03, 64.76, 40.46, 39.70,
32.33, 31.82, 30.78, 30.24, 29.60, 29.56, 29.26, 29.19, 28.81, 28.70, 25.54,
24.08, 23.62, 23.04, 22.94, 22.88, 22.59, 14.08, 14.06, 14.02, 11.28,
10.85,0.91; HRMS (ESI) m/z: [M+H]+ calcd for C70H94O10S4, 1223.5721;
found, 1223.5763.
δ
ppm): 9.84 (s, 1H), 7.23 (d, 1H), 6.89 (d, 1H), 6.79 (s, 1H), 6.64 (s,
1H), 4.13 (s, 4H), 2.71 (t,2H), 1.65 (t, 2H), 1.29 (m, 6H), 0.70 (s, 3H);
©
wileyonlinelibrary.com
Adv. Funct. Mater. 2012, 22, 1489–1501
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1499

www.afm-journal.de
www.MaterialsViews.com
6-((1E)-2-(5-((1E)-2-(2, 5-Bis(2-ethylhexyloxy)-4-((1E)-
2-(5-((E)-2-(3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]
dioxepin-6-yl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)vinyl)-2,3-
dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)-3,3-dibutyl-3,4-dihydro-2H-
thieno[3,4-b][1,4] dioxepine, E,E,E,E-45: Yield: 80%. 1H NMR (300 MHz,
CDCl3, δppm): 7.19 (d, 2H), 7.14 (d, 2H), 6.97 (d, 2H), 6.87 (d, 4H), 6.25
(s, 2H), 4.27 (s, 8H), 3.91 (d, 8H), 3.84 (d, 4H), 1.54 (t, 2H), 1.39 (m,
N-(4-((1E)-2-(6-(4-((1E)-2-(6-(4-(Diphenylamino)styryl)-3,3-dibutyl-
3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-8-yl)vinyl)-2,5-bis(octan-3-yloxy)
styryl)-3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-8-yl)vinyl)
phenyl)-N-phenylbenzenamine, E,E,E,E-51: Yield: 88%. 1H NMR (300
MHz, CDCl3, δppm): 77.62 (d, 4H), 7.60 (m, 16H), 7.24 (m, 16H), 6.95
(d, 4H), 4.26 (s, 8H), 4.20 (t, 4H), 3.92 (s, 4H), 1.81 (m, 2H), 1.21 (m,
40H), 1.15 (s, 6H), 0.72 (m, 18H); 13C NMR (75 MHz, CDCl3,
δppm):
40H), 0.80 (m, 24H); 13C NMR (75 MHz, CDCl3,
δ
ppm): 141.51, 139.18,
178.01, 149.98, 148.21, 145.62, 139.81, 136.08, 133.91, 132.84, 131.01,
128.97, 127.62, 126.54, 126.21, 125.82, 125.03, 124.94, 124.08, 118.2,
113.8, 97.2, 79.5, 77.79,.31.49, 31.40, 30.01, 28.65, 24.7, 23.6, 22.49,
21.70, 14.03; HRMS (ESI) m/z: [M+H]+ calcd for C96H116N2O6S2,
1457.8274; found, 1457.8189.
139.14, 126.32, 121.82, 121.16, 117.74, 116.52, 116.30, 115.61, 115.16,
109.71, 101.80, 71.58, 64.80, 43.58, 43.55, 39.77, 31.46, 31,42, 30.80,
29.62, 29.33, 24.12, 23.48, 23.08, 23.04, 22.58, 14.03, 13.93; HRMS (ESI)
m/z: [M+H]+ calcd for C72H98O10S4, 1251.6042; found, 1251.4038.
(1E,2E)-1-((2Z)-3-((3E)-4-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-(4-
(dibutylamino)styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)
but-3-en-2-ylidene)-1,4-dioxan-2-ylidene)-3-(4-(dibutylamino)phenyl)prop-
2-ene-1-thiol, E,E,E,E-46: Yield: 85%. 1H NMR (300 MHz, CDCl3, δppm):
7.23 (d, 4H), 7.18 (d, 4H), 7.07 (d, 2H), 6.95 (d, 4H), 6.69 (d, 2H), 6.58
(d, 4H), 4.27 (s, 8H), 3.92 (d, 4H), 3.26 (t, 8H), 1.81 (m, 2H), 1.57-1.38
6-(4-((1E)-2-(3,3-Dibutyl-6-((E)-2-(5-hexylthiophen-2-yl)vinyl)-3,4-
dihydro-2H-thieno[3,4-b]1,4]dioxepin-8-yl)vinyl)-2,5-bis(octan-3-yloxy)styryl)-
3,3-dibutyl-8-((E)-2-(5-hexyl thiophen-2-yl)vinyl)-3,4-dihydro-2H-thieno[3,4-b]
1
[1,4]dioxepine, E,E,E,E-52: Yield: 87%. H NMR (300 MHz, CDCl3, δppm):
7.27 (d, 4H), 6.99 (d, 2H), 6.83 (d, 4H), 6.77 (d, 2H), 6.60 (d, 2H), 4.3 (s,
8H), 3.92 (d, 4H), 2.71 (t, 4H), 1.81 (m, 2H), 1.54 (t, 4H), 1.29 (m, 28H),
(m, 32H), 0.94 (t, 24H); 13C NMR (75 MHz, CDCl3,
δ
ppm): 150.94, 147.46,
1.19 (m, 24H), 0.80 (m, 30H); 13C NMR (75 MHz, CDCl3,
δppm): 151.01,
139.22, 138.11, 127.39, 126.66, 126.32, 124.35, 120.47, 117.65, 116.71,
115.24, 112.91, 111.52, 109.60, 71.62, 64.88, 64.64, 50.68, 39.74, 30.81,
29.42, 29.22, 24.10, 23.07, 20.26, 14.14, 14.05, 13.93, 11.33; HRMS (ESI)
m/z: [M+H]+ calcd for C71H100N2O6S2, 1125.6709; found, 1125.7060.
4-((1E)-2-(5-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-(4-(diphenylamino)
styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)styryl)-2,3-dihydrothieno-
[3,4-b][1,4]dioxin-7-yl)vinyl)-N,N-diphenyl benzenamine, E,E,E,E-47: Yield:
80%. 1H NMR (300 MHz, CDCl3, δppm): 8.18(d, 4H), 7.62(d, 2H), 7.60
(m, 8H), 7.24(d, 8H), 7.04(d, 2H), 4.26(s, 8H), 4.20(t, 4H), 3.944(d,
4H), 1.83 (m, 6H), 1.61 (q, 4H), 1.47(m, 28H), 1.01(m, 12H), 0.87(t,
145.02, 140.73, 139.19 139.05, 126.35, 125.48, 124.60, 121.14, 119.90,
117.62, 116.51, 116.38, 115.24, 109.60, 71.55, 64.80 39.77, 31.54, 31,42,
30.37, 30.11, 29.66, 29.62, 29.33, 29.26, 28.72, 24.14, 23.11, 22.65, 22.54,
14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+ calcd for C80H118O6S4,
1303.7811; found, 1303.7853.
6-[(E)-2-[5-[(E)-2-[7-[(E)-2-[4-[(E)-2-[5-[(E)-2-[7-[(E)-2-(3,3-Dimethyl-2,4-
dihydrothieno[3,4-b][1,4]dioxepin-6-yl)vinyl]-2,3-dihydrothieno[3,4-b][1,4]
dioxin-5-yl]vinyl]-2,3-di
hydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]-2,5-bis(2-
ethylhexoxy)phenyl]vinyl]-2,3-dihydroth ieno[3,4-b][1,4]dioxin-5-yl]vinyl]-2,3-
dihydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]-3,3-dimethyl-2,4-
dihydrothieno[3,4-b][1,4]dioxepine, E,E,E,E,E,E-53: Yield: 86%. 1H NMR
(300 MHz, CDCl3, δppm): 7.19 (d, 2H), 7.04 (d, 4H), 6.97 (d, 4H), 6.87
(d, 4H), 6.25 (s, 2H), 4.27 (s, 8H), 3.91 (d, 16H), 3.84 (d, 4H), 1.54 (t,
6H); 13C NMR (75 MHz, CDCl3,
δppm): 151.01, 145.07, 140.73, 139.19,
139.16, 128.52, 126.35, 125.48, 124.60, 121.14, 116.51, 115.24, 109.60,
71.55, 64.80, 39.77, 31.54, 31.42, 30.85, 30.37, 29.66, 29.26, 28.72, 24.14,
23.11, 22.54, 14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+ calcd for
C78H80N2O6S2, 1205.5457; found, 1205.3567.
2-((1E)-2-(5-((1E)-2-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-((E)-2-(9-
hexyl-9H-carbozol-2-yl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)
phenyl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)-9-hexyl-9H-
carbazole, E,E,E,E-48: Yield: 85%. 1H NMR (300 MHz, CDCl3, δppm):
8.18 (d, 4H), 7.62 (d, 2H), 7.60 (m, 8H), 7.24 (d, 8H), 7.04 (d, 2H),
4.26 (s, 8H), 4.20 (t, 4H), 3.944 (d, 4H), 1.83 (m, 6H), 1.61 (q, 4H),
1.47 (m, 28H), 1.01 (m, 12H), 0.87 (t, 6H); 13C NMR (75 MHz, CDCl3,
2H), 1.39 (m, 40H), 0.80 (m, 24H); 13C NMR (75 MHz, CDCl3,
δppm):
141.51, 139.18, 139.14, 126.32, 121.82, 121.16, 117.74, 116.52, 116.30,
115.61, 115.16, 109.71, 101.80, 71.58, 64.80, 43.58, 43.55, 39.77, 31.46,
31,42, 30.80, 29.62, 29.33, 24.12, 23.48, 23.08, 23.04, 22.58, 14.03, 13.93;
HRMS (ESI) m/z: [M+H]+ calcd for C88H110O14S6, 1584.6219; found,
1584.6238.
5-[(E)-2-[7-[(E)-2-[2,5-Bis(2-ethylhexoxy)-4-[(E)-2-[5-[(E)-2-
[7-[(E)-2-(5-methyl-2-thienyl)vinyl]-2,3-dihydrothieno[3,4-b][1,4]
dioxin-5-yl]vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]phenyl]vinyl]-
2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl]vinyl]-7-[(E)-2-(5-methyl-2-thienyl)
vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxine, E,E,E,E,E,E-54: Yield: 90%. 1H
NMR (300 MHz, CDCl3, δppm): 7.19 (d, 4H), 6.89 (d, 2H), 6.80 (d, 4H),
6.77 (d, 4H), 6.60 (d, 4H), 4.27 (s, 16H), 3.90 (d, 4H), 2.71 (t, 4H), 1.54
δppm): 151.01, 145.07, 140.73, 139.19, 139.16, 128.52, 126.35, 125.48,
124.60, 121.14, 116.51, 115.24, 109.60, 71.55, 64.80, 39.77, 31.54, 31.42,
30.85, 30.37, 29.66, 29.26, 28.72, 24.14, 23.11, 22.54, 14.17, 14.05, 11.36;
HRMS (ESI) m/z: [M+H]+ calcd for C78H92N2O6S2, 1217.6396; found,
1217.5446.
(t, 4H), 1.29 (m, 28H), 0.80 (m, 18H); 13C NMR (75 MHz, CDCl3,
δppm):
(1E,2E)-1-((2Z)-3-((3E)-4-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-(3,4,5-
trimethoxystyryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)
but-3-en-2-ylidene)-1,4-dioxan-2-ylidene)-3-(3,4,5-trimethoxyphenyl)prop-
2-ene-1-thiol, E,E,E,E-49: Yield: 83%. 1H NMR (300 MHz, CDCl3, δppm):
7.23 (s, 2H), 6.97 (d, 4H), 6.78 (d, 4H), 6.78 (d, 4H), 6.19 (s, 2H), 4.24
(s, 8H). 3.89 (m, 22H), 1.82 (m, 2H), 1.23 (m, 16H), 0.85 (m, 12H);
151.01, 145.02, 140.73, 139.19 139.05, 126.35, 125.48, 124.60, 121.14,
119.90, 117.62, 116.51, 116.38, 115.24, 109.60, 71.55, 64.80 39.77, 31.54,
31,42, 30.37, 30.11, 29.66, 29.62, 29.33, 29.26, 28.72, 24.14, 23.11,
22.65, 22.54, 14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+ calcd for
C
78H94O10S6, 1383.5171; found, 1383.9637.
13C NMR (75 MHz, CDCl3,
δppm): 151.24, 148.76, 138.28, 136.11, 128.37,
126.66, 126.32, 124.55, 120.47, 117.65, 116.71, 115.24, 112.91, 111.52,
109.60, 71.62, 64.88, 64.64, 50.68, 56.06, 39.74, 30.81, 29.42, 29.22,
24.10, 23.07, 20.26, 14.14, 13.93, 11.33; HRMS (ESI) m/z: [M + H]+ calcd
for C61H78O12S2, 1067.4925; found, 1067.5809 (M+H+).
Acknowledgements
The authors thank the European Community Marie Curie Actions, Marie
Curie Research Training Network (BIMORE, Project No.: 35859, grant
agreement No: 2008206) and the Technion Funds for Security Research.
This article was amended on April 10, 2012 to correct an error in the
spelling of author K. N. Shivananda’s name that was present in the
version originally published online.
5-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-((E)-2-(5-hexylthiophen-2-yl)
vinyl)-2,3-dihy
drothieno[3,4-b][1,4]dioxin-7-yl)vinyl)styryl)-7-((E)-2-(5-
hexylthiophen-2-yl)vinyl)-2,3-dihy drothieno[3,4-][1,4]dioxine, E,E,E,E-50:
Yield: 91%. 1H NMR (300 MHz, CDCl3, δppm): 7.17 (d, 4H), 6.97 (d, 2H),
6.83 (d, 4H), 6.77 (d, 2H), 6.60 (d, 2H), 4.27 (s, 8H), 3.90 (d, 4H), 2.71
(t, 4H), 1.54 (t, 4H), 1.29 (m, 28H), 0.80 (m, 18H); 13C NMR (75 MHz,
Received: August 13, 2011
Published online: January 31, 2012
CDCl3,
δppm): 151.01, 145.02, 140.73, 139.19 139.05, 126.35, 125.48,
124.60, 121.14, 119.90, 117.62, 116.51, 116.38, 115.24, 109.60, 71.55,
64.80 39.77, 31.54, 31,42, 30.37, 30.11, 29.66, 29.62, 29.33, 29.26, 28.72,
24.14, 23.11, 22.65, 22.54, 14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+
calcd for C62H82O6S4,1051.4994; found, 1051.5013.
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1501