Synthesis and characterization of novel optically active polyarylene vinylenes with controlled effective conjugation length

Article abstract of DOI:10.1021/jo000761k

New chiral and soluble binaphthyl derivatives (12 and 13) endowed with carboxaldehyde or cyanomethyl functional groups have been prepared as suitable building blocks for the synthesis by Knoevenagel condensation of a series of optically active block copolymers (1-7) with controlled effective conjugation length. A variety of functionalized co-monomers (14-19) have been prepared by different synthetic procedures to be used in further polymerization reactions with binaphthyl derivatives 12 and 13. Depending upon the nature of the co-monomers, it is possible to tune the wavelength of the new polymers, which is very close to that of the respective repeating units. Fluorescence measurements on polymers 1-3 reveal a strong blue-green emission with Stokes shifts of 74-107 nm. Theoretical calculations at the semiempirical AM-1 level have been carried out on model compounds, and the calculated torsion angles are in agreement with the electronic spectra data. Finally, the redox properties of the polymers prepared (1-7) were determined by cyclic voltammetry, and an amphoteric behavior with oxidation potentials ranging from 1.1 to 1.6 V and reduction potentials close to - 1.5 V was found.

Full text of DOI:10.1021/jo000761k

J . Org. Chem. 2000, 65, 7501-7511
7501
Syn th esis a n d Ch a r a cter iza tion of Novel Op tica lly Active
P olya r ylen e Vin ylen es w ith Con tr olled Effective Con ju ga tion
Len gth †
Rafael G o´ mez, J os e´ L. Segura, and Nazario Mart ´ı n*
Departamento de Qu ı´ mica Org a´ nica, Facultad de Ciencias Qu ´ı micas, Universidad Complutense,
E-28040 Madrid, Spain
nazmar@eucmax.sim.ucm.es
Received May 18, 2000
New chiral and soluble binaphthyl derivatives (12 and 13) endowed with carboxaldehyde or
cyanomethyl functional groups have been prepared as suitable building blocks for the synthesis by
Knoevenagel condensation of a series of optically active block copolymers (1-7) with controlled
effective conjugation length. A variety of functionalized co-monomers (14-19) have been prepared
by different synthetic procedures to be used in further polymerization reactions with binaphthyl
derivatives 12 and 13. Depending upon the nature of the co-monomers, it is possible to tune the
wavelength of the new polymers, which is very close to that of the respective repeating units.
Fluorescence measurements on polymers 1-3 reveal a strong blue-green emission with Stokes shifts
of 74-107 nm. Theoretical calculations at the semiempirical AM-1 level have been carried out on
model compounds, and the calculated torsion angles are in agreement with the electronic spectra
data. Finally, the redox properties of the polymers prepared (1-7) were determined by cyclic
voltammetry, and an amphoteric behavior with oxidation potentials ranging from 1.1 to 1.6 V and
reduction potentials close to -1.5 V was found.
In tr od u ction
Binaphthyl derivatives are optically active materials,
their chirality being derived from the restricted rotation
of the two naphthalene rings. The angle between the
rings ranges from 60 to 120°, and therefore conjugation
between the two naphthalene units is minimal. Thus,
the conjugated system in polymers containing binaphthyl
The design of tailor-made π-conjugated polymers has
been a subject of intensive research during the past
decade because of their potential applications as novel
6
1
materials for optoelectronics given that they combine the
optical and electronic properties of semiconductors with
the processing advantages and mechanical properties of
polymers.
units is confined to the region between two binaphthyl
7-9
units (Figure 1a).
In this paper, we describe the
synthesis of a family of chiral conjugated-nonconjugated
block copolymers containing binaphthyl units in order
to efficiently tune the conjugation length. The structure
of these block copolymers can be schematically repre-
sented as in Figure 1b with consecutive conjugated
systems linked to each other in a noncoplanar way.
Although different luminescent fragments as well as
hole-transport and electron-transport materials have
been integrated in conjugated-nonconjugated polymeric
The HOMO-LUMO gap in semiconducting polymers
is roughly determined by the extent of π delocalization
along the backbone, the so-called effective conjugation
length, which is responsible for the emitting properties
of these materials. Introduction of nonconjugated seg-
ments into conjugated polymer backbones results in the
confinement of π electrons in the conjugated fragment.
Materials of this type can be seen as long chains of
separated small dye molecules connected by a variety of
nonconjugated spacer units including ether, ester,3
2
4
5
(3) (a) Oberski, J . M.; Clauswitz, K.-U.; L u¨ ssem, G.; Geffarth, F.;
Wendorff, J . H.; Greiner, A. Polym. Prepr. 1999, 40(2), 1187. (b)
L u¨ ssem, G.; Festag, R.; Greiner, A.; Schmidt, C.; Unterlechner, C.;
Heitz, W.; Wendorff, J . H.; Hopmeier, M.; Feldman, J . Adv. Mater.
1995, 7, 923. (c) Bouillud, A. D.; Mazerolle, L.; Gagnon, P.; Goldenberg,
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1236. (b) Van Hutten, P. F.; Gill, R. E.; Herrema, J . K.; Hadziioannou,
G. J . Phys. Chem. 1995, 99, 3218. (b) Silcoff, E. R.; Sheradsky, T.
Macromolecules 1998, 31, 9116.
amide, or sililene groups.
†
This work is dedicated to Professor Michael Hanack on the occasion
of his retirement.
(
1) (a) Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Angew. Chem., Int.
Ed. Engl. 1998, 37, 402. (b) Segura, J . L. Acta Polym. 1998, 49, 319.
c) Hide, F.; D ´ı az-Garc ´ı a, M. A.; Schwartz, B. J .; Heeger, A. J . Acc.
(
Chem. Res. 1997, 30, 430. (d) Greenham, N. C.; Friend, R. H. Solid
State Phys. 1995, 49, 1. (e) Handbook of Conducting Polymers, 2nd
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Dekker: New York, 1998. (f) Wallace, G. G.; Dastoor, P. C.; Officer,
D. L.; Too, C. O. Chem. Innovation 2000, 30, 14.
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W.-Y.; Kim, J .-J . Chem. Mater. 1995, 7, 1499. (b) Lee, J .-I.; Kang, I.-
N.; Hwang, D.-H.; Shim, H.-K.; J eoung, S. C.; Kim, D. Chem. Mater.
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nations; Cambridge University Press: New York, 1982; p 72.
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98, 2405. (c) In Electrical and Optical Polymer Systems; Pu, L., Wnek,
G. E., Trantolo, D. J ., Cooper, T. M., Gresser, J . D., Eds.; Marcel
Dekker: New York, 1998; Chapter 24.
1
996, 8, 1925. (c) Sarker, A. M.; Strehmel, B.; Neckers, D. C.
Macromolecules 1999, 32, 7409. (d) Pasco, S. T.; Lahti, P. M.; Karasz,
F. E. Macromolecules 1999, 32, 6933. (e) Keegstra, M. A.; Cimrov a´ ,
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Konstandakopoulou, F.; Gravalos, K.; Kallitsis, J . Macromolecules
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1
998, 31, 5264.
1
0.1021/jo000761k CCC: $19.00 © 2000 American Chemical Society
Published on Web 09/29/2000

7
502 J . Org. Chem., Vol. 65, No. 22, 2000
G o´ mez et al.
F igu r e 1. Structure of the conjugated-non-conjugated block copolymers showing the conjugated region.
systems,1b conjugated oligomers present special interest
from a chemical point of view because of the possibility
to tune their wavelength of emission as well as their
electron affinity and ionization potential by means of
synthetic strategies.10 Thus, in this paper, we describe a
synthetic strategy which allows us to copolymerize bi-
functionalized conjugated oligomers and binaphthyl de-
rivatives to yield conjugated-nonconjugated block co-
polymers in which the HOMO-LUMO band gap can be
efficiently tailored by the choice of appropriate conjugated
oligomers.
present high electron affinity and therefore exhibit a
relatively low threshold voltage and high quantum ef-
ficiency in LED devices even using stable aluminum
electrodes.11
To be able to perform this type of polymerization,
appropriate monomeric units have been synthesized.
1
. Syn th esis of Bin a p h th yl Mon om er s. The syn-
thesis of suitably functionalized binaphthyl derivatives
12 and 13) is depicted in Scheme 1. The resolution of
(
the (()-1,1′-bi-2-naphthol was carried out by using (-)-
N-benzylcinconidinium chloride as the chiral resolution
reagent,14 and the enantiomerically pure R isomer was
used in the subsequent reactions.
Resu lts a n d Discu ssion
Two different synthetic routes previously described in
the literature for analogous compounds have been fol-
lowed in order to synthesize derivatives (R)-12 and (R)-
The preparation of these main chain chiral cyano-
containing binaphthyl-based copolymers 1-7 (Figure 2)
was carried out using the Knoevenagel condensation11
of appropriately functionalized monomers.
1
3. The first route involves selective bromination of the
,1′-binaphthalenic unit in the 6,6′ positions by using
1
This type of polymerization allows the introduction of
nitrile groups on the vinylene linkages of PPV deriva-
tives.12 The introduction of the high electron affinity CN
group to a π-conjugated polymer system lowers the
energy level of the LUMO and reduces the barrier to
the electron injection in light-emitting devices (LED).
Thus, Holmes and co-workers showed that PPV deriva-
tives containing cyano groups on the vinylene linkage
bromine in dichloromethane to yield derivative (R)-9.
Subsequent Williamson reaction of (R)-9 with dodecyl
bromide using potassium carbonate as the base afforded
derivative (R)-11. Compound (R)-11 could be also ob-
tained by first introducing the alkyl chains to yield (R)-
1
3
1
0 followed by a selective bromination reaction. In our
hands, the first synthetic route has proven to be more
(
12) (a) Hanack, M.; Segura, J . L.; Spreitzer, H. Adv. Mater. 1996,
(
10) (a) In Electronic Materials: The Oligomer Approach; M u¨ llen,
8, 663. (b) Hohloch, M.; Segura, J . L.; D o¨ ttinger, S.; Hohnholz, D.;
Steinhuber, E.; Spreitzer, H.; Hanack, M. Synth. Met. 1997, 84, 319.
(c) Zarras, P.; Stenger-Smith, J . D.; Ostrom, G. S.; Merwin, L. H.;
Webber, C. K. Polym. Prepr. 1999, 40(2), 1176. (d) Kim, K.-D.; Park,
J .-S.; Kim, H. K.; Lee, T. B.; No, K. T. Macromolecules 1998, 31, 7267.
(e) Peng, Z.; Galvin, M. E. Chem. Mater. 1998, 10, 1785. (f) Chen, S.
A.; Chang, E.-C. Macromolecules 1998, 31, 4899. (g) Martinez-Ruiz,
P.; Behnisch, B.; Schweikart, K.; Hanack, M.; L u¨ er, L.; Oelkrug, D.
Chem.sEur. J . 2000, 6, 1294.
K., Wegner, G., Eds.; Wiley VCH: Weinheim, Germany, 1998. (b)
Martin, R. E.; Diederich, F. Angew. Chem., Int. Ed. 1999, 38, 1350. (c)
Scherf, U. Top. Curr. Chem. 1999, 201, 163. (c) Roncali, J . Chem. Rev.
1
997, 97, 173. (d) Tour, J . M. Chem. Rev. 1996, 96, 537.
11) (a) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend,
(
R. H.; Holmes, A. B. Nature 1993, 365, 628. (b) Moratti, S. C.; Cervini,
R.; Holmes, A. B.; Baigent, D. R.; Friend, R. H.; Greenham, N. C.;
Gr u¨ ner, J .; Hamer, P. J . Synth. Met. 1995, 71, 2117. (c) Holmes, A. B.;
Friend, R. H.; Moratti, S. C.; Baigent, D. R.; Bradley, D. D. C.; Cervini,
R.; Greenham, N. C.; Hamer, P. J . P. C. T. Int. Appl. WO94/29,883;
(13) Br e´ das, J .-L. Adv. Mater. 1995, 7, 263.
(14) Hu, Q. S.; Vitharama, D.; Pu, L. Tetrahedron: Asymmetry 1995,
6, 2123.
(
Chem. Abstr.) 1995, 123, 973318d.

Novel Optically Active Polyarylene Vinylenes
J . Org. Chem., Vol. 65, No. 22, 2000 7503
F igu r e 2. Main chain chiral cyano-containing binaphthyl-based copolymers 1-7.
effective (overall yield 79%) in comparison with the
second one (65%), which is in agreement with previous
bibliographic data.15 The presence of the long alkyl chains
in the monomeric units is important in order to obtain
soluble polymers useful to fabricate large area thin films
for LEDs or photovoltaic applications. After the Bou-
veault formylation reaction16 of dibromo derivative (R)-
Naphthalene derivatives 14 and 15 were synthesized
by following the multistep synthetic route developed by
12a
Hanack and co-workers. Although 2,5-thiophenedicar-
boxaldehyde (16) was commercially available, the related
bis(cyanomethyl) derivative 17 was prepared following
a previously described synthetic route.18 Reduction of 16
to the bis(hydroxymethyl) derivative was followed by
chlorination with thionyl chloride in dichloromethane and
finally cyanation with sodium cyanide in dimethylform-
1
1, the corresponding diformyl derivative (R)-12 was
obtained. Finally, the bis(cyanomethyl) derivative (R)-
3 could be obtained from dialdehyde (R)-12 upon treat-
1
9
1
amide. The synthesis of the versatile synthon diformyl-
oligonaphthylenevinylene 18 has been carried out by
using the synthetic route recently reported by our
group.20 Finally, oligomer 19 has been synthesized as
depicted in Scheme 2. Wittig reaction of commercially
available thiophene derivative 21 with 1,5-dihexyloxy-
2,6-bis[triphenylphosphonio(methyl)]naphthalene 20 af-
forded the dibromo derivative 22 as a mixture of the
trans,trans isomer together with the cis,trans and cis,cis
forms. Iodine-catalyzed thermal isomerization of the
mixture was carried out in xylene to afford the pure
trans,trans-22. Treatment of 22 with copper cyanide in
1
7
ment with tosylmethylisocyanide (TosMIC) and a base.
This reaction is carried out in one single step, offering
yields similar to those obtained by classical methods that
involve reduction of the aldehyde to the corresponding
alcohol and transformation of the alcohol to the halo-
genated derivative by nucleophilic substitution followed
by a new nucleophilic substitution to transform the
bromomethyl derivative into the corresponding cyano-
methyl analogue.
2
. Syn th esis of F u n ction a lized Co-m on om er s. The
remaining monomers used in the polymerization reac-
tions are depicted in Figure 3.
(
18) Garriges, B. Phosphorus, Sulfur Silicon Relat. Elem. 1990, 53,
(
15) Deussen, H. J .; Hendrickx, E.; Boutton, C.; Krog, D.; Clays, K.;
Bechgaard, K.; Persoons, A.; Bjornholm, T. J . Am. Chem. Soc. 1996,
18, 6841.
75.
(19) (a) Segura, J . L.; Mart ´ı n, N. Tetrahedron Lett. 1999, 40, 3239.
Segura, J . L.; G o´ mez, R.; Mart ´ı n, N.; Lvo, Ch.; Guldi, D. M. Chem.
Commun. 2000, 701.
(20) Segura, J . L.; Mart ´ı n, N.; Hanack, M. Eur. J . Org. Chem. 1999,
643, 3.
1
(
(
16) Meiler, D.; Semmelhack, M. F. Org. Synth. 1986, 64, 114.
17) Oldenziel, O. H.; Van Leusen, D.; Van Leusen, A. M. J . Org.
Chem. 1977, 42, 3114.

7
504 J . Org. Chem., Vol. 65, No. 22, 2000
G o´ mez et al.
Sch em e 1
F igu r e 3. Monomers used in the polymerization reactions.
using polystyrene standards, were between 9400 (poly-
dispersity of 1.62) for polymer 2 and 55 185 (polydisper-
sity of 5.61) for polymer 7. The reaction yields were in
all cases above 75%, and the obtained polymers were
soluble in common organic solvents such as tetrahydro-
furan, chloroform, or dichloromethane. The incorporation
of the flexible long alkyl chains both in the naphthalene
and binaphthyl units affords rather soluble materials.
Furthermore, the lack of planarity of the binaphthyl
system can reduce the characteristic chain stiffness of
conjugated polymers, thus contributing to the enhanced
solubility of these materials.
dimethylformamide21 led to the dicyano derivative 23,
which upon reduction with DIBAL-H yielded the target
compound 19.
3
. Syn th esis a n d Ch a r a cter iza tion of Bin a p h th yl-
Con ta in in g Cop olym er s. As previously stated, synthe-
ses of polymers 1-7 were carried out by using the
Knoevenagel condensation polymerization, between suit-
able monomers containing either two aldehyde groups
(12, 14, 16, 18, and 19) or two cyanomethyl functional-
1
ities (13, 15, and 17). Equimolecular amounts of dialde-
hyde and bis(cyanomethyl) derivative were dissolved in
a mixture of tert-butyl alcohol and tetrahydrofuran, and
the solution was heated to 50 °C. After addition of tetra-
butylammonium hydroxide and potassium tert-butoxide,
a colored solid precipitated in all cases. The resulting
pastelike polymeric product was fully precipitated from
the solution by further addition of methanol, collected,
and thoroughly washed with methanol and diethyl ether
to remove ionic species and unreacted compounds. The
polymerization results and optical properties of these new
compounds are summarized in Table 1.
FTIR, H NMR, and UV-vis spectrometry character-
ized the chemical structures of the resulting polymers.
Comparison of the polymers FTIR spectra with that of
monomers shows a drastic decrease of the bands at
-
1
around 1680 cm , which is expected to be present for
the strong aldehyde-carbonyl stretching band of the
dialdehyde monomer. On the other hand, a new sharp
-
1
absorption peak in the region 2210-2220 cm appears
in the polymers, corresponding to the conjugated nitrile
moiety.
1H NMR spectra of polymers exhibit the characteristic
vinylene proton at around δ 8.1 together with the
expected signals of the binaphthyl units (one singlet at
δ 8.2-8.3 corresponding to the H-5,5′ of the binaphthyl
unit and four doublets in the aromatic region because of
the four remaining protons on the binaphthyl system).
The average molecular weights (M
w
) of the polymers,
determined by gel permeation chromatography (GPC)
(21) Ellis, G. P.; Romney-Alexander, T. M. Chem. Rev. 1987, 87, 779.

Novel Optically Active Polyarylene Vinylenes
J . Org. Chem., Vol. 65, No. 22, 2000 7505
Sch em e 2
F igu r e 4. UV-vis spectra of polymers 1-7.
Because the polymers have been synthesized by using
enantiomerically pure (R)-binaphthyl derivatives (12 and
1
3), main-chain chiral polymers have been obtained with
the following observed optical rotations ([R] ): -305 (c
.2, CHCl ) for (R)-2, -220
c 0.7, CHCl
D
0
(
3
) for (R)-1, -832 (c 1.3, CHCl
3
-
4
3
) for (R)-3, -1800 (c 3 × 10 , CHCl
3
) for
-
4
(
1
R)-4, -516 (c 8 × 10 , CHCl
3
) for (R)-5, -490 (c 4 ×
-
4
-4
0
, CHCl
3
) for (R)-6, and -362 (c 5 × 10 , CHCl
3
) for
(
R)-7. Thus, these polymers rotate the plane of polarized
light in the direction opposite to that of the binaphthyl
dicyanomethyl species (R)-13 {[R] : +34 (c 0.6, CHCl )}
and in the same direction as the binaphthyldicarbalde-
hyde (R)-12 {[R] : -56 (c 0.7, CHCl )}. Optically active
D
3
D
3
conjugated polymers are potentially useful in areas such
as asymmetric electrosynthesis, polarization-sensitive
electro-optical devices, nonlinear optics, and enantio-
7
selective sensing. Furthermore, various studies on chiral
π-conjugated polymers substituted with enantiomerically
pure pendant groups or chiral dopants demonstrate a
strong optical rotation and circular dichroism (CD) of the
π-π* transition.22 Circularly polarized light can be
transformed into linearly polarized light with little loss
by using a suitable quarter-wave (λ/4) plate. Devices
emitting polarized light have proven to be particularly
useful as backlights for conventional liquid crystal dis-
plays (LCDs), because they could make the polarizer
(with its associated cost, weight, and power inefficient
Ta ble 1. P olym er iza tion Resu lts a n d Op tica l a n d Red ox
P r op er ties of th e Novel Com p ou n d s 1-7
yield
compd (%)
UV-vis
Eox
c,d
Ered
c,d
Mna
Mwa
PDIa (λmax,nm) (V)
b
(V)
2
3
absorptive loss) redundant. Most of the methods used
1
2
3
4
5
6
7
90
80
75
99
93
90
90
164 000 22 000 7.62
15 300 9400 1.62
382
422
378
472
454
438
482
1.19 -1.52
1.34 -1.54
1.32 -1.54
1.30 -1.55
1.62 -1.59
1.44 -1.51
1.32 -1.61
to obtain polarized luminescence from conjugated poly-
mers involve the orientation (mechanical, Langmuir-
Blodgett deposition, liquid-crystalline self-organization)
of highly anisotropic materials into a specific direction.
Thus, the possibility to obtain polarized luminescence
from chiral light-emitting polymers in combination with
a quarter-wave plate can avoid the complicated orienta-
tion step. Preliminary studies on polymers (R)-1-7 show
that they exhibit circular polarization of the fluorescence,
and therefore further studies should be focused on this
direction.
27 500 12 200 2.27
8496 29 440 3.47
9922 33 183 3.34
7210 11 382 1.58
9837 55 185 5.61
a
Mn (number average), Mw (weight average) molecular weights,
and PDI (polydispersity) of the polymers were determined by gel
permeation chromatography (GPC) using polystyrene standards.
b
c
In dichloromethane solutions. In dichloromethane solutions
-1
using Bu4NClO4 (0.3 mg mL ; SCE reference electrode and glassy
carbon as the working electrode). Values indicated correpond
d
respectively to the onset oxidation (Eox) and reduction (Ered)
potentials.
The UV-vis absorption spectra observed for these
polymers are depicted in Figure 4. It is worth mentioning
that the presence of additional naphthalene moieties
Dihexyloxynaphthalene-containing polymers show two
additional doublets in the aromatic region, whereas
thiophene-containing polymers exhibit an additional
singlet at δ 7.4. The methylene protons adjacent to the
oxygen atom in the hexyloxy and dodecyloxy groups are
observed as multiplets at around δ 4.0. The remaining
alkyl protons are observed at δ 0.8-1.9.
(22) (a) Harlev, E.; Wudl, F. In Conjugated Polymers and Related
Materials; Salaneck, W. R., Lundstr o¨ m, I., Ranby, R., Eds.; Oxford
University Press: Oxford, 1993; p 139. (b) Bouman, M. M.; Havinga,
E. E.; J anssen, R. A. J .; Meijer, E. W. Mol. Cryst. Liq. Cryst. 1994,
2
56, 439. (c) Peeters, E.; Delmotte, A.; J anssen, R. A. J .; Meijer, E. W.
Adv. Mater. 1997, 9, 493.
(23) Grell, M.; Bradley, D. D. C. Adv. Mater. 1999, 11, 895.

7
506 J . Org. Chem., Vol. 65, No. 22, 2000
G o´ mez et al.
F igu r e 5. Model compounds 24-30 containing the conjugated fragment of the parent polymeric materials 1-7.
Sch em e 3
shifts the absorption up to 482 nm (polymer 7). Further
red shift may be expected by introduction of longer
thienylenevinylene oligomers between the binaphthyl
units.
Compounds 24-30 (Figure 5) have been prepared as
the repeating units of the binaphthyl-based polymers.
Spectroscopic studies show that the absorption wave-
lengths of these repeating units are very close to those
of their corresponding polymers. This demonstrates that
the conjugation of the binaphthyl-based polymers is
mostly determined by the conjugation within their re-
peating units, and there is almost no extended conjuga-
tion between each adjacent repeating unit in the main
F igu r e 6. Comparison between the UV-vis spectra of poly-
mer 2 and model compound 25.
between the binaphthyl units red-shifts the absorption
of polymers. Thus, when the two binaphthyl units are
linked to each other (polymer 1), a λmax of 382 nm was
observed, whereas λmax’s of 422 and 438 nm were ob-
served after the introduction of one (polymer 2) and three
naphthalene units (polymer 6), respectively, between the
binaphthyl units. We have also introduced the thiophene
ring in these systems given that a strong red shift in the
absorption values has been reported for polymers con-
taining thienylene vinylene units with nitrile groups on
the vinylene moiety.24 Thus, by simple introduction of one
thiophene unit, a 90 nm bathochromic shift was observed
(24) (a) Baigent, D. R.; Hamer, P. J .; Friend, R. H.; Moratti, S. C.;
Holmes, A. B. Synth. Met. 1995, 71, 2175. (b) Moratti, S. C.; Bradley,
D. D. C.; Cervini, R.; Friend, R. H.; Greenham, N. C.; Holmes, A. B.
Proc. SPIE-Int. Soc. Opt. Eng. 1994, 2144, 108.
(polymer 4), whereas introduction of the thiophene-
containing oligomer 19 between the binaphthyl units

Novel Optically Active Polyarylene Vinylenes
J . Org. Chem., Vol. 65, No. 22, 2000 7507
F igu r e 7. AM1 equilibrium geometry optimized for a model compound of polymer 3.
chain. In Figure 6 are depicted for comparison purposes
the UV-vis spectra of polymer 2 together with that of
the model compound 25.
The synthesis of these compounds has been carried out
by Knoevenagel condensation between the monomers
AM1 theoretical calculations have been also performed
in order to rationalize the blue shift observed in the
absorption spectrum of polymer 3 in comparison with
polymer 2 (Figure 8).
Although in polymer 2 the nitrile group of the vinylene
linkage is close to the naphthalene moiety of the binaph-
thyl system, in polymer 3 the nitrile group is closer to
the dialkoxynaphthalene central ring. In Figure 8 are
depicted the AM1-optimized geometries of model com-
pounds of polymers 2 (left) and 3 (right). We have already
shown20 that, in contrast to the parent PPV system,
dialkoxy-substituted oligo(naphthylenevinylenes) are not
planar because of the steric interactions between the bulk
naphthalene system and the vinylene protons. The pres-
ence of nitrile groups in the vinylene linkage causes even
a larger steric hindrance. Because the steric hindrance
of the nitrile group with respect to the alkoxy group in
the naphthalene ring is larger than that observed when
the nitrile group is closer to the naphthalene ring of the
binaphthyl unit, a larger torsion of the chain is observed
for polymer 3 (torsion angles of 37 and 50° compared with
35 and 41° observed for polymer 2). This reduction of the
backbone’s planarity decreases the degree of conjugation
in the system, thus blue-shifting the absorption wave-
length values. A different trend is observed for polymers
1
4-19 depicted in Figure 3 and the new dodecyloxy-
naphthalene derivatives 33 and 34.
The synthesis of these new compounds (33 and 34) is
depicted in Scheme 3. After reaction of 6-bromo-2-
naphthol with dodecylbromide and potassium carbonate
with a catalytic amount of sodium iodide in acetone, the
corresponding derivative 32 was obtained. Further for-
mylation yielded aldehyde 33, which upon treatment with
TosMIC afforded the cyanomethyl derivative 34.
To rationalize the above-described UV-vis data for the
polymer and model compounds, we have carried out
geometry optimization using the Austin Model 1 (AM1)
semiempirical technique.25 We choose this method be-
cause previous studies on phenylene and polyene chains
have shown that the AM1 method gives good agreement
for both bond lengths and torsion angles with data
obtained from experimental and Hartree-Fock ab initio
calculations.26 Recently, this method has been success-
fully used to perform theoretical studies on torsion angles
and its effect on the structural and electronic properties
of substituted poly(p-phenylenevinylene)s. Figure 7
shows the AM1 equilibrium geometry optimized for a
model compound of polymer 3 in which the hexyloxy and
dodecyloxy chains have been replaced by methoxy sub-
stituents.
2
7
4
and 5 (Table 1), which can be accounted for by the
conjugation of the cyano groups. This finding is in
agreement with that observed for the model compounds
2
7 (λmax 458 nm) and 28 (λmax 432 nm).
In agreement with previous bibliographic references,
torsion angles of around 90° are observed between both
naphthalene units of the binaphthyl moiety, which
strongly suggests the lack of conjugation.
Because these polymers emit strong blue-green light
under an UV lamp, we decided to carry out fluorescence
measurements of selected members of the series (poly-
mers 1-3). The fluorescence spectrum of 1 shows emis-
sion maxima at λemi 475 nm when excited at 382 nm. The
fluorescence spectrum of 2 displays λemi 496 nm when
excited at 422 nm, and 3 exhibits an emission maxima
of λemi 485 nm when excited at 378 nm. The Stokes shifts
observed are of 93 nm for 1, 74 nm for 2, and 107 nm for
(
25) Dewar, M. S. J .; Zoebish, E. G.; Healy, R. F.; Stewart, J . J . P.
J . Am. Chem. Soc. 1985, 107, 3902.
26) (a) Lhost, A.; Br e´ das, J . L. J . Chem. Phys. 1992, 96, 5279. (b)
Fredricksson, C.; Br e´ das, J . L. J . Chem. Phys. 1993, 98, 4253.
27) (a) Fahlman, M.; Br e´ das, J . L. Synth. Met. 1996, 78, 39. (b)
Van der Loy, J . F. A.; Thys, G. J . H.; Dieltiens, P. E. M.; De Schrijver,
D.; Van Alsenoy, C.; Geise, H. J . Tetrahedron 1997, 53, 13811.
(
(
3
, which indicates only a small region of coincidence
(28) Cuntze, J .; Owens, L.; Alc a´ zar, V.; Seiler, P.; Diederich, F. Helv.
Chim. Acta 1995, 78, 367.
between the absorption and emission (Figure 9). This fact

7
508 J . Org. Chem., Vol. 65, No. 22, 2000
G o´ mez et al.
F igu r e 8. AM1 equilibrium geometry optimized for model compounds showing the steric hindrance of the nitrile group with
respect to the alkoxy group in the naphthalene ring.
Su m m a r y
In summary, we have developed a general synthetic
route for the preparation of optically active block copoly-
mers containing binaphthyl units. The synthesis of
binaphthyl derivatives bifunctionalized with either car-
boxaldehyde or cyanomethyl groups will allow us to
extend this synthetic route to many other difunctional-
ized chromophores and lumophores. In the present study,
we have focused our attention on the preparation of chiral
soluble polymers which offer the possibility of tuning both
optical and redox properties by means of chemical
modification of the monomeric structure. Considering the
very large number of functionalized fluorophores syn-
F igu r e 9. UV-vis and fluorescence spectra obtained for
thesized in recent years with specific electrochemical and
photophysical properties, we see that a remarkable
aspect of this contribution is that it might provide an
effective approach to the synthesis of luminescent poly-
meric materials in which the emission colors, electron
affinity, and ionization potentials can be efficiently
tailored.
The good solubility imparted by the long alkyl chains
and the high electron afinity provided by the cyano-
vinylene linkage make these types of polymers good
candidates for the fabrication of LEDs in which the
luminescent properties can be efficiently tailored. Fur-
thermore, because of the main chain chiral character of
these polymers, the observation of circularly polarized
photo- and electroluminescence can be expected, which
may be of use as backlights for conventional liquid crystal
displays (LCDs).
polymer 3.
indicates that the reabsorption of the emitted light is
almost negligible, which is very important in order to
avoid undesired loses in the LED performance.
Cyclic voltammetry studies of polymers 1-7 were
carried out in a three-electrode cell in dichloromethane
4 4
at room temperature using Bu NClO as the supporting
-
1
electrolyte (0.3 mg mL ; SCE reference electrode and
glassy carbon as the working electrode). It was found that
all of the polymers are oxidized at potentials above 1.19
V (vs SCE; Table 1), which is a high value compared with
other related polymers (0.6-1.0 V).2 On the other hand,
all of the polymers were found to be reducible at
potentials around -1.5 V (vs SCE). The relatively good
acceptor ability of these polymers can be ascribed to the
presence of cyanovinylene moieties on the conjugated
system. Because of the presence of the π-excedent
thiophene system, polymers 4, 5, and 7 show the highest
reduction potentials.
4b
Exp er im en ta l Section
All melting points were measured with a melting point
apparatus and are uncorrected. IR spectra were recorded
1
3
1
As previously stated, Holmes and co-workers showed
that PPV derivatives containing cyano groups on the
vinylene linkage exhibit a relatively low threshold voltage
and high quantum efficiency in LED devices, even using
stable aluminum electrodes, because of their relatively
high electron affinity, which reduces the barrier to the
electron injection in light-emitting devices (LED).11
either as KBr pellets or neat films. C and H NMR spectra
were recorded with a 300 MHz for 1H and 75 MHz for
spectrometer. Chemical shifts are given as δ values (internal
standard: TMS). [R] values were determined using the light
13
C
D
of a sodium lamp (λ ) 589 nm), at room temperature in a
cylindric cell with a length of 1 dm and a volume of 1 mL.
GPC measurements were carried out using chloroform as the
eluent in a system consisting of a pump, a UV detector, and

Novel Optically Active Polyarylene Vinylenes
J . Org. Chem., Vol. 65, No. 22, 2000 7509
4
3
three mStyragel columns of 10 , 10 , and 500 Å. The columns
were calibrated with a polystyrene standard with a narrow
distribution of molecular weights. Semiempirical calculations
(
3
of triphenylphosphonium salt 20 in 20 mL of dry ethanol,
heated to 50 °C and under argon atmosphere, was added 0.07
mL of formylthiophene 21 and 0.7 mL of a 1 M solution of
sodium ethoxide in ethanol. The formation of a yellow pre-
cipitate which consisted of the pure trans,trans compound 22
was observed. The precipitate was filtered and washed with
methanol to afford the pure trans,trans compound. The mother
liquors were vacuum evaporated, and the solid residue was
chromatographed (silica gel, hexane/dichloromethane (9:1)) to
yield a mixture of isomers. This mixture was suspended in 10
mL of xylene and heated to reflux for 24 h, after addition of a
catalytic amount of iodine. After the reaction mixture was
cooled, methanol was added, leading to a second crop of pure
AM1) were performed using the program Hyperchem (version
.0) with a PC compatible at 200 MHz. For each structure,
the minimum energy was determined after reminimization.
Cyclic voltammograms were recorded on a potentiostat/gal-
vanostat equipped with a software electrochemical analysis
by using a GCE (glassy carbon) as working electrode, SCE as
reference electrode, Bu
dichloromethane as solvent and at a scan rate of 200 mV/s.
()-2,2′-Dihydroxy-1,1′-binaphthalene and 6-bromo-2-hydroxy-
4 4
NClO as supporting electrolyte, and
(
naphthalene are commercially available and were used with-
out further purification. tBuOH and tetrahydrofuran were
dried with sodium, dimethylformamide was dried with calcium
hydride, chloroform and dichloromethane were distilled from
, and all were distilled before use.
Mon om er Syn t h eses. (R)-2,2′-Did od ecyloxy-6,6′-d i-
trans,trans isomer. Mp: 167-169 °C. 1H NMR (CDCl
, 300
3
MHz): δ 7.78 (d, 2 H, J ) 8.8 Hz), 7.60 (d, 2 H, J ) 8.9 Hz),
7.32 (d, 2 H, J trans ) 16.3 Hz), 7.20 (d, 2 H, J trans ) 16.1 Hz),
6.98 (d, 2 H, J ) 3.9 Hz), 6.84 (d, 2 H, J ) 3.7 Hz), 3.91 (t, 4
P
2
O
5
1
3
H), 1.89 (q, 4 H), 1.59 (m, 4 H), 1.37 (m, 8 H), 0.59 (t, 6 H).
C
for m yl-1,1′-bin a p h th a len e (12). To a solution of 4 g (51
mmol) of (R)-6,6′-dibromo-2,2′-didodecyloxy-1,1′-binaphthalene
NMR (CDCl , 75 MHz): δ 153.3, 130.6, 129.7, 126.4, 125.9,
3
123.4, 122.0, 118.8, 111.3, 75.9, 31.9, 30.5, 26.2, 22.8, 14.2.
2
8
-1
(11) in 50 mL of dry tetrahydrofuran (THF) was added
FTIR (KBr, cm ): 2926, 2856, 1466, 1260, 1234. EM (EI) m/z
+
dropwise under argon atmosphere 13 mL of a 1.6 M solution
of n-butyllithium (20 mmol) in hexane, at -78 °C. The reaction
was stirred at this temperature for 4 h, and then 2.6 mL (180
mmol) of dry N,N-dimethylformamide was added. After 1 h,
the reaction was allowed to reach room temperature and was
poured, under vigorous stirring, on a water/ice/HCl mixture
(%I): 702 (M , 100), 617 (38), 533 (18), 453 (38). Anal. Calcd
for C34
2 2 2
H38Br O S : C, 58.28; H, 5.47; S, 9.13. Found: C, 57.82;
H, 5.55; S, 9.04.
2,6-Bis[2-(5-cya n o-2-t h ien yl)vin yl]-1,5-b is(h exyloxy)-
n a p h th a len e (23). A mixture of 100 mg (0.15 mmol) of
dibromo derivative 22, 40 mg (0.45 mmol) of potassium
cyanide, and a catalytic amount of sodium iodide suspended
in 10 mL of dry N,N-dimethylformamide was refluxed for 72
h under argon atmosphere. Then the reaction mixture was
poured into a 15 wt % aqueous ammonia solution. The yellow
precipitate was filtered off, washed with ammonia solution and
water, and vacuum dried. Chromatographic purification (silica
gel, hexane/dichlorometane (6:4)) yielded 33 mg (37%) of
(pH < 1). The mixture was extracted three times with
methylene dichloride, and the organic layers were combined
and washed twice with water and dried over magnesium
sulfate. After vacuum evaporation of the solvent, an orange
oil was obtained, which was chromatographically purified
(
silica gel, hexane/diethyl ether (8:2)) to yield 2.93 g (80%) of
1
1
2 as a yellow solid. Mp: 45 °C. H NMR (CDCl
δ 10.09 (s, 2 H, CHO), 8.29 (d, 2 H, J ) 1.5 Hz), 8.00 (d, 2 H,
J ) 9.0 Hz), 7.62 (dd, 2 H, J ) 8.8, J ) 1.6 Hz), 7.49 (d, 2 H,
J ) 9.0 Hz), 7.19 (d, 2 H, J ) 8.8 Hz), 4.01-3.84 (m, 4 H),
.45-1.00 (m, 40 H), 0.81 (t, 6 H). 13C NMR (CDCl
, 75 MHz):
δ 192.0 (CHO), 157.2, 137.4, 135.0, 132.2, 131.5, 128.0, 126.2,
3
, 300 MHz):
1
compound 23 as a yellow solid. Mp: 128-130 °C. H NMR
1
2
3
(CDCl , 300 MHz): δ 7.88 (d, 2 H, J ) 8.8 Hz), 7.63 (d, 2 H, J
) 8.9 Hz), 7.56 (d, 2 H, J trans ) 16.3 Hz), 7.54 (d, 2 H, J ) 4.0
Hz), 7.29 (d, 2 H, J trans ) 16.3 Hz), 7.09 (d, 2 H, J ) 4.0 Hz),
3.92 (t, 4 H), 1.90 (q, 4 H), 1.58 (s, 4 H), 1.36 (m, 8 H), 0.89 (t,
1
3
1
2
1
3
23.3, 119.8, 115.6, 69.3, 32.0, 29.7, 29.5, 29.4, 29.2, 29.1, 26.0,
6 H). 13C NMR (CDCl
126.8, 125.5, 125.4, 123.3, 120.7, 118.9, 114.4, 107.1, 68.2, 31.6,
30.2, 29.5, 29.2, 25.9, 22.5, 13.9. FTIR (KBr, cm ): 2926, 2856,
2214, 1728, 1275, 1124, 1070. EM (EI) m/z (%I): 594 (M , 29),
3
, 75 MHz): δ 154.0, 150.3, 137.9, 129.8,
2.8, 14.2. FTIR (KBr, cm-1): 3055, 2923, 2852, 1693, 1620,
+
-1
593, 1274, 1230. MS (EI) m/z (%I): 678 (M , 100), 510 (30),
+
42 (59). Anal. Calcd for C46
H
62
O
4
: C, 81.37; H, 9.21. Found:
C, 81.18; H, 9.33.
38 2 2 2
510 (10), 426 (45), 149 (100). Anal. Calcd for C36H N O S :
(
R)-2,2′-Dicya n om et h yl-6,6′-d ifor m yl-1,1′-b in a p h t h a -
C, 72.69; H, 6.44; N, 4.71. Found: C, 72.05; H, 8.13; N, 2.06.
2,6-Bis[2-(5-for m yl-2-th ien yl)vin yl]-1,5-bis(h exyloxy)-
n a p h th a len e (19). To a refluxing solution of 200 mg (0.34
mmol) of dicyano derivative 23 in 25 mL of dry dichloro-
methane under argon atmosphere was added dropwise 0.68
mL (0.68 mmol) of a 1 M solution of DIBAL-H in dichloro-
methane. After 5 h, the reaction mixture was allowed to reach
room temperature and methanol was added to the crude. The
precipitated yellow solid was treated portionwise with con-
centrated HCl solution until dissolution of the solid. The
mixture was extracted with chloroform, and the organic layers
were combined and dried over magnesium sulfate. After
vacuum evaporation of the solvent, the remaining residue was
chromatographically purified (silica gel, hexane/dichloromethane
len e (13). A solution of 85 mg (43.0 mmol) of tosylmethyliso-
cyanide (TosMIC) in dry THF was added dropwise under argon
atmosphere to another solution of 107 mg (0.9 mmol) of
potassium tert-butoxide in 2 mL of dry THF, and the mixture
was cooled to -30 °C. Afterward, a solution of 136 mg (0.2
mmol) of dialdehyde 12 was added and stirred for 30 min at
-
30 °C. Then 3 mL of methanol was added, and the mixture
was heated to 80 °C for 15 min. Then the crude reaction was
allowed to reach room temperature, and the solvent was
vacuum evaporated. A 1 mL portion of glacial acetic acid and
a 20 mL portion of water were added to the solid residue
obtained. The mixture was extracted three times with chlo-
roform, and the combined organic layers were washed twice
with a 10% NaHCO
3
aqueous solution and then with water.
(3:7)) to yield 130 mg (64%) of compound 19 as a yellowish
1
After the compound was dried over magnesium sulfate, the
solvent was vacuum evaporated to yield an oil residue, which
was further purified chromatographically (silica gel, hexane/
solid. Mp: 150-151 °C. H NMR (CDCl
3
, 300 MHz): δ 9.89 (s,
2 H, -CHO), 7.89 (d, 2 H, J ) 8.8 Hz), 7.72 (d, 2 H, J ) 8.8
Hz), 7.67 (d, 2 H, J trans ) 15.9 Hz), 7.69 (d, 2 H, J ) 3.9 Hz),
7.34 (d, 2 H, J trans ) 16.1 Hz), 7.21 (d, 2 H, J ) 3.9 Hz), 4.01
(t, 4 H), 1.98 (q, 4 H), 1.65 (s, 4 H), 1.43 (m, 8 H), 0.95 (t, 6 H).
diethyl ether (7:3)) to afford 70 mg (50%) of 13 as a greenish
1
oil. H NMR (CDCl
3
, 300 MHz): δ 7.85 (d, 2 H, J ) 9.0 Hz),
1
3
7
3
.83 (s, 2 H), 7.36 (d, 2 H, J ) 9.0 Hz), 7.07-6.97 (m, 4 H),
.93 (t, 4 H), 3.82 (s, 4 H), 0.91-0.61 (m, 40 H), 0.54 (t, 6 H).
3
C NMR (CDCl , 75 MHz): δ 182.5, 154.2, 137.2, 130.0, 127.3,
130.0, 127.3, 126.7, 125.7, 123.5, 121.8, 119.1, 76.0, 31.8, 30.4,
26.0, 22.7, 14.1. FTIR (KBr, cm ): 2926, 2854, 1661, 1226.
EM (EI) m/z (%I): 600 (M , 87), 516 (20), 432 (100). Anal. Calcd
1
3
-1
C NMR (CDCl
3
, 75 MHz): δ 155.0, 133.5, 129.0, 128.9, 126.8,
+
1
2
26.4, 125.8, 124.6, 120.1, 117.9, 116.3, 69.6, 31.9, 30.6, 30.3,
9.7, 29.5, 29.4, 29.3, 29.1, 25.6, 23.5, 22.7, 14.1. FTIR (neat
for C36
40 4 2
H O S : C, 71.97; H, 6.71; S, 10.67. Found: C, 71.29;
-
1
film, cm ): 2923, 2852, 2252, 1597, 1275, 1248. MS (EI) m/z
H, 6.85; S, 9.69.
+
(
%I): 700 (M , 100), 532 (32), 364 (84). Anal. Calcd for
: C, 82.24; H, 9.20; N, 4.00. Found: C, 82.30; H,
.30; N, 3.83.
,6-Bis[2-(5-br om o-2-th ien yl)vin yl]-1,5-bis(h exyloxy)-
n a p h th a len e (22). To a stirred solution of 300 mg (0.28 mmol)
6-Br om o-2-d od ecyloxyn a p h th a len e (32). To a solution
of 7.0 g (31 mmol) of 6-bromo-2-hydroxynaphthalene (31) in
40 mL of dry acetone was added 8.6 g (62 mmol) of anhydrous
potassium carbonate, 23 mL (93 mmol) of 1-bromododecane,
and a catalytic amount of sodium iodide, and the mixture was
48 64 2 2
C H O N
9
2

7
510 J . Org. Chem., Vol. 65, No. 22, 2000
G o´ mez et al.
refluxed for 72 h. After the reaction was cooled, 50 mL of water
was added, and then the mixture was extracted three times
with dichloromethane. The combined organic layers were
washed with water and dried with magnesium sulfate. The
solvent was vacuum evaporated to yield an oil which was
vacuum distilled to remove unreacted 1-bromododecane. After
chromatography (silica gel, hexane/dichloromethane (9:1)) of
to cool to room temperature. Afterward, the polymers were
precipitated with the addition of methanol. Further purifica-
tion was accomplished by washing the polymers twice with
methanol and once with diethyl ether. Dry vacuuming for a
few hours gives the polymers as colored solids.
Ch a r a cter iza tion of P olym er 1. By following the general
procedure and using monomers 12 and 13 as starting materi-
the residue, 11 g (90%) of 32 was obtained as a white solid.
als, we obtained polymer 1 as a dark yellow solid. Yield: 90%.
H NMR (CDCl , 300 MHz): δ 8.40 (s, 2 H), 8.22 (s, 2 H), 8.02
3
1
1
Mp: 62-63 °C. H NMR (CDCl
3
, 300 MHz): δ 7.90 (d, 1 H, J
)
1.7 Hz), 7.62 (d, 1 H, J ) 8.5 Hz), 7.53 (m, 1 H), 7.48 (dd, 1
H, J ) 8.5, J ) 1.9 Hz), 7.15 (dd, 1 H, J ) 8.8, J ) 2.4 Hz),
.08 (d, 1 H, J ) 2.4 Hz), 3.85 (t, 2 H), 1.64 (q, 2 H), 1.08 (s,
8 H), 0.69 (t, 3 H). 13C NMR (CDCl
, 75 MHz): δ 157.4, 133.0,
(m, 4 H), 7.80 (d, 2 H, J ) 9.0 Hz), 7.67 (s, 2 H), 7.52 (d, 2 H,
J ) 9.1 Hz), 7.45 (m, 4 H), 7.20 (d, 4 H, J ) 8.8 Hz), 3.98 (s,
8 H), 1.60 (s, 4 H), 1.42 (s, 8 H), 1.19 (s, 68 H), 0.83 (s, 12 H).
1
2
1
2
7
1
1
2
-1
3
FTIR (film, cm ): 3050, 2926, 2853, 2213, 1621, 1593. Anal.
29.9, 129.6, 129.4, 128.3, 128.2, 120.0, 116.8, 106.4, 68.0, 31.9,
9.6, 29.6, 29.6, 29.4, 29.3, 29.1, 26.0, 22.6, 14.1. FTIR (KBr,
122 2 4 n
Calcd for [C94H N O ] : C, 84.00; H, 9.15; N, 2.08. Found:
C, 83.66; H, 9.25; N, 2.04.
Ch a r a cter iza tion of P olym er 2. By following the general
procedure and using monomers 13 and 14 as starting materi-
-
1
cm ): 3018, 1627, 1591, 1500, 1261, 1215. MS (EI) m/z (%I):
+
3
90 (M , 30), 224 (100). Anal. Calcd for C22
H, 8.01. Found: C, 67.60; H, 7.98.
-Dod ecyloxy-6-for m yln a p h th a len e (33). To a solution
H31OBr: C, 67.67;
als, we obtained polymer 2 as a dark yellow solid. Yield: 80%.
1
2
3
H NMR (CDCl , 300 MHz): δ 8.44 (d, 2 H, J ) 9.0 Hz), 8.30
of 10 g (25 mmol) of 32 in 100 mL of dry THF at -78 °C under
argon atmosphere was added 31 mL of a 1.5 M solution of
n-butyllithium (50 mmol) in hexane. After 6 h, 26.3 mL of dry
N,N-dimethylformamide was added, and the reaction was
allowed to stay at -78 °C for an additional 2 h. Then it was
poured, under vigorous stirring, on a water/ice/HCl mixture
(s, 2 H), 8.18 (s, 2 H), 8.07 (d, 2 H, J ) 9.0 Hz), 8.00 (d, 2 H,
J ) 8.8 Hz), 7.61 (d, 2 H, J ) 9.2 Hz), 7.51 (d, 2 H, J ) 9.2
Hz), 7.26 (d, 2 H, J ) 8.8 Hz), 4.03 (m, 8 H), 1.9 (m, 4 H), 1.5
(m, 4 H), 1.4-0.9 (m, 48 H), 0.8 (m, 12 H). 13C NMR (CDCl
,
3
75 MHz): δ 155.9, 155.6, 135.0, 134.2, 130.2, 129.3, 128.8,
126.7, 126.3, 125.0, 124.8, 122.4, 119.8, 119.1, 118.1, 117.5,
116.1, 112.6, 77.1, 69.4, 31.8, 31.6, 30.3, 29.7, 29.6, 29.5, 29.3,
(pH < 1). The mixture was extracted three times with
-
1
methylene dichloride, and the organic layers were combined
and washed twice with water and dried over magnesium
sulfate. After vacuum evaporation of the solvent, an orange
oil was obtained which was chromatographically purified
29.2, 29.1, 25.9, 25.6, 22.6, 22.5, 14.0, 13.9. FTIR (film, cm ):
3060, 2855, 2214, 1682, 1621. Anal. Calcd for [C72
92 2 4 n
H N O ] :
C, 82.40; H, 8.83; N, 2.67. Found: C, 81.00; H, 8.84; N, 2.45.
Ch a r a cter iza tion of P olym er 3. By following the general
procedure and using monomers 12 and 15 as starting materi-
(
silica gel, hexane/diethyl ether (95:5)) to yield 8 g (94%) of 12
1
1
as a white solid. Mp: 45-47 °C. H NMR (CDCl
3
, 300 MHz):
als, we obtained polymer 3 as an orange solid. Yield: 90%. H
δ 10.08 (s, 1 H, CHO), 8.23 (s, 1 H), 7.91 (m, 1 H), 7.87 (m, 1
NMR (CDCl , 300 MHz): δ 8.37 (s, 2 H), 8.04 (d, 2 H), 7.79 (d,
3
H), 7.79 (d, 1 H, J ) 8.4 Hz), 7.24 (dd, 1 H, J
1
) 9.9 Hz, J
2
)
2 H), 7.98 (d, 2 H), 7.78 (s, 2 H), 7.59 (d, 2 H), 7.42 (d, 2 H),
2
1
.5 Hz), 7.16 (d, 1 H, J ) 2.2 Hz), 4.14 (t, 2 H), 1.90 (q, 2 H),
7.07 (d, 2 H), 3.95 (s, 8 H), 1.77 (s, 8 H), 1.38-0.98 (m, 48 H),
1
3
-1
.30 (s, 18 t), 0.91 (t, 3 H). C NMR (CDCl
3
, 75 MHz): δ 191.8
0.77 (s, 12 H). FTIR (film, cm ): 3028, 2969, 2214, 1622. Anal.
(CHO), 159.7, 138.2, 134.1, 132.1, 130.9, 127.7, 127.5, 123.4,
Calcd for [C72
92 2 4 n
H N O ] : C, 82.40; H, 8.83; N, 2.67. Found: C,
1
1
20.0, 106.6, 68.1, 31.7, 29.5, 29.4, 29.2, 29.2, 28.9, 25.9, 22.5,
82.06; H, 8.77; N, 2.74.
Ch a r a cter iza tion of P olym er 4. By following the general
procedure and using monomers 13 and 16 as starting materi-
-1
3.9. FTIR (KBr, cm ): 2954, 2849, 1691, 1625, 1261. MS (EI)
+
m/z (%I): 340 (M , 18), 172 (100). Anal. Calcd for C23
C, 81.12; H, 9.48. Found: C, 81.19; H, 9.48.
32 2
H O :
1
als, we obtained polymer 4 as a red solid. Yield: 99%. H NMR
6
-Cya n om eth yl-2-d od ecyloxyn a p h th a len e (34). Under
3
(CDCl , 300 MHz): δ 8.13 (s, 2 H), 7.95 (d, 2 H, J ) 8.9 Hz),
an argon atmosphere, a solution of 2.7 g (14.0 mmol) of
tosylmethylisocyanide (TosMIC) in 45 mL of dry THF was
added dropwise to another solution of 3.41 g (14 mmol) of
potassium tert-butoxide in 45 mL of dry THF, and the mixture
was cooled to -30 °C. Afterward, a solution of 4 g (12 mmol)
of aldehyde 33 in 70 mL of dry THF was added and stirred
for 30 min at -30 °C. Then 65 mL of methanol was added,
and the mixture was heated to 80 °C for 15 min. Then the
crude reaction was allowed to reach room temperature, and
the solvent was vacuum evaporated. A 3 mL portion of glacial
acetic acid and a 60 mL portion of water were added to the
solid residue obtained. The mixture was extracted three times
with chloroform, and the combined organic layers were washed
7.73 (s, 2 H), 7.58 (s, 2 H), 7.40 (d, 4 H, J ) 8.9 Hz), 7.12 (m,
2 H), 3.92 (s, 4 H), 1.36 (s, 4 H), 1.13 (s, 18 H), 0.92 (s, 18 H),
0.78 (t, 6 H). 13C NMR (CDCl
, 75 MHz): δ 155.8, 141.0, 134.3,
3
131.6, 131.2, 128.9, 128.4, 126.8, 122.2, 120.0, 118.6, 116.1,
111.8, 110.6, 104.7, 69.2, 31.9, 29.7, 29.4, 29.3, 29.1, 25.7, 22.7,
-
1
14.1. FTIR (film, cm ): 3040, 2923, 2212, 1619, 1593, 1276,
1246. Anal. Calcd for [C54 S] : C, 80.55; H, 8.01; N,
H
64
N
2
O
2
n
3.48; S, 3.98. Found: C, 78.88; H, 8.01; N, 3.72; S, 4.32.
Ch a r a cter iza tion of P olym er 5. By following the general
procedure and using monomers 12 and 17 as starting materi-
als, we obtained polymer 5 as a dark yellow solid. Yield: 93%.
1
H NMR (CDCl , 300 MHz): δ 8.25 (s, 2 H), 7.96 (d, 2 H, J )
3
8.8 Hz), 7.75 (d, 2 H, J ) 8.9 Hz), 7.40 (s, 4 H), 7.34 (s, 2 H),
7.19-7.12 (m, 2 H), 3.92 (s, 4 H), 1.36 (s, 4 H), 1.13 (s, 18 H),
3
twice with 10% NaHCO aqueous solution and then with
water. After drying over magnesium sulfate, we vacuum
evaporated the solvent to yield an oil residue, which was
further purified chromatographically (silica gel, hexane/diethyl
ether (8:2)) to afford 2.1 g (50%) of 34 as a white solid. Mp:
7-88 °C. H NMR (CDCl
.05 (m, 3 H), 3.99 (s, 2 H), 3.80 (s, 2 H), 1.77 (s, 2 H), 1.20 (s,
8 H), 0.81 (s, 3 H). C NMR (CDCl
29.0, 129.0, 127.7, 126.6, 125.8, 125.0, 120.0, 106.4, 68.1, 31.9,
9.6, 29.4, 29.2, 26.1, 23.6, 22.6, 14.1. FTIR (KBr, cm ): 2918,
0.92 (s, 18 H), 0.78 (t, 6 H). 13C NMR (CDCl
3
, 75 MHz): δ 156.5,
140.4, 135.2, 131.1, 130.7, 128.7, 128.4, 127.5, 126.3, 125.5,
119.8, 116.8, 115.9, 104.0, 69.4, 32.0, 29.8, 29.8, 29.6, 29.5, 29.3,
-
1
29.2, 25.8, 22.8, 14.2. FTIR (film, cm ): 3052, 2924, 2215,
1618, 1577, 1275, 1250. Anal. Calcd for [C54 S] : C,
1
8
7
1
1
2
2
3
, 300 MHz): δ 7.65 (s, 3 H), 7.28-
H
64
N
2
O
2
n
80.55; H, 8.01; N, 3.48; S, 3.98. Found: C, 79.10; H, 7.94; N,
3.47; S, 3.69.
Ch a r a cter iza tion of P olym er 6. By following the general
procedure and using monomers 13 and 18 (in this case
dialdehyde 18 was dissolved in dichloromethane instead of
1
3
3
, 75 MHz): δ 158.2, 134.8,
-1
+
253, 1606, 1265, 1225. MS (EI) m/z (%I): 351 (M , 45), 183
+
(
9
M , 100), 157 (19). Anal. Calcd for C24
H
33NO: C, 82.00; H,
THF) as starting materials, we obtained polymer 6 as a yellow
1
.46; N, 3.98. Found: C, 81.97; H, 9.47; N, 3.88.
Syn th esis of P olym er s. Gen er a l P r oced u r e. Under an
argon atmosphere, a solution of 0.14 mmol of the dialdehyde
in 2 mL of dry THF was added to a solution of the correspond-
ing bis(cyanomethyl) derivative in 5 mL of tert-butanol. Then
5 mg (0.14 mmol) of BuOK and a few drops of a 1 M solution
of tetrabutylammonium hydroxide in methanol were added.
The reaction was heated to 50 °C for 20 min and then allowed
solid. Yield: 90%. H NMR (CDCl
3
, 300 MHz): δ 8.44 (d, 2 H,
J ) 9.02 Hz), 8.30 (s, 4 H), 8.18 (s, 4 H), 8.09-7.87 (m, 8 H),
7.79 (s, 4 H), 7.64-7.45 (m, 4 H), 7.17-7.13 (m, 2 H), 4.04 (s,
16 H), 1.99 (s, 14 H), 1.69 (s, 14 H), 1.44 (s, 28 H), 1.21 (s, 16
H), 0.95 (s, 16 H), 0.85-0.79 (m, 24 H). 13C-RMN (CDCl
, 75
3
t
4
MHz): δ 156.1, 155.6, 153.5, 153.3, 135.4, 134.2, 133.6, 131.1,
130.1, 129.8, 129.7, 129.6, 128.9, 128.3, 126.9, 126.8, 126.6,
126.4, 124.6, 123.8, 123.7, 123.5, 122.5, 120.0, 119.0, 118.4,

Novel Optically Active Polyarylene Vinylenes
J . Org. Chem., Vol. 65, No. 22, 2000 7511
1
2
16.2, 111.8, 76.0, 69.5, 31.9, 31.8, 31.7, 30.6, 30.5, 29.7, 29.6,
9.4, 29.2, 26.2, 26.0, 25.7, 22.7, 22.7, 22.6, 14.1, 14.0. FTIR
Ch a r a cter iza tion of Mod el Com p ou n d 27. By following
the general procedure and using 16 and 34 as starting
materials, we obtained model compound 26 as a red solid.
-
1
(
film, cm ): 3068, 2955, 2924, 2215, 1618, 1593, 1275. Anal.
Calcd for [C110 : C, 80.83; H, 9.62; N, 1.71. Found:
C, 78.99; H, 9.42; N, 1.69.
H
156
N
2
O
8
]
n
Yield: 85%. Mp: 131-132 °C.
1
H NMR (CDCl , 300 MHz): δ
3
8
.02 (s, 2 H), 7.88 (d, 2 H, J ) 8.04 Hz), 7.80-7.71 (m, 4 H),
Ch a r a cter iza tion of P olym er 7. By following the general
procedure and using monomers 13 and 19 as starting materi-
als, we obtained polymer 7 as a red solid. Yield: 90%. H NMR
7.64-1.43 (m, 4 H), 7.20-7.02 (m, 4 H), 4.09 (t, 4 H), 1.77-
1.73 (m, 4 H), 1.20 (s, 36 H), 0.81 (t, 6 H). 13C NMR (CDCl3,
75 MHz): δ 159.9, 135.6, 132.4, 130.7, 129.3, 128.5, 121.3,
1
(
CDCl
3
, 300 MHz): δ 8.18 (s, 2 H), 8.01 (d, 2 H, J ) 8.2 Hz),
.88 (d, 2 H, J ) 8.4 Hz), 7.72-7.38 (m, 10 H), 7.21-7.16 (m,
H), 3.99 (s, 8 H), 1.59 (s, 8 H), 1.43 (s, 16 H), 1.21 (s, 24 H),
.94 (s, 8 H), 0.90-0.85 (m, 12 H). 13C NMR (CDCl
, 75 MHz):
1
3
1
4
20.9, 120.4, 120.0, 118.8, 118.4, 113.2, 107.3, 68.9, 32.6, 30.3,
0.0, 29.9, 26.8, 23.4, 14.8. FTIR (KBr): 2928, 2852, 2216,
7
8
0
+
630, 1473, 1207, 848, 794. EM (ESI) m/z (%I): 829 (M + 23,
3
8), 685 (100). Anal. Calcd for C54
66 2 2
H N O S: C, 80.35; H, 8.24;
δ 155.6, 153.8, 137.0, 134.0, 133.1, 132.5, 130.0, 129.9, 129.8,
N, 3.47; S, 3.97. Found: C, 80.09; H, 8.50; N, 3.65; S, 4.00.
1
1
2
1
28.9, 126.6, 126.3, 126.0, 123.6, 122.3, 120.0, 119.0, 118.4,
16.2, 107.8, 69.5, 31.9, 31.7, 30.4, 29.7, 29.6, 29.4, 29.2, 26.0,
Ch a r a cter iza tion of Mod el Com p ou n d 28. By following
the general procedure and using 17 and 33 as starting
5.7, 22.7, 22.7, 14.1. FTIR (film, cm- ): 3045, 2926, 2209,
1
materials, we obtained model compound 28 as a red solid.
620, 1592, 1277. Anal. Calcd for [C84
100 2 4 2 n
H N O S ] : C, 79.70;
1
H, 7.96; N, 2.21; S, 5.07. Found: C, 78.50; H, 7.99; N, 2.33; S,
.91.
Syn th esis of Mod el Com p ou n d s. Gen er a l P r oced u r e.
Yield: 85%. Mp: 125-128 °C. H NMR (CDCl
3
, 300 MHz): δ
4
8.11 (s, 2 H), 8.00 (s, 2 H), 7.90 (s, 2 H), 7.74 (s, 4 H), 7.56 (s,
4
1
H), 7.40 (s, 2 H), 4.21 (s, 4 H), 1.98 (s, 4 H), 1.41 (s, 36 H),
.02 (s, 6 H). 13C NMR (CDCl
, 75 MHz): δ 159.1, 139.8, 140.5,
Under an argon atmosphere, a solution of 0.4 mmol of the
monoaldehyde-substituted (or 0.2 mmol of the dialdehyde-
substituted) derivative in dry THF was added to a solution of
3
136.0, 130.9, 130.5, 128.5, 127.7, 127.3, 125.5, 120.2, 116.7,
106.7, 103.9, 68.3, 32.0, 29.7, 29.4, 29.2, 26.1, 22.8, 14.2. FTIR
-
1
0
.2 mmol of the bis(cyanomethyl)-substituted derivative (or 0.4
(KBr, cm ): 2920, 2850, 2214, 1628, 1276. EM (ESI) m/z
+
mmol of the mono(cyanomethyl)-substituted derivative) in 5
(%I): 829 (M + 23, 100), 685 (18). Anal. Calcd for
t
mL of tert-butanol. Then 0.4 mmol of BuOK and a few drops
54 66 2 2
C H N O S: C, 80.35; H, 8.24; N, 3.47; S, 3.97. Found: C,
of a 1 M solution of tetrabutylammonium hydroxide in
methanol were added. After heating to 50 °C for 30 min, we
allowed the reaction to cool to room temperature, and the
model compounds were precipitated with the addition of
methanol and then filtered.
Ch a r a cter iza tion of Mod el Com p ou n d 24. By following
the general procedure and using 33 and 34 (in this case,
equimolecular amounts of both reactives) as starting materials,
77.92; H, 7.96; N, 3.48; S, 3.98.
Ch a r a cter iza tion of Mod el Com p ou n d 29. By following
the general procedure and using 18 and 34 as starting
materials, we obtained model compound 29 as a red solid.
1
Yield: 92%. Mp: 146-148 °C. H NMR (CDCl
3
, 300 MHz): δ
8
2
.42 (d, 2 H, J ) 9.0 Hz), 8.20 (s, 2 H), 8.16 (s, 2 H), 8.02 (d,
H, J ) 9.3 Hz), 7.98-7.89 (m, 8 H), 7.84 (s, 2 H), 7.80-7.79
(
m, 6 H), 7.23-7.20 (m, 2 H), 7.16 (m, 4 H), 4.08 (t, 16 H),
2.03-1.68 (m, 20 H), 1.68-1.57 (m, 8 H), 1.57-1.56 (m, 8 H),
we obtained model compound 24 as a white solid. Yield: 90%.
1
Mp: 173 °C. H NMR (CDCl
(
1
3
, 300 MHz): δ 8.05 (s, 1 H), 7.93
1
3
1
.46-0.97 (m, 52 H), 0.89 (t, 12 H), 0.88 (t, 12 H). C NMR
(CDCl , 75 MHz): δ 158.2, 156.2, 153.6, 153.4, 135.8, 134.9,
31.2, 130.0, 129.8, 128.9, 128.7, 128.4, 127.7, 126.8, 126.1,
s, 2 H), 7.66-7.94 (m, 6 H), 7.09-6.97 (m, 4 H), 3.91 (s, 4H),
.69 (s, 4 H), 1.11 (s, 36 H), 0.72 (s, 6 H). 1 C NMR (CDCl
3
3
3
, 75
1
1
1
MHz): δ 158.7, 158.0, 141.1, 135.5, 134.4, 130.0, 129.7, 129.4,
24.5, 124.5, 123.8, 123.6, 122.9, 120.1, 119.0, 118.5, 111.9,
06.6, 68.2, 31.9, 31.9, 31.7, 30.6, 30.5, 29.6, 29.4, 29.4, 29.2,
1
1
29.0, 128.5, 128.4, 127.4, 127.2, 125.6, 122.8, 120.0, 119.8,
10.0, 106.5, 68.0, 31.7, 29.4, 29.1, 29.0, 25.9, 22.5, 14.0. FTIR
-
1
-1
(KBr, cm ): 2955, 2224, 1628, 1603, 1244, 1202. MS (EI) m/z
26.2, 26.0, 25.9, 22.8, 22.7, 22.7, 14.1, 14.0. FTIR (KBr, cm ):
2924, 2852, 2224, 1628, 1603. EM (ESI) m/z (%I): 1777 (M
23, 100).
+
+
(
9
%I): 674 (M , 100). Anal. Calcd for C47
.43; N, 2.08. Found: C, 83.75; H, 9.25; N, 2.02.
Ch a r a cter iza tion of Mod el Com p ou n d 25. By following
H
63NO
2
: C, 83.75; H,
+
Ch a r a cter iza tion of Mod el Com p ou n d 30. By following
the general procedure and using 19 and 33 as starting
the general procedure and using 14 and 34 as starting
materials, we obtained model compound 25 as a yellow solid.
materials, we obtained model compound 30 as a red solid.
1
Yield: 90%. Mp: 130-133 °C. H NMR (CDCl
3
, 200 MHz): δ
1
Yield: 95%. Mp: 174-176 °C. H NMR (CDCl
3
, 300 MHz): δ
8
.49 (d, 2 H, J ) 8.9 Hz), 8.20 (d, 4 H, J ) 2.3 Hz), 8.06 (d, 2
8
.03 (s, 2 H), 7.87 (d, 2 H, J ) 8.8 Hz), 7.74 (d, 2 H, J ) 8.8
H, J ) 8.9 Hz), 7.88 (s, 2 H), 7.83 (d, 4 H, J ) 2.3 Hz), 7.30-
Hz), 7.69-7.65 (m, 4 H), 7.64 (s, 4 H), 7.60-7.58 (m, 2 H),
7
8
.23 (m, 2 H), 7.20 (s, 2 H), 4.16-4.05 (m, 8 H), 2.05-1.83 (m,
7
7
1
0
.53 (d, 2 H, J trans ) 16.6 Hz), 7.31 (d, 2 H, J trans ) 16.3 Hz),
.20-7.10 (m, 6 H), 4.09-3.98 (m, 8 H), 2.03-1.96 (m, 4 H),
.86-1.81 (m, 4 H), 1.67 (s, 4 H), 1.46-1.44 (m, 44 H), 1.00-
13
3
H), 1.61-1.32 (m, 48 H), 0.90 (t, 12 H). C NMR (CDCl , 75
MHz): δ 158.1, 155.9, 135.1, 134.7, 130.1, 129.8, 129.3, 128.4,
1
1
2
2
27.5, 126.0, 124.9, 124.8, 122.6, 119.9, 119.1, 118.1, 112.5,
.85 (m, 12 H). 13C NMR (CDCl
, 75 MHz): δ 158.1, 153.8,
3
06.3, 77.0, 67.9, 31.7, 31.5, 30.3, 29.4, 29.2, 29.2, 29.0, 25.9,
5.8, 22.5, 22.4, 13.9, 13.8. FTIR (KBr, cm-1): 2920, 2849,
137.0, 134.6, 133.0, 132.5, 129.8, 129.0, 128.7, 127.6, 126.6,
126.0, 123.6, 122.0, 121.9, 120.1, 119.0, 113.5, 112.0, 111.1,
+
215, 1601, 1273. MS (ESI) m/z (%I): 1073 (M + 23, 100), 685
57). Anal. Calcd for C72H N O : C, 82.24; H, 9.01; N, 2.66.
94 2 4
1
06.6, 67.7, 31.9, 31.8, 30.4, 29.6, 29.4, 26.0, 22.7, 14.1. FTIR
(
-
1
(KBr, cm ): 2922, 2851, 2216, 1628, 1601. EM (ESI) m/z
Found: C, 82.40; H, 8.94; N, 2.61.
Ch a r a cter iza tion of Mod el Com p ou n d 26. By following
the general procedure and using 15 and 33 as starting
+
(
%I): 1289 (M + 23, 48), 685 (100). Anal. Calcd for
84 102 2 4 2
C H N O S : C, 79.58; H, 8.11; N, 2.21; S, 5.06. Found: C,
7
9.00; H, 8.08; N, 2.29; S, 5.06.
materials, we obtained model compound 26 as a yellow solid.
1
Yield: 45%. Mp: 119-120 °C. H NMR (CDCl
3
, 300 MHz): δ
8
.04 (s, 2 H), 7.96 (d, 2 H, J ) 8.6 Hz), 7.82 (d, 2 H, J ) 8.7
Ack n ow led gm en t. This work has been supported
Hz), 7.63 (s, 6 H), 7.46 (d, 2 H, J ) 8.4 Hz), 7.02 (d, 2 H, J )
by the DGESIC of Spain (Project PB98-0818). R.G.
is indebted to the European Commission (Contract
J OR3CT980206). We are also indebted to Dr. G. Orel-
lana for the photoluminescence measurements, Dr. J .
San Rom a´ n and A. Gallardo for GPC measurements,
and Centro de Espectroscop ´ı a de la UCM.
5
0
1
1
2
.7 Hz), 6.96 (s, 2 H), 3.85 (t, 8 H), 1.65 (s, 8 H), 1.06 (s, 48 H),
1
3
.63 (t, 12 H). C NMR (CDCl , 75 MHz): δ 158.7, 153.2, 147.3,
3
35.7, 130.5, 130.2, 128.9, 128.2, 127.3, 126.9, 125.5, 125.3,
19.9, 119.0, 118.5, 106.4, 105.9, 75.0, 68.0, 31.7, 31.4, 30.1,
9.5, 29.2, 29.0, 25.9, 25.7, 22.5, 22.4, 13.9, 13.8. FTIR (KBr,
-
1
cm ): 2924, 2852, 2212, 1624, 1605, 1265. MS (ESI) m/z
+
(
%I): 1073 (M + 23, 100), 685 (14). Anal. Calcd for
: C, 82.24; H, 9.01; N, 2.66. Found: C, 82.17; H,
.05; N, 2.62.
72 94 2 4
C H N O
9
J O000761K