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Felix Steybe°, Franz Effenbergera*, Ulrich Gubler b, Christian Bosshard b*, and Peter Gth'aterb
Abstract: A series of new chiral donor-acceptor substituted mono- (la,b), bi- (2a,b,f) and terthiophenes (3)
as well as thienyl- and bithienylpyridinium salts ld-f and 2bk with various counterions has been synthesized.
This class of thiophenes exhibit excellent molecular nonlinear optical properties such as second-order polari-
zahilities 13 or second-order hyperpolarizabilities 7. With respect to an application as nonlinear optical mate-
rials, some of these compounds have been investigated by Kurtz powder technique as well as by X-ray
crystallographic analysis, The second-harmonic generation (SHG) powder efficiencies are measured at 1.064
pra and 1.3 ~an with urea as reference. Furthermore, the influence of the chiral donors prolinol and methoxy-
methylpyrrolidine in the thiophene derivatives as well as the variation of counterions in the pyridinium salts
on the orientation of the chromophores in the crystalline lattice was investigated. © 1998 ElsevierScience Ltd. All
rights reserved.
Keywords: Chromophores;Donor-acceptorsystems;Electronic spectra; Thiophenes
Introduction
New nonlinear optical (NLO) materials showing large macroscopic susceptibilities (Z(")) have attracted
considerable attention since they may be of interest for numerous applications.l It is well established that n-
donor-acceptor compounds with large differences between ground state and excited state dipole moments as
well as large transition dipole moments hold positively promise as NLO materials. Based on these criteria
chromophores with thiophene subunits are excellent candidates and have been investigated intensively in the
last few years. 2 It is nowaday undisputed that they exhibit enhanced second order polarizabilities (15) com-
pared to n-systems with phenylene bridges. For applications in electrooptical devices the NLO chromophores
should be thermally and photochemically stable at continuous operating temperatures of 80°C. As far as
thermal stability is concerned, c~-oligothiophenes strike a good compromise between the stability of the phe-
nyl ring and the excellent polarizability of a polyene.3, 4a With respect to photostability they tend to be more
stable compared to stilbenes where 2+2 cycloaddition reaction even in the solid phase was observed. 5
In recem publications a series of novel donor-acceptor substituted oligothiophenes with particularly attrac-
tive molecular nonlinear optical properties has been described. 4 Nevertheless for observable second-order
bulk effects (g (z)) such as second harmonic generation (SHG) or electrooptical effects it is imperative that the
molecule resides in a noncentrosymmetric stable environment with a high chromophoric density. Besides
glassy as well as liquid crystal mono- and polymers, self-assembly multilayers or Langmuir-Blodgett films
single crystals are a promising approach to produce long-living stable chemical structures, since a time con-
stant orientation of the chromophore in the lattice can be imposed.l Unfortunately, about 75% of all known
achiral compounds crystallize in centrosymmetric space groups and thus have vanishing Z(2).6 A strategy for
insuring noncentrosymmetric crystal structures is the incorporation of chiral substituents. Prototypical exam-
pies for this approach are N-(4-nitrophenyl)-(L)-prolinol (NPP) 7a and 2-(N-prolinol)-5-nitropyridine (pNp).7b
These nonlinear optical materials have a large SHG powder efficiency (100 times that of urea). The simul-
taneous chiral and hydrogen bonding character of the prolinol electron donating group leads to a quasioptimal
angle between the molecular transition dipole moments and the twofold axis of the monoclinic P2~ crystal
structures.
Meredith,S and more recentlyMardcr ct al.5,6,9and othersI0 have demonstrated thatmolecular saltswherein
one ion possesses a large molecular hyperpolarizability03) exhibited in many cases large macroscopic
second-order nonlinearities.One of thc most successfulexamples for the development of second-order N L O
materials is 4'-N,N-dimethylamino-4-N-mcthylstilbazolium toluenc-p-sulfonate(DAST). This material has
values for S H G powder efficiency1000 times that of urea and very large electroopticcoefficients(rllabout
90 p m V "~at ~.=720 nm). lI
Another possibilityis thc supramolecular syntheticapproach, which is the design of molecular or ionic ag-
gregates or assemblics to favour the desirablecrystalpacking. The induction of a net dipole in a co-crystal
was firstdemonstrated by Ettcr ct al.12with the complimentary host-guestpair of 4-aminobenzoic acid and
3,5-dinitrobenzoicacid. However, thc S H G signal generated by this co-crystalwas in the order of the urea
standard.12Itwas recentlyreported that extended molccules such as merocyanine dyes can be co-crystallized
and yield largcsecond-ordcr nonlinearities.13
In this paper wc report on donor-acceptor substitutedthiophenes and oligothiophencs bearing chiral
methoxyprolinc or prolinolsubstituentsas donors. As an attempt to furtherdefine the scope and limitationsof
the "saltmethodology" a number of D A S T analogous thiophene-4-mcthyl pyridinium derivativeswith dif-
ferent chain length wcrc synthesized.In order to induce nonccntrosyrnmetriccrystalstructuresthe counter-
ions of the pyridinium saltswcrc varied. The resultson experiments with crystalsarc reported and crystal
structuresarc presented.
F. Steybe et al. /Tetrahedron 54 (I 998) 8469--8480 8471
/"~"~~..-Me X@
Me2N1 ~ ' ~ b E) XG M e 2 N ' ~ S ~
~,~,,N~.Me
ld (X=I) 2i (X=I)
• (X=CF3SO3) j (X=CF3SO3)
f (X=tosylate) k (X=tosylate)
la lb 1c 2a 2b 2c 2d 2e 2f 3
Scheme 1.
The chiral thiophene lb was prepared according to la by aromatic nucleophilic substitution. 14 According to
terthiophene 34a the compounds 2a-c,f were synthesized by PdCI2(PPh3)2 catalyzed cross coupling reactions
of (trimethylstannyl)thiophenes 4b with acceptor-substituted bromo or iodoaromatic compounds. Starting from
thiophene lc and bithiophene 2c the pyridinium salts ld-f and 2J-k, respectively, were obtained by methy-
lation under standard conditions (see Experimental). The NPP analogue bithiophene 2g was prepared by HF
pyridine assisted removal of the silyl protecting group in 2a. The tricyanovinyl derivative 2h was synthesized
in a one-pot reaction by initial addition of HCN to 2b and subsequent oxidization of the adduct with
Pb(OAc)4.15 The compounds have been characterized by NMR and elemental analysis.
electrooptical absorption (EOA) measurements cannot be applied to the pyridinium salts ld-f and 2i-k, 16a the
second-order polarizability [3 has been measured in the case of I f by hyper-Rayleigh scattering (HRS).I6b The
l[~-value in acetonitrile at 1500 nm, given in Taylor series convention, 17 is 13= (163+24)'10 "s° Cm3v'Z. 18 Un-
fortunately, fluorescence emission of a three photon absorption falsified the HRS result for 2k as bithiophene
analogue to DAST.
The second-order hyperpolarizability y(-3co,co,o),co)was measured by third-harmonic generation (THG) in
solution ]9 at an incident wavelength of 2.1 I~m. The third harmonic frequency at 700 nm is only slightly ab-
sorbed by the samples (e < 30 l.cm'lmol "l) and therefore the y values are only little resonance enhanced.
Molecular second- and third-order polarizabilities as well as dipole moments are sensitive to the nature of
both the n-conjugation and donor-acceptor substitution. From the nitro (2f) to the dicyanovinyl substituted
bithiophene 2b an increase by about a factor of two in the value of y, given in Taylor series convention, 17 is
observed ((62.3± 1.2).10 .6o Cm4V "3 for 2f, (129± 10).10 .60 Cm4V "3 for 2b). The higher acceptor strength of
the dicyanovinyl compared with the nitro group is therefore not only preferable for the first-order
hyperpolarizability [34a but also for the second-order hyperpolarizability 7. Such an increase ofy with increas-
ing acceptor strength has also been reported for other molecules.20a, b We can compare the third-order non-
linearities measured here with similar molecular systems. Substituted biphenyls 20¢ exhibit smaller values of ~,
than bithiophenes 2f, 2b confirming the positive impact of the phenyl replacement by thiophene. The bithio-
phenes have also larger values o f y than stilbenes, 2°¢ what could be due to the slight resonance enhancement
in our measurements.
Compounds 2f and 2b also form nice crystals with an almost parallel alignment of the chromophores in the
crystal lattice. Based on the oriented gas model 2°d and the crystallographic data we can extrapolate huge
values of the macroscopic third-order susceptibility ~3333
.(3) of about 4000 resp. 7000 times g fs
(a) of fused silica
(3~ = 3.9.10 "22 m2V-2).20e
gf~
The synthesized chiral thiophane and oligothiophene derivatives were examined for second harmonic ge-
neration activity using the Kurtz powder technique. 21 The powder efficiencies are summarized in Table 1.
Whereas the phenyl and stilbene systems (NPP and DAST) had powder SHG signals 100 and 1000 times
greater than that of urea, most of the prolinol- and methoxyproline-substituted thiophene, bithiophene and
terthiophene chromophores and the dimethylamino-substituted thiophene and bithiophene pyridinium salts
gave negligible SHG. Only thiophenes la and lb exhibited SHG with an efficiency smaller than that of the
urea reference by using 1064 nm fundamental light. In a qualitative manner the examined materials are
therefore not considered to be of interest for second-order nonlinear optics using single crystals.
F. Steybe et al. /Tetrahedron 54 (1998) 8469-8480 8473
Table 1
Second harmonic powder test of some thiophenes I and oligothiophenes 2, 3 according to Kurtz and Perry at
1.064 gm and 1.3 pm
In order to study the orientation of the chromophores in the crystalline lattice by X-ray we conducted ex-
periments on crystal growth for various compounds. Slow recrystallization from isooctane/benzene on eva-
poration of solvent for la,b, from cyclohexane/benzene/isooctane on evaporation of solvent for 2f, by diffu-
sion of n-hexane, a non-solvent, into a chloroform solution of 2b and 2g, from methanol/ethanol for 2k provi-
ded suitable crystals for X-ray diffraction. Exemplary unit cells of 2f and 2k which crystallized in the acentric
point group 222 and the centric point group 1, respectively, are displayed in Figure 1.
(a (b)
Figure 1. Crystal packing of 2f (a) and 2k (b) viewed along the a axis. Hydrogen atoms were omitted for clarity.
8474 F. Steybe et al. / Tetrahedron 54 (1998) 8469-8480
The basic structures are in accordance with the prediction based on the experimental data described above.
Although the chiral donors in la,b, 2f and 2g induce an acentfic space group (see Experimental), adjacent
rows of chromophores are oriented in an antiparallel manner as can been seen for 2f (Figure la). The pub-
lished positive influence of the prolinol donor7 in comparison with the methoxyproline donor on the
alignment of the molecules in NPP could not be confirmed for the examined thiophene and bithiophene
derivatives. Whereas in DAST the tosylate counterions form sheets which tend to align rows of the dipolar
cations in a parallel manner so as to maximize the Madelung stabilization, 6 a similar effect was not observed
in the pyridinium salt 2k. As can be seen from the powder tests, neither the length variation of the cation nor
the variation of the counterion allowed to tune the packing of the derivatives 1d-f and 2i-k.
Molecular conformation
B
Figure 2. XP drawing from SHELXTL of2k (a) and 2b (b). Two molecules A, B (disorder of the oxygen of the meth-
oxy group in molecule B) crystallized in the asymmetric unit of 2b.
2b is almost coplanar resulting in excellent electronic interactions between the two end groups. The small
twist angles between the aromatic rings in crystal 2k enable an efficient charge transfer between the donor
and the acceptor group. The experimental values for selected C-C-bond lengths in the n-system of 2b and 2k
reveal one more time the ability of oligothiophenes to form quinoid resonance structures. Compared to simple
thiophenes 22,23 and aniline 24 shorter amine-N aryl-C bonds, shorter aryl-C-C single bonds and larger aryl-C-
C double bonds were found for 2b and 2k due to high contributions of the charge-transfer form. A mero-
cyanine-type character of these chromophores is therefore assumed. Nevertheless due to the relatively low
resolution of the crystal structure of 2b no significant reduction of the central C-C-bond compared to 2d 4d,22
was found.
Conclusions
The concept of introducing the chiral methoxyproline or prolinol substituent in donor-acceptor substituted
thiophenes 1-3 did not open an approach to favorable packing of the NLO active chromophores for signifi-
cant SHG efficiencies. In comparison, the phenyl and thiophene systems are approximately linear whereas the
F. Steybe et al./ Tetrahedron 54 (1998) 8469-8480 8475
latter has higher asymmetry in his quinoid form. With prospect of success for NLO crystals we have syn-
thesized the thiophene systems ld-f and 2i-k with the pyridinium acceptor group and various eounterions in
analogy to known crystalline stilbene derivatives. The well-known effect that in neutral dipolar systems with
increasing geometric asymmetry the probability of noncentrosymmetric crystallization appears to increase
could not be confirmed. Further work will be concentrated on third-order nonlinear applications because the
antiparallel alignment of the chromophores for this type of device is not disturbing.
Experimental Section
Powder test
For the powder test Nd:YAG lasers at ~, = 1064 nm and 1318 nm were used. The beam was focused onto
the sample and, if generated, the emitted green or red second-harmonic light was recorded. As reference
materials urea and DAST powder samples were used.
2-[(R)-2-(tert-Butyldiphenylsilyloxy)pyrrolidino]thiophene
Under Ar atmosphere at room temperature a solution of tert-butyldiphenylchlorosilane (2.17 g, 7.89
mmol) and imidazole (1.06 g, 15.5 mmol) in DMF (28 ml) was added dropwise within 10 min to a solution of
(R)-2-(hydroxymethylpyrrolidino)thiophene (1.18 g, 6.44 mmol) in DMF (8 ml), synthesized from mercapto-
8476 F. Steybe et al. /Tetrahedron 54 (1998) 8469--8480
thiophene and (R)-prolinol analogous to ref.4a. The reaction mixture was stirred for 6.5 h (TLC control).
After hydrolysis with l N NaHCO3 solution and extraction with CH2CI2, the combined extracts were washed
with water, dried (MgSO4), concentrated, and the residue was fractionally distilled bulb-to-bulb to yield 2.21
g (81%) as colourless viscous oil, bp 130°C/0.5.10"3Torr; [ct]2° = +43.1 (c 1.0, benzene).
2-(R)-(2-Methoxymethyl)pyrrolidino-5-nitrothiophene (lb)
Analogous to ref.4a from 2-iodo-5-nitrothiophene 4b (0.51 g, 2.0 mmol) and (R)-2-(methoxymethyl)pyr-
rolidine (0.48 g, 4.2 retool) in ethanol, reaction time 19 h at reflux; reerystallization from 55 ml toluene/n-
hexane (1:3) yielded 0.432 g (89%) as orange-yellow crystals, mp 128-129°C; IH NMR (CDCI3): ~2.16 (m,
4 H, pyrrolidino-H3,4), 3.36 (m, 4 H, pyrrolidino-H5, CH20), 3.48 (s, 3 H, CH30), 3.90 (m, l H, pyrrolidino-
H2), 5.88 (d, J = 4.9 Hz, 1 H, H3), 7.78 (d, 1 H, H4). Anal. Calcd for CIoHI4N203S: C, 49.57; H, 5.82; N,
I 1.56; S, 13.23. Found: C, 49.66; H, 5.86; N, 11.45; S, 12.97.
and 8.70 (each d, J = 7.0 Hz, 4 H, pyfidine), 8.14 (d, J = 4.2 Hz, 1 H, H4'). Anal. Calcd for C23H24N203S3:
C, 58.45; H, 5.12; N, 5.93; S, 20.35. Found: C, 58.45; H, 5.27; N, 5.91; S, 20.19.
X-Ray crystallography
Intensities were collected with a Nicolet P3/F at 293 K, with graphite-monochromated MoKa radiation
(~,=0.71073 A), 0-2 0 scan mode with 2 0 scan limits. The structure was solved by direct methods (SHELXS-
86 program), and refined by full matrix least-squares calculations based on IF21(SHELXL-93 program). H
atoms were refined isotropically. Crystallographic data (excluding structure factors) have been deposited with
the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-100784.
la lb 2b 2f 2g 2k
Formula C9HI2N203S CIoHI4N203S CmHI~N30S2 Ct4HI6N203S2 CI3HI+N203S2 C23H24N203S3
Mol. weight 228.3 242.3 355.5 324.4 310.4 472.7
Crystal size (ram) 0.8x0.1x0.07 1.0x0.3x0.2 0.65x0.1x0.05 0.6x0.2x0.04 1.0x0.3x0.05 0.8x0.5x0.4
Crystal system orthorhombic orthorhombic monoclinic orthorhombic monoclinic triclinic
Space group P212~21 P2t2121 P2j P212121 P2j PI
a(A) 6.937(1) 7.459(1) 6.927(2) 5.4520(8) 8.060(2) 9.112(1)
b (A) 12.330(2) 11.707(3) 35.717(1I) 7.867(1) 7.054(1) 10.845(2)
c(A) 12.339(1) 13.280(3) 7.767(2) 35.619(6) 24.418(4) 12.913(2)
¢x(o) 90 90 90 90 90 92.34(2)
[3(o) 90 90 114.12(2) 90 93.66(1) 94.49(1)
y (°) 90 90 90 90 90 114.54(1)
V (A3) 1060.5(2) 1159.6(4) 1753.9(9) 1527.7(4) 1 3 8 5 . 5 ( 5 ) 1153.4(3)
p ~ (g/cm 3) 1.43 1.388 1.346 1.410 1.488 1.361
Z 4 4 4 4 4 2
2 0 range (°) 2-50 2-55 2- 46 1.1- 48 2.5-55 2-50
Total reflections 1105 1539 2716 1445 3619 4336
independent 1105 1539 2493 1445 3404 4055
observed (I>2a (1)) 830 1328 1299 976 2528 3547
R, Rw 0.057, 0.106 0.046,0.106 0.0873,0.132 0.055, 0.094 0.053,0.103 0.0378,0.0987
p (e A3) +0.265/-0.181+0.241/-0.248 +0.273/-0.349 +0.198/-0.250 +0.280/-0.271 +0.313/-0.237
Acknowledgments
The authors would like to thank Prof. Ch. Br~luchle and Dr. S. Stadler for the HRS measurements.
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