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Reviews

H. Meier

Conjugated Oligomers

Conjugated Oligomers with Terminal DonorAcceptor


Substitution
Herbert Meier*

Keywords:
absorption conjugation
intramolecular charge transfer
nonlinear optics
oligomers

Angewandte

Chemie

2482

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/anie.200461146

Angew. Chem. Int. Ed. 2005, 44, 2482 2506

Angewandte

Conjugated Oligomers

Chemie

Conjugated oligomers represent a prominent class of compounds


from a viewpoint of their theory, synthesis, and applications in
materials science. Push-pull substitution with an electron donor D
at one end of the conjugation and an electron acceptor A at the
other end results in them having outstanding optical and electronical properties. This Review highlights fundamental synthetic
strategies for the preparation of such oligomers with n repeat units
(n = 1, 2, 3, 4, ) and the rules that govern their linear and
nonlinear optical properties (absorption, frequency doubling and
tripling). The unification of chemical, physical, and theoretical
aspects with an interdisciplinary image of this class of compounds
is attempted herein.

1. Introduction
Conjugated oligomers are target compounds for numerous applications in materials science because of their interesting electrical, optical, and optoelectronic properties and
they are also model compounds for the corresponding
conjugated polymers.[1] A topic of high topicality in terms of
nonlinear optics and electroluminescence concerns p systems
substituted with donor and acceptor groups in which conjugated oligomers form the p-electron linker. The compounds
can have a linear or a star-shaped architecture. Scheme 1
provides an overview of the most important structural types.

From the Contents


1. Introduction

2483

2. Long-Wavelength Electron
Transitions in Conjugated Oligomers 2484
3. Push-Pull-Substituted Oligomers:
Synthetic Concepts and Absorption
Behavior

2486

4. Nonlinear Optics in Series of


Oligomers with DonorAcceptor
Substitution

2496

5. VB and MO Models of D-p-A


Systems

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6. Summary and Outlook

2502

The push-pull effect of this class of compounds depends on


the strength of the donor and acceptor groups; however, it
also depends on the conjugated p system, to which a
zwitterionic resonance structure should contribute
(Scheme 2). The energy of the dipolar resonance structure is

Scheme 2. Participation of zwitterionic resonance structures for the


illustration of the push-pull effect in conjugated oligomers.

determined by the charge separation as well as the change in


the p system. The latter influence is certainly smaller for an
oligoene chain (1) than for repeat units consisting of aromatic
rings (2), whose zwitterionic resonance structures have pquinoid character.
Several parameters, such as BLA,[25] MIX,[6] and c2,[79]
have been suggested for quantification of the contribution of
zwitterionic resonance structures. This will be discussed
further in Section 5. However, it should be noted here that
the weight of resonance structures depends on external
factors such as the solvent or an applied electrical field.

Scheme 1. Construction of donoracceptor-substituted conjugated


oligomers consisting of donor groups D, a p-electron linker, and
acceptor groups A; selected examples are shown.
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

[*] Prof. Dr. H. Meier


Johannes Gutenberg-Universitt
Duesbergweg 1014
55099 Mainz (Germany)
Fax: (+ 49) 6131-392-5396
E-mail: hmeier@mail.uni-mainz.de

DOI: 10.1002/anie.200461146

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

2483

Reviews

H. Meier

A special case, which is occasionally referred to in this


article, is represented by the symmetrical, charged, all-Econfigured polymethines 3 a and 3 b (Scheme 3). At larger
values of n (beyond the so-called cyanine limit) it needs to be

oligomers to converge towards a certain limiting value E


for n!. The hyperbolic function described by Equation (1)
En c f

n1

seems to be adequate for polyenes. However, simple HMO


theory [Eq. (2)] supplies the limiting value (zero). Only the
lim En c 0

n!1

Scheme 3. Symmetrical charged polymethines (cyanines).

considered[10] whether the resonance should be substituted by


a fast equilibration (automerization) as soon as the C2v symmetry is abandoned in favor of a Cs symmetry.[1016]
A special aspect of series of conjugated oligomers is given
by the expectance that certain properties P(n) converge
towards a limiting value P for increasing numbers n of repeat
units, or at least their derivatives dP(n)/dn converge towards
P. The long-wavelength electron transition S0 !S1 provides
an example of the first case [lmax(n)!l],[1722] while the
hyperpolarizability of second order g is an example of the
latter case [dg(n)/dn!g].[23] In most cases lmax(n) increases
monotonously with n and reaches the limiting value l at the
so-called effective conjugation length nECL.[1a, 18] In contrast,
the slope of the curves g(n) and logg(n), respectively,
decreases with increasing n.[23, 24]
Recently it was found that certain conjugated oligomers
with terminal donoracceptor substitution can exhibit a
monotonously decreasing value for lmax with increasing
numbers n of repeat units;[25] the behavior of the hyperpolarizabilities b and g of such series is currently unknown.
Both effects will be discussed in Sections 3 and 4, while
quantum mechanical models for D-p-A systems will be
discussed in Section 5.

consideration of perturbation theory of first or second order


results in a limiting value which is different from zero
[Eq. (3)].[26] Db is the difference in the resonance integrals of
lim En

n!1

neighboring bonds. The perturbation is based on the fact that


polyenes have alternating single and double bonds of different lengths and consequently different b values.
Wenz, Wegner et al. derived a function on the basis of the
electron gas theory[27, 28] as Equation (4) with a limiting value
1

En c f
n 0:5

of c
6 0.[29] Root laws, such as Equation (5) used by Drefahl
p
lmax n c b n

and Pltner[30] for the long-wavelength absorption maxima,


and the corresponding functions for l2 suggested by Lewis and
Calvin[31] on the basis of coupled oscillator models were
modified by Hirayama[32, 33] to Equation (6) and revised by
l2maxn c b an

lim lmax

n!1

As already expressed in the Introduction, one expects the


lowest electron excitation energies E(n) for conjugated
Herbert Meier was born 1939 in Prague. He
studied chemistry and mathematics at the
University of Tbingen and the Free University in Berlin and in 1968 he completed his
doctoral thesis in organic chemistry with
Prof. E. Mller in Tbingen. After a habilitation in organic chemistry and photochemistry he became a docent in 1972 and a full
Professor in 1975. In 1982 he accepted the
chair of Prof. L. Horner at Mainz University.
His research focuses on organic compounds
with interesting properties for materials science and on heterocycles with a possible
activity spectrum. He is co-author of the
textbook Spectroscopic Methods in Organic
Chemistry.

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

4
Db > 0
p

Dhne und Radeglia.[34] Since a < 1, Equation (6) yields a


finite limiting value as shown by Equation (7). Equation (5)[30]

2. Long-Wavelength Electron Transitions in


Conjugated Oligomers

2484

p
c

and the related Equation (8)[23] are in principle suited for an


En E1 nn

interpolation but not for the extrapolation (n!). Finally,


the matrix method, conceived by Pade,[35] could also succeed
[Eq. (9)].

However, it turned out that none of these procedures


correctly reflect the saturation phenomenon for series of
oligomers having high numbers (n) of repeat units. The OPV

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Angewandte

Conjugated Oligomers

Chemie

series 4[18, 19, 36] will be used here as an example. Figure 1


demonstrates that a linear function of type (1) fits for the first
members (n = 18) of the series, but it is not suitable for the
higher oligomers (n = 11, 15) or for the extrapolation to the

Figure 2. Electron transitions in aggregates, visualized for aggregated


molecule pairs, whose transition moments M lie along the longitudinal
molecular axis. The energy of the allowed transition (c) and of the
forbidden transition (a) depends on the stacking angle a. Jelley
aggregates (J, a = 0) exhibit a bathochromic shift (n < n) and H
aggregates (a = 908) hypsochromic shifts (n > n).
Figure 1. Energies of the long-wavelength absorption maxima of 4 aj
and 4 p in chloroform and their exponential fit function (dotted line),
which approaches the value of the corresponding polymer 4 p. The
linear function of (n + 1)1 furnishes an erroneous limiting value.

(infinitely long) polymer chain. Exponential functions E(n)


and lmax(n) can be used here according to Equations (10) and
(11) as natural growth functions for such a case.[18, 19] The
effective conjugation length amounts to Equation (12).
En E1 E1 E1 ean1

10

lmax n l1 l1 l1 ebn1

11

lnl1 l1
1
6

12

nECL

Aggregation has to be avoided, especially for UV/Vis


measurements of higher oligomers, which means that series of
decreasing concentrations need to be measured in a good
solvent. Comparative measurements with a constant product
of molar concentration and cell thickness, namely, c d =
(101 c)(10 d) = (102 c)(100 d), proved to be particularly successful. Even a minor influence of the aggregation results in
deviation of the absorption curves. Aggregates whose absorptions differ little from the monomer absorption are particularly tricky. Figure 2 shows the modification of the transitions S0 !S1 when aggregation occurs. To simplify matters it
is assumed that the transition moments M of aggregated
molecules lie along their longitudinal axes. The van der Waals
interaction W1 leads to an energy level which is subjected to a
Davidov splitting W2. The allowed transition corresponds to
the sum M + M, and the forbidden transition to the difference
MM = 0. The transition energy E depends on the orientation of the molecules in the aggregate; E is lowest for pure
J aggregates (a = 08) and highest for pure H aggregates (a =
908). The function W2(a) in Figure 2 illustrates that W2 is zero
at the magic angle (a = 54.738), which means there is no
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

discernible energy change. Aggregation can also lead to a


steric effect, with the molecules less distorted and consequently absorb at longer wavelengths on aggregation.
The extension of conjugation by increasing numbers of
repeat units n normally leads to a monotonously decreasing
excitation energy E(n) which converges towards E.[18, 37] The
exponent a in Equation (10) determines the rate of convergence. Some time ago we found series of conjugated
oligomers which show a monotonous hypsochromic
effect.[25, 3841] Such a behavior is typical for certain p linkers
(see Section 3.1) with strong donors D and strong acceptors A
in the terminal positions. The convergence can then also be
determined by an equation of the form (10) or (11). The
energy EDA(n) [Eq. (13)] of an electron transition in D-p-A
systems can be split into two parts; the first part ES(n)
[defined by Eq. (14)] takes the extension of conjugation in the
purely donor- or purely acceptor-substituted[42] system into
consideration, the second term DEDA [defined by Eq. (15)] is a
correction term for the push-pull effect in series with terminal
donoracceptor substitution.[25]
EDA n ES nDEDA n

13

ES nE1 ES 1E1 ean1

14

DEDA n ES 1EDA 1eDan1

15

[ES(n)E] has a monotonously declining and DEDA(n)


a monotonously rising fitting function. Both approach to zero
for increasing numbers n of repeat unitsclearly, this is also
valid for their sum [EDA(n)E]. Figure 3 shows different
cases of summation. A monotonously decreasing
EDA(n) value results for type (a), which means such an
oligomer series exhibits a uniform bathochromic effect:
EDA(n)  EDA(n+1)  E. An oligomer series with a uniform
hypsochromic effect is realized in type (b): EDA(n)  EDA(n+1)  E. The borderline case (a)/(b) between (a) and (b) is
present for EDA(n)  E, that is, when the energy of the

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2485

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H. Meier

Table 1: Absorption in CHCl3 and color of the crystals of the transstilbenes 5 a5 f.[a]
Compound 5
[21, 25]

a
b[21, 25]
c[21, 25]
d[21, 25]
e[39]
f[39]

lmax [nm]

Crystal color

H
CN
CHO
NO2
HC=C(CN)2
C(CN)=C(CN)2

366
401
423
461
525
670

colorless
yellow
orange
red
dark red
blue

[a] Since the e values are not known for many UV/Vis data discussed in
this article, they are omitted completely.

Scheme 4. Push-pull-substituted oligo(1,4-phenylenevinylene)s (OPVs)


58/bf and the comparitive series 5 a8 a.

Figure 3. Variants for the convergence of excitation energies EDA(n)!


E of the long-wavelength electron transition in series of push-pull-substituted conjugated oligomers: a) uniform bathochromic behavior,
b) uniform hypsochromic behavior, c) hypsochromic convergence after
passing through a minimum of EDA(n).

electron transition is nearly independent of n (of the size of


the chromophore). A rapidly decreasing term [ES(n)E]
with increasing numbers n can also lead to the fact that EDA(n)
goes through a minimum before it approaches to E
(type (c)). Examples of oligomer series D-p-A for the
considered cases are given in the following sections; the
theoretically imaginable case, in which EDA(n) goes through a
maximum, is to my knowledge not unequivocally proven
experimentally to date.

pronounced as the acceptor strength increases. Since the


corresponding excitation S0 !S1 is connected to an intramolecular charge transfer (ICT), the long-wavelength band is
called a charge transfer band.
An exciting question is how does the intramolecular
charge transfer change when the distance between donor and
acceptor groups increases, that is, when the number n of
repeat units in the p linker is increased. Since dialkylamino
groups with long alkyl chains have a solubilizing character, a
systematic study of the oligo(1,4-phenylenevinylene)s
(OPVs) 5 ae, 6 ae, 7 ae, and 8 ae could be performed.[21, 25]
Compounds 5 c8 c were constructed from 9 by means of a
WittigHorner reaction and a simple protecton strategy
(Scheme 5). Phosphonate 10 served as an extension
reagent. After a condensation reaction in an alkaline
medium, the deprotection of the masked formyl group in 10

3. Push-Pull-Substituted Oligomers: Synthetic


Concepts and Absorption Behavior
3.1. Linear Oligomers D-p-A
The push-pull effect has a strong influence on the longwavelength electron transitions in conjugated oligomers with
terminal donoracceptor substituents (see Section 5). Table 1
shows as an example the trans-stilbenes 5 af (Scheme 4)
which bear a branched dialkylamino group in the 4-position
and various substituents R in the 4-position.[21, 25, 39] Compared
to 5 a with R = H, the compounds with acceptor groups R
exhibit a bathochromic shift, which is more and more

2486

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Scheme 5. Coupled convergent synthetic strategy for the OPV series


58/ae.

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Angewandte

Conjugated Oligomers

Chemie

occurred directly in the acidic work-up, so that a free


aldehyde function was available for the next extension step.
The compounds 9, 5 c, 6 c, and 7 c were then reacted in an
end-capping process with the phosphonates 11 a,b,d to give
the series 5 a8 a, 5 b8 b, and 5 d8 d.[21, 25] A condensation
reaction of the aldehydes 5 c8 c with malononitrile 12 can be
recommended for the end capping for the preparation of
the series 5 e8 e.[39] It was possible to obtain the series of five
oligomers through a minimum number of synthetic steps by
applying this coupled, convergent synthetic strategy.
Figure 4 depicts the maxima of the long-wavelength
absorptions of the OPVs 58 ae measured in CHCl3. A

to a bathochromic shift, which is shown by a decreasing


difference of ESE for the series 5 a8 a. The push-pullsubstituted OPV series 5 b8 b bearing the relatively weak
acceptor R = CN is characterized by a correction term DEDA
which weakens the bathochromic shift. In the series 5 d8 d,
with the nitro group as strong acceptor, the term ESE is
over-compensated by the term DEDA ; thus, a hypsochromic
effect results. The two terms generally cancel each other out
in 5 c8 c (formyl series), so that the absorption maxima are
almost independent of the length of the chromophore.[43]
The compounds 58/ae show, without exception, positive
solvatochromic effects, which originate from intramolecular
charge transfer (ICT). As soon as the push-pull effect is
suspended by protonation of the amino group, the bathochromic shift in the series 5 b8 b is strengthened and the
hypsochromic shift in the series 5 d8 d is reversed to a
bathochromic shift (Figure 6). However, the entire absorption

Figure 4. Maxima of the long-wavelength absorptions in the OPV


series 58/ae in CHCl3.

pronounced bathochromic effect can be realized for 5 a8 a, a


decreased bathochromic effect for 5 b8 b, lmax values of 5 c
8 c which are fairly independent of the size of the chromophore, a hypsochromic effect for 5 d8 d, and an even stronger
hypsochromic effect for 5 e8 e.
The evaluation according to Equations (13)(15) is demonstrated in Figure 5. The extension of the conjugation leads

Figure 5. Partition of the energies of the electron transition S0 !S1 into


a term (EsE) which reflects the bathochromic shift caused by the
extension of conjugation and a term DEDA which takes the decrease
of the ICT and its consequence on the absorption into account. The
measured data of 58/ad in CHCl3 shown in Figure 4 are the basis
for this distribution.[43]
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

Figure 6. Absorption maxima in the OPV series 5 d8 d (n = 14); top


curve: measurement in CHCl3, bottom curve: measurement in CHCl3/
CF3COOH (10:1).

range is located at essentially higher energy when the ICT is


cancelled out (see Section 5).
An extension of conjugation in push-pull-substituted
OPVs results in a bathochromic shift, but the decrease of
the ICT and its effect on the absorption causes an opposite
hypsochromic shift (see Section 5). Depending on the
strength of the acceptor, a bathochromic or hypsochromic
net effect results for systems with the same donor; this
includes the case in which both effects cancel each other out.
Exclusive bathochromic effects were found for OPV linkers
with weaker donors, such as alkoxy groups. Compounds
13[4446] and 14[46, 47] in Scheme 6 illustrate this statement.
Among the depicted variants E(n) in Figure 3, the cases (a)
and (b) as well as the borderline case (a)/(b) are realized in
push-pull-substituted OPVs.
The trans-configured double bond in the repeat unit of 5
8/ae is replaced in the donoracceptor-substituted oligo(1,4phenyleneethynylene)s (OPEs) 1518/ae shown in Scheme 7

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2487

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H. Meier

The long-wavelength absorption data for compounds 15


18/ae are summarized in Table 2.[41] The evaluation of the
UV/Vis spectra is somewhat more difficult in the OPE series
than in the OPV series because the long-wavelength absorption band (S0 !S1) is superimposed by the higher energy
electron transition S0 !S2 (Figure 7 demonstrates this using
Table 2: Long-wavelength UV/Vis absorption of the OPE compounds
1518/ae in CHCl3.
Scheme 6. Push-pull-substituted OPVs with alkoxy groups as donor
groups; absorption maxima in CHCl3.

Scheme 7. Push-pull-substituted OPE series 1518/be, comparitive


series 15 a18 a, and precursors 15 f17 f and 15 g17 g.[41, 48]

by a triple bond, and the didodecylamino group serves as a


solubilizing donor function.[41] The preparation of the
oligomer series 1518/ae again takes place by a coupled,
convergent strategy. The SonogashiraHagihara reaction and
a simple protection strategy form the preparative basis.[41]
Starting from 19 and 20, the auxiliary series 15 f17 f and
15 g17 g were first prepared (Scheme 8). The extension

Compound

nmax [103 cm1]

lmax [nm]

15 a
16 a
17 a
18 a
15 b
16 b
17 b
18 b
15 c
16 c
17 c
18 c
15 d
16 d
17 d
18 d
15 e
16 e
17 e
18 e

1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4

29.33  0.07
26.74  0.07
26.28  0.18
26.16  0.30
25.84  0.07
25.84  0.07
25.97  0.18
26.09  0.30
25.00  0.06
25.64  0.06
26.00  0.20
26.02  0.25
23.15  0.06
24.81  0.06
26.15  0.30
26.15  0.30
20.45  0.05
22.62  0.07
24.75  1.00
26.8  0.30

341
374
379[a]
378[a]
387
387
384[a]
379[a]
400
390
382[a]
388[a]
432
403
380[a]
382[a]
489
442
384[a]
373[a]

[a] The lmax values differ in these cases from 1/nmax of the separated longwavelength band because of the superposition of the bands.

Figure 7. UV/Vis spectrum of 16 d in CHCl3 (c) and its dissection


into two bands according to Equations (16)(18).[41]

Scheme 8. Coupled convergent synthetic strategy for the OPE series


1518/ae with the precursor series 15 f17 f and 15 g17 g.

reagent 20 was utilized for the Pd-catalyzed CC coupling


step; the subsequent alkaline deprotection left the ethynyl
component open for the next extension step. The SonogashiraHagihara reaction with the corresponding iodobenzene,
which contained the desired p-substituent (R = H, CN, CHO,
NO2), was used then as the end-capping step.[41] The OPE
series 15 e18 e could be obtained by the condensation
reaction of 15 c18 c and malononitrile.[46]

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 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

16 d as an example). A separation of the bands can be


performed for example with an algorithm based on Gauss
functions.[49] Since non-overlapping absorption bands at long
wavelengths are also slightly unsymmetric in these series,
exponential functions of type (16) proved to be a success.
 

~
n~
nmax
n ~
e~
n emax exp  max
~
n D~
n

16

with D~
n j0:5~
n2 ~
n1 j

17

n2 emax e1
and e~
n1 e~

18

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Chemie

The evaluation of the data of 1518/ad is visualized in


Figure 8, which corresponds more or less to Figure 5 for the
analogous donoracceptor-substituted OPV systems 58/a
d.[50] The interpretation of Figure 8 corresponds to the
interpretation of Figure 5. The bathochromic effect resulting

Only single examples of push-pull-substituted oligoenes


(OEs) of type 1 (polymethine dyes) or 24 a,b29 a,b (n = 1,2,3,
) are known; an exception is represented by the aldehydes
24 c29 c (R = CH3),[52ac] which were prepared from the
Zincke aldehyde by chain extensions with Grignard reagents
and hydrolysis of the corresponding cyanines (Scheme 10).[52a]

Scheme 10. Push-pull-substituted oligoenes: Maxima of the long-wavelength absorption in CH2Cl2.


Figure 8. Partition of the electron transition energies (S0 !S1) of 15
18/ad into a term (ESE) which reflects the bathochromic shift
caused by the extension of conjugation and a term DEDA which takes
the decrease of the ICT and its consequence on the absorption into
account.

from the extension of conjugation is surpassed in the NO2


series by the hypsochromic effect, which arises from the
decrease in the ICT; the same is true to a lesser extent in the
CHO series 15 c18 c; the two effects cancel themselves out
almost completely in the CN series 15 b18 b. Altogether, the
OPE linker is still somewhat more prone than the OPV linker
to exhibit the unusual hypsochromic effect with increasing
numbers n.[51] This situation has the consequence that even
methoxy groups (as weaker donors) do not show a red-shift
when in combination with strong acceptors such as NO2.
Compounds 22 and 23 in Scheme 9 are shown here as

The absorption spectra of 24 c29 c measured in CH2Cl2


show a pronounced bathochromic shift for increasing numbers n of repeat units. Even the stronger electron-withdrawing
dicyanovinyl group does not change this effectnor when the
trans double bonds are fixed in a transoid arrangement by
incorporation in rings.[52d] Bathochromic effects were also
observed by Lehn, Blanchard-Desce, Zyss, and co-workers in
the series 30 a32 a and 30 b32 b, which contain carotinoid
units as p linkers (Scheme 11). The synthesis of these com-

Scheme 9. Maxima of the long-wavelength absorptions of push-pullsubstituted OPEs with methoxy groups as donors and CN or NO2
groups as acceptors (CHCl3 as solvent).

Scheme 11. Carotinoid push-pull compounds and the maxima of their


long-wavelength absorption in CHCl3.[5355]

examples. Whereas lmax(2)lmax(1) amounts to + 16 nm for


22 a/23 a, a value of 3 nm was found for 22 b/23 b.[46] The
dialkylamino group (a strong donor) does not effect an
inversion of the red-shift in the series 15 g17 g bearing the
ethynyl group (a weak acceptor group).

pounds was performed by one-sided Wittig and Wittig


Horner reactions, respectively, of the carotinoid dialdehydes
and the corresponding phosphorus reagents of 1,3-benzodithiole followed by subsequent condensation of the stillpresent aldehyde function with malononitrile.[53, 54]

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H. Meier

The bathochromic shift for increasing length of the


chromophore was also found by Blanchard-Desce, Barzoukas, Marder, and co-workers who studied the series 3335,
which includes an aromatic or heteroaromatic ring in the
p linker at the donor end (Scheme 12).[3, 56, 57] The synthetic
strategy for 3335 is depicted in Scheme 13. The aldehyde

Table 3: Maxima of the long-wavelength absorption lmax [nm] of the


oligoenes 33 b (n = 04), 33 d (n = 03), 34 a (n = 14), 34 b (n = 05),
34 f (n = 03), and 35 c (n = 02) in CHCl3.
n

33 b[56]

33 d[57]

0
1
2
3
4
5

443
507
540
571
586

603
695
773
826

34 a[56]

34 b[56]

34 f[56]

35 c[57]

413
446
469
486

458
531
572
594
606
613

494
542
556
566

512
619
710

strength increases; lmax(n+1) > lmax(n) is valid within each


series. Analogous bathochromic effects were measured for
series of compounds with 1,3-benzodithiole donor groups and
carotinoid linkers which contain an aromatic or heteroaromatic ring (4-nitrophenyl, 4-cyanophenyl, 4-pyridyl) at the
acceptor end.[53, 55]
Push-pull-substituted oligoenes bearing aromatic rings at
both chain ends[53, 55, 58b, 59] show a diminished bathochromic
effect. A comparison of the series 38 a41 a and 38 b41 b
(Scheme 14) shows a characteristic result.[46, 58b, 59] Compounds

Scheme 14. Maxima of the long-wavelength absorption of oligoenes


with terminal dimethylamino/nitro substitution, which include a
benzene ring in the p linker on the donor side (38 a41 a) as well
as on the donor and acceptor sides (38 b41 b); measured in CHCl3.
Scheme 12. Oligoenes with (hetero)aromatic rings as donors as well as
various acceptors.

Scheme 13. Synthetic strategy for the series of compounds 3335.[57]

series 33 a, 34 a, and 35 a with the corresponding donor groups


D acted as the central series and were constructed by means
of the Wittig reaction with the extension reagent 36. The
condensation reaction with the active methylene components
37 be was then selected as the end capping.[57] The maxima
of the long-wavelength absorptions of a selection of compounds 3335 are listed in Table 3. For constant values of n,
the lmax value becomes higher as the donor and acceptor

2490

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

analogous to 38 b40 b, but with a CN group instead of the


NO2 group, were investigated in the context of their dual
fluorescence and twisted intramolecular charge transfer
(TICT) states;[6066] however, a discussion of these states is
beyond the scope of the present Review.
Push-pull-substituted oligoynes (OIs) are scarcely
reported in the literature to date.[67] The aminoketones 42
and 43 and the aminonitro compounds 44 and 45 are given
here as examples (Scheme 15). Benzene rings at the ends of
the p linker cause a hypsochromic effect for neither the pushpull-substituted oligoenes nor the corresponding oligoynes
in contrast with the accordingly substituted OPV and OPE
systems.

Scheme 15. Maxima of the long-wavelength absorption of oligoynes


with push-pull substitution.[6871]

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Oligo(1,4-phenylene)s (OPs) differ from the OPVs,


OPEs, OEs, and OIs discussed so far as a result of a strong
torsion of the benzene rings along the chain. Torsional angles
between 30 and 408 can be assumed, which considerably
influence the conjugation and the ICT.[71, 72] Since the resonance integrals do not only depend on the different atomic
distances in the p linker but also on the torsion of the
p orbitals, an acceleration of the convergence E(n)!E can in
principal be expected for increasing torsion angles. A
considerable planarization of the 1,4-phenylene chain by
anelated five-membered rings results in a bathochromic
shift;[7173] Table 4 shows a comparision of biphenyls 46 a
49 a and fluorenes 46 b49 b (see Scheme 16 for structures).
Table 4: Maxima of the long-wavelength absorption of the
biphenyls 46 a49 a and comparison with the corresponding
fluorenes 46 b49 b.[71, 73]
R1

R2

Biphenyl driva- lmax [nm] Fluorene deriva- lmax [nm]


tives
tives

H
H
N(CH3)2
N(CH3)2

H
NO2
H
NO2

46 a
47 a
48 a
49 a

252[a]
304[a]
301[b]
390[b]

262[a]
328[a]
310[b]
417[b]

46 b
47 b
48 b
49 b

[a] Measurement in 1,4-dioxane. [b] Measurement in CHCl3.

Scheme 16. Planarization of the torsional angles of biphenyls in


fluorenes (see Table 4 for R1, R2).

The synthetic strategy of oligo(1,4-phenylene)s is based


on usual Pd-catalyzed arylaryl CC coupling reactions such
as the Suzuki, Negishi, Stille, Yamamoto, or Kumada
reactions.[1k] The preparation of the series 54 with D = N(CH3)2 and A = CN are described here as an example
(Scheme 17). Negishi couplings of 50 with 51 led to the

Scheme 17. Synthetic strategy for the construction of donoracceptorsubstituted OPs 54.[74]
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

construction of the auxiliary series 52. The primary


insertion of the Pd into the CBr bond of 51 is decisive for
this step. Compounds 51 and 52 were then subjected to a
cross-coupling reaction with 53.[74]
Since the range of the ICT is considerably shorter than
the conjugation (see Section 5), the continuous torsions along
an oligo(1,4-phenylene) chain can lead to a fast decrease in
the ED(n)E value (see Figure 3 c). Consequently, the
energy EDA(n) for the electron transition S0 !S1 can pass
through a minimum, and lmax(n) accordingly through a
maximum (type (c), Figure 3)in particular, when the correction term DEDA of the ICT is large, that is, when a push-pull
effect of a strong donor and a not too weak acceptor is
present. This is realized for 54 and 55 (Table 5); the maximum
Table 5: Maxima of the long-wavelength absorption of donoracceptor
substituted oligo(1,4-phenylene)s D-[-C6H4-]n-A: 54 ad,[75] 55 ad,[71, 76]
56 ac,[71] and 57 ac.[46, 77, 78]
Compound

lmax [nm]

Solvent

54 a
54 b
54 c
54 d
55 a
55 b
55 c
55 d
56 a
56 b
56 c
57 a
57 b
57 c

CN

N(CH3)2

NO2

NH2

NO2

OCH3

CN

OCH3

1
2
3
4
1
2
3
4
1
2
3
1
2
3

290
342
332
314
373
378
358
340
302
332
340
247
292
302

CCl4
CCl4
CCl4
CCl4
EtOH
EtOH
EtOH
EtOH
1,4-dioxane
1,4-dioxane
1,4-dioxane
DMSO
DMSO
DMSO

value of lmax is found in both cases for n = 2, but can be solvent


dependent. When the amino function is substituted by the
less-strong donor OCH3, shifts to longer wavelengths are
obtained for the series with A = NO2 as well as for the series
with A = CN with increasing values of n (type (a), Figure 3).
The introduction of thiophene or furan rings instead of
benzene rings in the p linker results in the absorption maxima
shifting to longer wavelengths (Scheme 18 shows some
examples).[71] Push-pull-substituted oligomers whose p linkers consist exclusively of five-membered-ring heterocycles,
were studied in particular for the thiophene series. Table 6
offers a comparison of bithiophenes with various donor and
acceptor groups; it can be seen that the combination of a 1pyrrolidine group and a nitro group in particular results in a
far-red-shifted CT band. Thus, an interesting dependence of
the absorption on the number n of repeat units can be
expected for the push-pull-substituted oligothiophenes (OT;
oligo(2,5-thienylene)s) studied by Effenberger and Wrthner.[7981] Table 7 shows a comparison of the methoxy-nitro
series 66 ad (n = 14) and the 1-pyrrolidino-nitro series 67 a
d (n = 14). Whereas a monotonous bathochromic shift with
increasing n was found for 66 ad, the lmax value of 67 ad
passes through a maximum at n = 3.[82] Hence, the latter
oligomer series belongs to type (c) in Figure 3 and resembles
the corresponding OPs 54 ad and 55 ad. To date, there are

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69 ad, which were recently prepared by a Sonogashira


Hagihara reaction, should also be mentioned (Scheme 19).[46]
The series 68 ac belongs to type (a) in Figure 3, whereas the
series 69 ad exhibits an S0 !S1 transition, which is independent of the length of the chromophore.

Scheme 18. Red-shift of the long-wavelength absorption band on


replacement of the benzene rings in the p linker by thiophene or furan
rings.

Table 6: Maxima of the long-wavelength absorption of donoracceptorsubstituted bithiophenes in n-hexane.[79, 80]

Compound

lmax [nm]

63
64
65
66 b
61

OCH3
N(CH3)2
SCH3
OCH3
N(CH3)2

CHO
CHO
NO2
NO2
NO2

372
421
391
408
466

NO2

499

67 b

Scheme 19. Maxima of the long-wavelength absorption of donor


acceptor-substituted oligo(2,5-thienyleneethynylene)s 68 ac and
69 ad (measured in CHCl3).[46]

It remains to state at the end of this section that D-p-A


systems can also be generated by protonation of suitable D-pD systems. Not only does the protonation of terminal amino
groups have to be considered, but also the thiophene ring
itself, as demonstrated in Scheme 20. Protonation of 70 a,b in
CD2Cl2/CF3COOH leads to a shift of more than 200 nm to
longer wavelengths.[84]

Table 7: Maxima of the long-wavelength absorptions of the oligothiophenes 66 ad and 67 ad in n-hexane.[7981]


Scheme 20. Protonation of symmetrical oligothiophenes for the
generation of D-p-A systems.
Compound

lmax [nm]

66 a
66 b
66 c
66 d

OCH3

NO2

1
2
3
4

340
408
442
454

408

2
3
4

499
505
497

67 a

NO2

67 b
67 c
67 d

3.2. Oligomers with D-p-A-p-D or A-p-D-p-A Structures

few D-p-A series with repeat units consisting of thiophene


rings and CC double or triple bonds.[83] Oligo(2,5-thienylenevinylene)s (OTVs) which bear 4-diethylaminophenyl
groups as the donor and NO2, CHO, or CH=C(CN)2 groups
as the acceptor have to be mentioned in this context; all these
cases correspond to bathochromic series (type (a)).[83a,b]
The oligo(2,5-thienyleneethinylene)s (OTEs) 68 ac and

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Conjugated oligomers with a donoracceptordonor


structure require bidentate acceptor groups in the center of
the molecule. The presence of carbonyl and related groups in
this position leads to cross-conjugation. An example is
presented by Michlers ketone 72 (m = n = 1) and its higher
homologues, though little is known about them.[85] Single
examples of linearly conjugated D-p-A-p-D compounds exist
in the series of azobenzenes 73,[46, 8688] pyridazines 74,[89]
pyrazines 75,[90] and 1,2,4,5-tetrazines 76;[46, 91] a systematic
study was only performed for the squaraine series 77 ad[92]
(Scheme 21).
Compounds 77, which are obtained by coupling the
corresponding resorcinols and squaric acid, show an absorp-

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An extended planarization of the chromophore, in 77


through the formation of intramolecular hydrogen bridges, is
an essential precondition for an efficient push-pull effect.
Figure 10 shows, using compound 78 as an example, how the
absorption is shifted from the NIR range to the UV range

Scheme 21. Examples of D-p-A-p-D systems.


Figure 10. Absorption of squaraine 78 in CHCl3 and in CHCl3/EtOH
mixtures.

tion with a strong red-shift on going from n = 0 to n = 1; the


blue dye 77 a is thereby converted into the NIR dye 77 b.[92]
The electron transition which is predominantly localized in
the squaraine ring[93] in 77 a becomes a transition in a pushpull-substituted stilbenoid compound and hence results in a
pronounced hypsochromic effect for n = 2, 3.[92] This effect
occurs only when the measurements are made in an organic
solvent such as CHCl3 (Figure 9)when an acidic medium
such as CF3COOH is used, the amino groups become
protonated and consequently lose their donor character; the
generated cations then have an A-p-A-p-A structure and
show the expected bathochromic shift (from n = 0 to n = 3).

(Dlmax > 450 nm) by the addition of ethanol which acts as a


hydrogen bridge donor.[94] The benzene rings turn out of the
plane of the squaraine rings when intermolecular hydrogen
bridges are formed.
Compounds of the type A-p-D-p-A require bidentate
donors such as O, S, or NH. No oligomer series of this type
currently exists. Recently, the two first members (n = 1, 2) of
the series 79 (Scheme 22) with ferrocene as a strong donor
were studied; they exhibit a bathochromic effect: lmax(2) >
lmax(1).[95]

Scheme 22. Maxima of the long-wavelenth absorption of A-p-D-p-A


compounds with ferrocene as the central donor (measured in CHCl3).

3.3. Star-Shaped Compounds A-(p-D)3 and D-(p-A)3

Figure 9. Maxima of the long-wavelength absorption of the squaraines


77 ad (n = 03) in CHCl3 ~ and in CF3COOH &.
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

Tridentate cores have to be considered in addition to


the bidentate central acceptors or donors described in
Section 2.3. Scheme 23 shows some central building blocks.

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H. Meier

Scheme 23. Central building blocks for conjugated three-arm


oligomers: a) acceptor groups for star-shaped compounds
A-(p-D)3, b) donor groups for star-shaped compounds D-(p-A)3.

The series of methylium salts 80 ad (Scheme 24) was


prepared; they can be regarded as higher homologues of the
well-known triphenylmethane dyes.[96] The synthesis of 80 ad
was realized from the corresponding carbinol bases, whose

Figure 11. Maxima of the long-wavelength absorptions of the


trifluoroacetates 80 ad (n = 14) in CHCl3/CF3CO2H (7:3) and the
corresponding carbinols (bottom curve) in CHCl3. Extrapolation to l
by application of Equation (11).

Table 8: Maxima of the long-wavelength absorption of the colored salts


81 a,b, 82 a,b, and 83 ac.

[97]

81 a
81 b[99]
82 a[97]
82 b[99]
83 a[100]
83 b[100]
83 c[100]

Scheme 24. Methylium salts with OPV chains which bear terminal
donor groups.

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

lmax[a] [nm]

H
CH3
H
CH3
H
H
H

OCH3
OCH3
N(CH3)2
N(CH3)2
N[CH2CH(C6H13)2]2
N[CH2CH(C6H13)2]2
N[CH2CH(C6H13)2]2

1
1
1
1
1
2
3

718
733
609
615
622
740
790

[a] End values of lmax at a high excess of CF3COOH.

treatment with acid led to the elimination of the OH group


bound on the central carbon atom. The cations 80 ad, strictly
as their carbinol bases, exhibit monotonously growing lmax
values with nof course shifted by the push-pull effect from
the UV/Vis region to the Vis/NIR region (Figure 11). The
same is valid for methylium ions which are linked through
polyene chains -(CH=CH)n- to ferrocene as the terminal
donor group; the lmax value rises from 618 to 1187 nm on
going from n = 2 to 14.[97]
In contrast to the weakly pH-dependent alkoxy-substituted color salts 80 ad and 81 a,b, the dialkylamino compounds 82 a,b and 83 ac (Table 8) exhibit absorptions which
depend strongly on the concentration of H+ ions.[98101] The
formation of the cations from the carbinols or their ethers on
interaction with strong acids leads first to absorption maxima
which are located far in the NIR region. A lmax value of
1003 nm is found for 82 b,[100] and further addition of
CF3COOH induces a decrease in the intensity of this band

2494

and a slight blue-shift. Simultaneously, a new band appears at


lmax = 530 nm, which increases strongly and is red-shifted to
615 nm at high excess of CF3COOH.[100] Table 8 shows the
lmax values at the end of this titration when all three
terminal amino groups of 82 b are protonated. Hence, the
push-pull character in the three arms is lost. Thus, it is
understandable that the lmax values of the methoxy compounds 81 a,b with n = 1 are higher than those of the
dialkylamino compounds 82 a,b and 83 a.
Of the central acceptors for three-star oligomers shown in
Scheme 21, the 1,3,5-triazines deserve special mention. The
alkoxy-substituted compounds 8486 and the dialkylamino
compounds 87 and 88 were prepared by alkaline condensation
reactions of 2,4,6-trimethyl-1,3,5-triazine with the corresponding aldehydes (Scheme 25).[101] The influence of the
push-pull effect in 84 and the even stronger effect in 87 can be
seen by comparison to the unsubstituted 2,4,6-tristyryl-1,3,5triazine, which has a lmax value of 327 nm. The absorption for

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Figure 12. Top: long-wavelength absorption bands of the 1,3,5-triazines


86 ad (n = 14) in CH2Cl2 ; bottom: extrapolation of the lmax values
according to Equation (11) and determination of the effective
conjugation length according to Equation (12).
Scheme 25. 1,3,5-Triazines with donor-substituted OPV chains and the
maxima of their long-wavelength absorption (measurement of 8486
in CH2Cl2, of 87 and 88 in CHCl3).[101]

the series 86 ad is red-shifted as the length of the conjugated


arms increases. The absorption quickly approaches (nECL = 7)
a limiting value of l = 427 nm (Figure 12). An interesting
feature is given by the indicator behavior of 87. Unexpectedly, the first protonation on addition of trifluoroacetic acid
occurs at the triazine ring, even though, for example, N,Ndimethylaniline has a higher basicity than 1,3,5-triazine. The
yellow solution in CHCl3 turns deep violet (lmax = 549 nm).
Further addition of CF3COOH leads to a protonation of the
terminal amino groups and the solution bleaches (lmax =
365 nm).[102] The primary red-shift is based on an increase in
the push-pull effect. However, as soon as the amino functions
become protonated, their donor character is lost and an A-(pA)3 system is obtained.
Since the protonated 1,3,5-triazine ring is a strong
acceptor and the amino group a strong donor, an extension
of the chromophore should result in a hypsochromic effect.
We established this relationship by comparing 88 a and 88 b
(Figure 13). Compound 88 a, like 87, shows a red-shift upon
weak acidification, and afterwards a blue-shift on increased
acidification. The higher homologue 86 b behaves in exactly
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

the opposite way: the primary blue-shift is followed by a redshift. The logical explanation is the following: the extension of
the chromophore causes a bathochromic effect (445!
458 nm) for 88 itself; a much stronger push-pull effect is
present in the species with a protonated 1,3,5-triazine ring and
the extension of the chromophore leads to a hypsochromic
effect (551!394 nm); there is no push-pull effect in the
completely protonated compounds; the normal extension of
the conjugation then results in a bathochromic shift (368!
459 nm).[103]
The benzene system seems to be the most interesting
among the central donor groups listed in Scheme 23; however, until now only a few examples, such as 89 a,b
(Scheme 26), have been prepared and studied.[104] Compound
89 and analogous benzene derivatives bearing three acceptor
groups and three conjugated arms with terminal donor
substituents (see Scheme 23) can be regarded as parent
systems of hexasubstituted benzenes 91 having an octupolar
character and therefore special significance for nonlinear
optics.[70] Scheme 27 shows a synthetic approach to 91 based
on the trimerization of alkynes. To my knowledge, series of
conjugated compounds of type 91 with systematically
extended p linkers are currently unknown.

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H. Meier

Scheme 27. Octupole 91 with a benzene core obtained by


cyclotrimerization of alkynes 90 with push-pull character.

4. Nonlinear Optics in Series of Oligomers with


DonorAcceptor Substitution
Nonlinear optical properties (NLO) of organic materials
are of great interest for optical data storage, data processing,
and data transfer,[1p, 105] and conjugated NLO chromophores
with a pronounced push-pull character are of high significance. Figure 14[106] provides an explanation for this: if light is

Figure 13. Top: bathochromic shift of the absorptions band of 88 a


(c) by protonation of the 1,3,5-triazine ring (d) and subsequent
hypsochromic shift by complete protonation (g) in CHCl3/
CF3COOH; bottom: hypsochromic shift of the absorption band of 88 b
(c) by protonation of the 1,3,5-triazine ring (d) and subsequent
bathochromic shift by complete protonation (g) in CHCl3/
CF3COOH.

Figure 14. Description of nonlinear optics of D-p-A systems (SHG:


second harmonic generation, THG: third harmonic generation).[106]

shining on a compound consisting of D-p-A molecules, the


E vector causes a high polarization P(E). The periodicity of
E(t) of the light wave corresponds to the periodicity P(t);
however, the function P(t) is not a sine function. Its Fourier
transformation leads to a progression (19), which contains the
optical susceptibilities c(n) of nth order. For a single molecule,
this corresponds to Equation (20) for the induced dipole
moment.

Scheme 26. Three-star compounds 89 a,b with central donor and


terminal acceptor groups (absorption maxima in CHCl3).

2496

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

P e0 c1 E c2 E2 c3 E3 . . .

19

mind: aE bE2 gE3 . . .

20

Apart from the linear polarizability a, there are hyperpolarizabilities b and g (of first and second order, respectively) which are many magnitudes smaller. Since b and g are
very small (factors of 1010, 1017), high intensity laser light is
needed to measure the frequency doubling and tripling. The
advantage of donoracceptor-substituted conjugated p systems arises from the fact that the shift of electrons from the
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donor to the acceptor is highly efficient (Figure 14); that


becomes particularly apparent in the b values. Although D-pA molecules are not centrosymmetric, they can crystallize in
centrosymmetric space groups. The centrosymmetry must
then also be valid for the function P(E) [Eq. (21)]. This
PE PE

21

requires that c(2) = b = 0 in the progressions (19) and (20).


Many compounds with donoracceptor substitution unfortunately crystallize in centrosymmetric crystal classes. Starshaped systems of type 89 or 91 avoid this.
The influence of the substitution, in particular of the pushpull substitution, on b and g becomes evident in the transstilbene derivatives in Table 9. Strong donors and strong
Scheme 28. Comparison of the b0 values of D-p-A compounds having
the same length of p linker but a different number of benzene
acceptors enhance the b and g valuesin analogy to the
rings.[58b]
dipole moment m. However, a direct relationship between m
and b or g does not exist, as the comparison of 13 a and 96 in
Table 9 reveals.
independent, so-called static, b0 values can be made on the
Since strengthening the push-pull effect also shifts the CT
basis of the two-level model[108, 109] which works for D-p-A
band to higher lmax values (see Section 3.1), a power law b ~
systems because of the domination of the CT transitions.[110]
k
[107]
lmax or logb ~ loglmax seems to apply.
The second order
The deterioration of the conjugation as a consequence of
hyperpolarizability g of trans-stilbenes scales with b.[107] The
the torsion in oligo(1,4-phenylene)s (OPs) is already
expressed in the lmax values, but it is also noticeable in the
push-pull compounds N,N-dimethyl-4-nitroaniline and (E)-4dimethylamino-4-nitrostilbene (DANS; 38 b) represent NLO
hyperpolarizabilities b. Table 10 shows a comparison of
standards that are often used.
biphenyls and the corresponding fairly planar fluorenes for
Incorporation of a triple bond instead of a trans-configthis purpose. The correlation is much more complex for the
ured double bond results in b and g decreasing considerably
g values, as the comparison of 47 a,b and 56 a,b demonstrates.
and m decreasing to a small extent. For 4dimethylaminophenyl-4-nitrophenyleTable 10: Comparison of dipole moments m and hyperpolarizabilities b and g of biphenyls and the
thyne b = 46  1030 esu, g = 151  1036 esu,
corresponding fluorenes.[71]
18
[71]
and m = 6.1  10 esu (CHCl3).
The
incorporation of benzene rings also
proved to be unfavorable relative to equally
extended p linkers consisting of olefinic
R1
R2
Biphenyl[a]
1018 m
1030 b
1036 g
Fluorene[a]
1018 m
1030 b
1036 g
double bonds (Scheme 28).
[esu]
[esu]
[esu]
[esu]
[esu]
[esu]
The b values, which were obtained, for
H
H
46 a
0
0
10
46 b
0
0
example, by the EFISHG method (electric
H
NO2
47 a
3.8
4.1
15
47 b
4.1
5.1
29
field induced second harmonic generation),
OCH3
NO2
56 a
4.5
9.2
39
56 b
4.7
11
28
depend somewhat on the applied waveNO2
49 a
5.5
5.0
130
49 b
6.0
55
N(CH3)2
length. A simple correction to wavelength[a] Measurement of 46 a,b, 47 a,b, 56 a,b in 1,4-dioxane, of 49 a,b in CHCl .
3

Table 9: Dipole moments m and hyperpolarizabilities b and g of transstilbenes and their derivatives which bear a donor group in the 4-position
and/or an acceptor group in the 4-position.[107]
Compound

Solvent

4-R

4-R

1018 m
[esu][a]

1030 b
[esu][a]

1036 g
[esu][a]

92
93
94
38 b
95
13 a
96
97
98

CHCl3
1,4-dioxane
1,4-dioxane
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3

H
N(CH3)2
H
N(CH3)2
NH2
OCH3
SCH3
N(CH3)2
OCH3

H
H
NO2
NO2
NO2
NO2
NO2
CN
CN

0
2.1
4.2
6.6
5.1
4.5
4.3
5.7
3.8

0
10
11
73
40
34
34
36
19

26
64
61
225
147
93
100
125
54

[a] esu: electrostatic units; m: 1030 Cm = 0.2998  1018 esu = 0.2998 D;


b:
1050 Cm3 V2 = 2.694  1030 esu;
g:
1060 Cm4 V3 = 8.078 
36
10 esu.
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

The extension of the p linker in D-OP-A systems can


result in an increase in the b values;[71, 111, 112] similar to lmax(n),
it is possible to pass through a maximum of b(n). The first case
is realized with 56 ac (D = OCH3/A = NO2) and the latter
with 55 ad (D = NH2/A = NO2). The g values always increase
with increasing n. The effects are less pronounced in each case
compared to the oligoenes 101 and 102 (Table 11)even
when the oligoenes bear benzene rings on one or both ends
of the p linker. Consequently, oligoenes form the
focus in NLO investigations of push-pull-substituted
oligomers.[3, 53, 54, 56, 57, 58a,b, 71, 113119] Some examples are summarized in Table 12.
Analogous results are obtained for OEs with carotinoid
linkers (see Section 3.1).[54, 113, 115, 116, 117, 119] The incorporation of
five-membered-ring heterocycles, such as furan or thiophene,
in the p linker generates higher hyperpolarizabilities b than

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H. Meier

Table 11: Hyperpolarizabilities b and g of push-pull-substituted


oligo(1,4-phenylene)s (55, 56) and oligoenes with one (101) or two
terminal benzene rings (102).[3, 71]

Compound
56 a
56 b
56 c
55 a
55 b
55 c
55 d
101 a
101 b
101 c
102 a
102 b
102 c
102 d

OCH3

NH2

NO2

NO2

N(CH3)2

CHO

OCH3

NO2

1
2
3
1
2
3
4
1
2
3
1
2
3
4

Solvent
1,4-dDioxane

NMP

CHCl3

CHCl3

1030 b
[esu]

1036 g
[esu]

5.1
9.2
11.0
10
24
16
11
30
52
88
34
47
76
101

10
39
21
96
124
133
63
140
257
93
130
230

Table 12: Dipole moments m and hyperpolarizabilities b0 and g of


oligoenes.[56] (Structures shown in Scheme 12.)
Compound

m [D]

1030 b0 [esu]

33 b

0
1
2
3
4
0
1
2
3
4
5

8.8
9.3
9.8
10
10
9.7
9.0
10.2
10.5
11
11

74
195
361
642
1229
63
195
423
810
1043
1530

34 b

1036 g [esu]
378
1724
7363

395

for the corresponding benzene systems with comparable


linker lengths, but lower b values than analogous compounds
with diene building blocks. Table 13 shows comparisons of
compounds 52/61, 38 b/59/58, and 56 c/60/66 c/102 b.
Empirical laws were proposed many times on the basis of
measured data for the hyperpolarizabilities b and g. These
laws reflect the influence of the substituents[71] and the
influence of the number n of repeat units in the oligomers,[54, 56, 57, 110, 112, 116, 129] and include equations such as (22) and
(24). Additional power laws derived on a theoretical or
b0  nk or log b0  log n
e:g: k 1:9,56
2:0,110 2:454

2498

22

23

Table 13: Comparison of the hyperpolarizabilities b0


compounds with and without heterocycles in the p linker.
Compound

Structural formula

of

D-p-A

1030 b0 [esu]

52[79, 81]

33

61[79, 81]

54

38 b[71]

73

59[71]

83

58[71]

98

56 c[71]

11

60[71]

40

66 c[81]

41

102 b[71]

47

semitheoretical basis also exist.[23] The rare case in which the


value of b does not increase monotonously with n, as for
example in the OP series 55 ad, cannot be covered by
Equation (22). The individual exponents k und refer to the
measurement of a certain series of donoracceptor-substituted oligomers under certain conditions; moreover, they
always refer to a narrow range of repeat units 1  n  5. The
expression > k is always valid for an oligomer series, which
means that the g values increase more strongly than the
b values for increasing numbers n. The exponents k and
should virtually be functions of n: k(n), (n). However, an
essential distinction arises from the fact that b0 should
approach a limiting value b for high numbers n, whereas
this is only valid in the case of g for dg/dn.[23, 24] A calculation
(ZINDO, CEO) was performed for oligoene linkers up to n =
40.[120, 121] Experimental values for such D-p-A systems do not
exist, nor for systems which are nearly as large. The
convergence problem of b and g/n can be compared
analogously to lmax !l by the aid of exponential functions.[122] Since the length L of the chromophore in conjugated
oligomers is a linear function of n, b(n) and g(n) can be
described as functions b(L) and g(L).
A simple calculation of b0 can be made with the energy hc/
lmax of the long-wavelength transition S0 !S1, the corresponding transiton moment m01, and the difference Dm of the dipole
moments m(S1) and m(S0)[123] by applying the two-level model
suggested by Oudar and Chemla.[108, 109] Equation (26) prob0

6m201Dml2max
h2 c2

g  n or log g  log n

24

e:g: 4:2,56 2:7116

25

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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26

vides the possibility to determine b0 for the normally


accessible region located away from the limiting value by
normal absorption measurements of lmax and m01 as well as by
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Conjugated Oligomers

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electrooptical absorption measurements (EOAM) of Dm. If


m01(n), Dm(n), and lmax(n) all increase with n, it is also valid for
b0(n).[79, 81] The situation is more critical when m201Dm increases
but l2max decreases. We obtained b0 values of 198, 287, and
346  1050 Cm3 V for the series 5 d7 d (n = 13), which means
that the value of b0 also increases in the case of a
hypsochromic series.[25] The fact that b0 increases with n,
irrespective of whether lmax increases or decreases, reveals
that a fitting function b0(lmax) is generally not meaningful.
However, the linear function log b = f(lmax) can give evidence
for substituent effects in compounds (for example, transstilbenes) which have the same p linker (see compounds in
Table 9).[107] Substituent effects, but not necessarily the pushpull effect, have an effect on the size of g. Hence, there are
examples for which the g values of D-p-A compounds are in
between the g values of D-p-D and A-p-A compounds.[116]
The power laws (27) and (28) suggested by Flytzanis and
c3  L6d or

27

log c3  log Ld
c3  l6max or

28

log c3  log lmax

co-workers[124, 125] only make sense when lmax increases with


the so-called delocalization length Ld.[126] The relation (27) is
problematic for short p linkers with Ld  n[105a] and the
correlation of c(3) or g with lmax is also not generally valid.
In the hypsochromic series 15 d, 16 d, , lmax(n) decreases
with growing n, but g(n) increases.[127] The relation (29) is
g  nm or log g  m log n

29

zwitterionic Z and an electroneutral resonance structure N


[Equations 30 and 31].
D -p-A Z $ D-p-A N
30

p
yS0 cyZ  1c2 yN
yS1

p
1c2 yZ cyN

31

Several suggestions were made for the determination of


the weights of the two limiting structures. Wortmann and
co-workers[79] proposed the parameter c2, which can be
obtained by Equation (32); the participation of Z and N is
c2



1
Dm
1 q
2
4m201 Dm2

32

considered therein to be included in the difference in the


dipole moments m(S1)m(S0) = Dm and the transition moment
m01. Integration of the absorption curve or an approximation
formula provide m01; Dm is accessable for example by electrooptical absorption measurements (EOAM). The difference D
of the dipole moments of Z and N is related to Dm and c2
according to Equation (33). Barzoukas et al.[6] used sin q/2
Dm
12c2
D

33

instead of c in Equation (30) and defined the mixed


parameter MIX as cosq which corresponds to (2c21) in
Equation (33).
Marder et al.[25] introduced the parameter BLA for the
alternation of bond lengths in linear D-p-A chains. The
parameter BOA for the alternating bond orders is closely
connected to the alternation of bond lengths. BLA is
accessible from X-ray data and is empiricly related to MIX
[Eq. (34)].[6] However, BLA is not very useful if the p linker

even reliable in such a case, in which m(n) decreases with n


and approaches the limiting value of 1.[105a] This convergence
defines an effective conjugation length n0ECL, which can,
however, be different from nECL obtained from the convergence of the long-wavelength absorption. The absorption
34
BLA in  0:11 MIX
takes S0 and S1 into account, and an essential-state model of
three, four, or more states is taken as the basis for the THG.
contains aromatic rings, because aromatic rings will keep their
To summarize Section 4, the statement can be made that
typical adjusted bond lengths.
in addition to the substituent effects of D and A on g and the
push-pull effect on b, the nature of the p linker (type, length)
Table 14 shows the relationship between the polarizabilplays a decisive role in the size of the b and g values. Even the
ities a, b, and g and the discussed parameters c2, MIX, and
same linker has a different effect when its polarization is
BLA. The parameter f proposed by Lu, Chen et al.,[128] was
different with various D/A pairs. An explanation for this is
also included in the table; f and MIX are connected by
provided in Section 5 in the context of VB
Table 14: Dependence of the polarizabilities a, b, and g on the parameters c2, MIX, f, and BLA with the
theory.
corresponding weigths of the resonance structures Z and A.

5. VB and MO Models of D-p-A


Systems

amax
b=0
j b j max
g=0

c2 [a]

Weights N/Z or Z/N

MIX[b]

f[a]

Weights N/Z or Z/N

BLA[c] []

0.5
0.5
0.211

50:50
50:50
79:21

0
0
1
 p5
1
p
q5

0.5
0.5
0.5  0.224
0.5  0.224

50:50
50:50
72:28
72:28

0
0
 0.049
 0.049

0.5  0.327
0.5

83:17
50:50

 0.072
0

As already stated in Scheme 2, the


model usually applied for D-p-A systems
in the literature is a valence-bond model. It
describes the ground state S0 and the first
electronically excited singlet state S1 of such
compounds by a linear combination of a

[a] 0 < c2 < 1, 0 < f < 1. [b] 1 < MIX < 1. [c] BLA is varied between the bond lengths L(C=C) = 1.34 
and L(=CC=) = 1.45  by about 0.11 ; if Equation (33) is not used, optimum BLA values of 0.04 
0.01  and 0.06  0.01 , respectively, are proposed for j b j max and j c1 j max.[129]

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j g1 j max
j g2 j max


0

3
7

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H. Meier

Equation (35). Moreover, for a better illustration, the


weights N/Z (and equivalent Z/N) valid for c2 and for
f

MIX 1
2

35

MIX and f are included in Table 14. The maximum of a is


reached for a 50:50 ratio of Z and A, that is, for a complete
equalization of the bonds (cyanine limit). Here, b = 0 (in
reality b is very small). The maximum of b is reached for an N/
Z ratio of about 3:1 (and its reciprocal); but then g = 0. A
parameter value close to the maximum of g can be
recommended for a simultaneous optimization of b and g.[129]
The parameters proved to be successful for relatively
short D-p-A systems with OE linkers. These parameters are
not adequate when c2 or f are close to 0 or 1 (MIX close to 1
or + 1), and the VB model with the y functions (30) and (31)
is generally not suitable for these cases.[21] An S1 structure
with predominant Z character (1c2  0.9) has a small
probability for an extended chromophore which has a
predominant N character in S0 (c2  0.1). The resonance
structure Z should have a similar energy as the resonance
structure N so that the resonance Z$N is combined with a
noticeable energy gain. The latter is certainly not realized
when the p linker consists of repeat units which contain
benzene rings or other aromatic ring systems.
An MO model appears to be much more suitable for such
oligomers. In this model, partial dipole moments are present
on the donor and the acceptor sides, and each partial moment
is itself composed of an intrinsic part (mD, mA) and a part which
is induced in each case by the dipole on the other chain end
(mDi, mAi). The induced parts become smaller with increasing
separation of the donor and acceptor. The extent of the
polarization from the ends of the chain in the direction of its
center should rapidly decrease. This was also demonstrated by
means of BLA values and partial charges obtained by a DFT/
B3LYP/6-31G* calculation.[130]
Semiempirical methods need to be considered for the
calculation of higher oligomers. We chose the AM1 method
for the optimization of the geometry and the INDO/S method
for the electron transitions.[21, 22] Scheme 29 shows the polarization derived from AM1) calculations of the olefinic double
bonds of the OPVs 5 d7 d and the corresponding triple bonds
of the OPEs 15 d17 din each case expressed in terms of the
charge differences Dq and Dq, respectively. The positive and
negative partial charges are related to the standards transstilbene and tolane, respectively.[131] The Dd and Dd values
reflect the differences in the chemical shifts of the 13C nuclei
of the double and triple bonds. A direct correlation can be
seen: a large Dq() value results in a large Dd() value. The
essential polarization can be found on the chain ends.[132] The
effect decreases strongly towards the center of the chain. This
trend of Dq() is even more pronounced for longer chains (n 
4).[21, 22] 13C NMR signals are a good indicator of partial
charges. The correlations of the 13C chemical shifts and their
differences Dd() (obtained by the aid of the 2D HMBC
technique) agree very well with the Dq() values, and therefore
support nicely the MO model. The decreasing significance of
the zwitterionic resonance structure Z with increasing dis-

2500

 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Scheme 29. MO model for conjugated oligomers with donoracceptor


substitution: Calculated charge differences Dq at the double bonds of
the OPVs 5 d7 d (n = 13) and Dq at the triple bonds of the OPEs
15 d17 d (n = 13); the differences Dd and Dd of the 13C chemical
shifts were measured in CDCl3.[21, 22]

tance of D and A can be also recognized in the compounds


(CH3)2N-OE-CHO 24 c26 c, in which the rotational barrier
of the CN bond decreases strongly with increasing values of
n.[52b,c]
Whereas the electron transitions S0 !S1 in trans-stilbene
and tolane are still almost pure HOMO!LUMO transitions,
other orbitals mix in for the D-OPV-A and D-OPE-A
systems, even for n = 1. The energy of HOMO1 approaches
constantly closer to the HOMO, and the LUMO + 1 constantly closer to the LUMO, as n increases. The transitions
HOMO1!LUMO,
HOMO!LUMO + 1,
and
HOMO1!LUMO + 1 become more and more important
for the long-wavelength absorption, especially since the
overlap density of the HOMO and LUMO becomes smaller
and smaller. Figure 15 shows as an example the OPEs 15 d
(n = 1) and 18 d (n = 4), with the AM1-INDO/S calculation
performed with dimethylamino groups instead of didodecylamino groups, which are necessary for solubilization. The
HOMO!LUMO transitions are characterized by a strong
intramolecular charge transfer (ICT) from the donor to the
acceptor side. Figure 15 reveals that the ICT plays a very
minor role in the other transitions. The long-wavelength
absorption band (the charge transfer band) of D-p-A systems
is essentially determined by the ICT.
D and A not only influence the orbital energies, they also
alter the electron correlation. In terms of a self-consistent
field (SCF) approximation, both the differences in the orbital
energies DE0 and also the configuration interactions of oneelectron functions need to be considered for the excitation
energies E(S0 !S1). Equation (36) contains the Coulomb
E DE0 J 2 K

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Conjugated Oligomers

Chemie

Figure 15. Calculation of the frontier orbitals of the OPEs 15 d and 18 d


and their partipication in the electron transition S0 !S1 by the AM1INDO/S method.

repulsion integral J and the exchange integral K.[133] E < DE0


is always valid because 0 % 2K < J. A charge transfer within
the chromophore diminishes the negative portion (2 KJ),
because the overlap density decreases. Thus, E becomes
smaller, which means that the band of the electron transition
is shifted to longer wavelengths. A reduction in the ICT
effects accordingly shifts the band to shorter wavelengths (see
Figure 3). The classical example is given by anthracene and
azulene. Although DE0 is the same, the excitation energy E of
the blue azulene is essentially smaller than E of the colorless
anthracene because an ICT from the five-membered ring to
the seven-membered ring takes place in the S0 !S1 transition
of azulene. This is not possible in the symmetric anthracene.[134] Figure 16 illustrates the relationship of Equation (36) in a simplified picture of a HOMO!LUMO
transition.

Figure 16. Influence of the donoracceptor substitution in D-p-A


systems on the energy of the long-wavelength electron excitation.
(Exclusive regard of HOMO and LUMO, DE0 as the difference of the
ionization energy and negative electron affinity EA according to
Koopmans theorem.)

The stronger the electron-releasing effect of D and the


electron-withdrawing effect of A is, the lower is the transiton
energy E (S0 !S1) of D-p-A systems with a constant number n
of repeat units. The decrease of the ICT for increasing
numbers n and a certain terminal D/A substitution is
expressed in the DEDA(n) term in Equation (13). Figure 17
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

Figure 17. Bottom: partipication of the HOMO!LUMO transition in


the long-wavelength absorption of 15 d18 d (n = 14) calculated by
AM1-INDO/S; middle: corresponding decrease in the term DEDA(n);
top: decrease in the calculated difference of the dipole moments
Dm(n) = m(S1)m(S0).

shows the calculated decrease of the HOMO!LUMO


fraction of S0 !S1 resulting from increasing numbers n in
the series 15 d18 d (D = N(CH3)2, A = NO2, n = 14).[22]
Simultaneously, the values of DEDA(n) and Dm = m(S1)m(S0)
decrease. As already explained in Section 2, the DEDA term is
able to diminish, cancel out, or reverse (to hypsochromic) the
bathochromic effect in a series of conjugated oligomers.
Analogous results were obtained for compounds 5 d8 d
with an OPV linker instead of the OPE linker.[21] Therefore, it
is not necessary to show here a picture of the highest occupied
and the lowest unoccupied orbitals.[21, 25] The stronger the
donor and acceptor are, the faster the participation of the
HOMO!LUMO transition decreases for the long-wavelength absorption, the more the topology of the other
involved orbitals determines the decrease of the ICT, and
the more rapidly the ICT-affected correction term DEDA(n)
approaches zero (Figure 18).

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H. Meier

Figure 18. Partipication of the HOMO!LUMO transition in the longwavelength absorption of OPVs with an increasing number n of repeat
units (AM1-INDO/S calculation); b) dependence of the ICT term DEDA
on the fraction of H!L transition in the push-pull series (H3C)2NOPV-NO2 and (H3C)2N-OPV-CN.

6. Summary and Outlook


Conjugated oligomers with terminal donoracceptor substitution are examples of molecular wires[135] which are
predestinated to have special optical and optoelectronic
effects. The preparation of such an oligomer series with an
increasing number of repeat units in the p linker is best
started on the donor side which bears solubilizing groups
(such as NR2, OR). The p linker is then extended by the
application of an extension reagent and a protection group
strategy until the acceptor group is attached in an end-capping
step. This approach is recommended for the construction of
parallel series with different acceptor groups to generate a
central series from which other series are accessible by
coupled, convergent syntheses.
The excitation of electrons in the linear or star-shaped
oligomers of this type is characterized by an intramolecular

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 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

charge transfer (ICT). The charge-transfer band reacts quite


differently upon the extension of the chromophore, because a
hypsochromic effect resulting from the decrease in the ICT is
opposed to the bathochromic effect caused by the extension
of the conjugation. This becomes apparent as soon as the
number n of repeat units is increased, and consequently the
distance between the donor and acceptor enhanced. The
superposition of both influences leads to the variants for the
S0 !S1 transitions which are summarized in Table 15. In
addition to the strength of donor and acceptor in the present
D/A pair, the type of p linker plays a decisive role. Until now,
exclusively bathochromic series exist for the oligoenes (DOE-A) and oligoynes (D-OI-A; type (a): lmax(n) <
lmax(n+1)  l). In contrast, oligo(1,4-phenylenevinylene)s
(D-OPV-A) and oligo(1,4-phenyleneethynylene)s (D-OPEA) bearing strong donors and strong acceptors as end-groups
can exhibit a hypsochromic behavior (type (b): lmax(n) >
lmax(n+1)  l). A certain weakening of the donor or
acceptor strength may then give rise to a borderline case, in
which the long-wavelength absorption is independent of the
size of the chromophore (type (a)/(b): lmax(n)  lmax(n+1) 
l). OPV and OPE series with weak donors and weak
acceptors show a bathochromic behavior. Oligo(1,4-phenylene)s (D-OP-A) and oligo(2,5-thienylene)s (D-OT-A) are
special cases of type (c), in which lmax(n) passes through a
maximum. Torsions along the p linker have a decisive
influence on the CT band.[136] The fourth imaginable case, in
which lmax passes through a minimum, has not been unequivocally proven to date.[137] The number of investigated
compounds of oligo(2,5-thienylenevinylene)s (D-OTV-A) or
oligo(2,5-thienyleneethynylene)s (D-OTE-A) is too small for
a reliable conclusion to be drawn.
The superposition of conjugation effect and opposite
ICT effect can be rationalized by the superposition of two
exponential functions (Figure 3); both effects exhibit a
convergence behavior (n!). The intramolecular charge
transfer diminishes the electron correlation, which is of
special importance for the HOMO!LUMO excitation.
However, semiemprical quantum mechanics (AM1, INDO/
S) studies on D-OPV-A and D-OPE-A systems reveal that
the HOMO!LUMO fraction of the long-wavelength absorption decreases continuously as n grows, that is, as the size of
the chromophore grows (Figure 15). Together with this, Dm =
m(S1)m(S0) and the correction term of the ICT in the
absorption decrease (Figures 17 and 18).
The VB model D-p-A$D+-p-A often used in the
literature is primarily suitable for the case in which short
oligoenes are used as a p linker. This model with its
zwitterionic resonance structure is not very useful for other
p linkers, particularly not for p linkers which contain aromatic rings. In contrast, an MO model proved to be successful,
which implies a decreasing polarization from the donor as
well as from the acceptor side towards the center of the
p linker (Scheme 29).
In the field of nonlinear optics (NLO), laws were often
temptatively proposed that correlated the hyperpolarizabilites b and g with lmax values. This approach, however, fails for
hypsochromic series. Power laws or logarithmic functions
can be used which contain the length L of the chromophores

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Conjugated Oligomers

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Table 15: Classification of the absorption behavior of series of donoracceptor-substituted conjugated


oligomers according to their dependence on the D/A combination and the p linker.
p
linker

Monotonously bathochromic series type (a)

Borderline
type (a)/(b)

Monotonously hypsochromic series type (b)

OPV

NR2/CN
OR/NO2
OR/CHO
OR/squaraine
ferrocene/NO2
OR/C+
NR2/1,3,5-triazine
OR/1,3,5-triazine
NR2/C CH
OR/CN

NR2/CHO

NR2/NO2
NR2/CH=C(CN)2
NR2/squaraine
NR2/1,3,5-triazinium

OR/NO2
NR2/CN

NR2/NO2
NR2/CH=C(CN)2
NR2/CHO

OPE

OE[a]
OI
OP

all investigated D/A combinations


NR2/NO2
OR/NO2
OR/CN
OR/NO2
NR2/NO2
NR2/CH=(C(CN)2
SR/NO2
OR/NO2

Series with an energy


minimum type (c)

D-p-A structures tailored for certain electrooptical applications


(molecular engineering) represent
the final, highly promising goal.[142]
I am grateful to the Deutsche Forschungsgemeinschaft, the Volkswagen Foundation, the Fonds der
Chemischen Industrie, and the
Center of Materials Science of the
University of Mainz for financial
support of my own work cited in this
article.
Received: July 1, 2004

NR2/NO2
NR2/CN
NR2/NO2

[1] Selected
monographs
and
reviews: a) H.-H. Hrhold, M.
OT
Helbig, D. Raabe, J. Opfermann,
OTV[b]
U. Scherf, R. Stockmann, D.
Wei, Z. Chem. 1987, 27, 126
OTE
137; b) J. L. Brdas, R. Silbly,
Conjugated Polymers, Kluwer,
[a] D: NR2, OR, SR, ferrocene, A: NO2, CHO, CN, CH=CR2 containing electron-withdrawing groups R,
Dordrecht, 1991; c) K. Mllen,
C+; the OE linkers also include benzene or thiophene rings on one or both ends of the chain. [b] The OTV
Pure Appl. Chem. 1993, 65, 89
linker includes a terminal benzene ring on the donor side.
96; d) W. R. Salaneck, I. Lundstrm, B. R. Rnby, Conjugated
Polymers and Related Materials,
or the number n of repeat units in their argument. In contrast
Oxford University Press, Oxford, 1993; e) J. M. Tour, Chem.
to lmax and b, g does not approach a limiting value for n!,
Rev. 1996, 96, 537 553; f) R. Giesa, J. Macromol. Sci. Rev.
but g/n does.[23] The effective conjugation lengths nECL
Macromol. Chem. Phys. 1996, 36, 631 670; g) J. S. Moore, Acc.
Chem. Res. 1997, 30, 402 413; h) L. Jones II, J. S. Schumm,
required for nonlinear optical properties are much greater
J. M. Tour, J. Org. Chem. 1997, 62, 1388 1410; i) J. Roncali,
than for linear optics. Therefore, an experimental proof of the
Chem. Rev. 1997, 97, 173 205; j) A. Kraft, A. C. Grimsdale,
convergence of b and g/n is much more difficult.
A. B. Holmes, Angew. Chem. 1998, 110, 416 443; Angew.
Besides the selected D/A combination, the nature and
Chem. Int. Ed. 1998, 37, 403 428; k) Electronic Materials: The
length of the p linker are decisive for b and even to a greater
Oligomer Approach (Eds: K. Mllen, G. Wegner), Wiley-VCH,
extent for g. 1,4-Phenylene units in an OP linker show a
Weinheim, 1998; l) T. M. Swager, Acc. Chem. Res. 1998, 31,
torsion along the chain which is unfavorable for large
201 207; m) P. F. H. Schwab, M. D. Levin, J. Michl, Chem. Rev.
1999, 99, 1863 1933; n) U. Scherf, Top. Curr. Chem. 1999, 201,
hyperpolarizabilities. On the whole, a comparison of b and
163 222; o) R. E. Martin, F. Diederich, Angew. Chem. 1999,
g values of various series D-p-A is essentially more difficult
111, 1440 1469; Angew. Chem. Int. Ed. 1999, 38, 1350 1377;
than a comparison of linear optical properties. The errors of
p) J. J. Wolff, R. Wortmann, Adv. Phys. Org. Chem. 1999, 32,
the methods are considerably larger than, for example, for
121 217; q) U. H. F. Bunz, Chem. Rev. 2000, 100, 1605 1644;
lmax values, even when static, that is, wavelength-independent
r) J. L. Segura, N. Martin, J. Mater. Chem. 2000, 10, 2403 2435;
b0 values and nonresonant g values are used. Relative quans) G. Hadziioannou, P. F. van Hutten, Semiconductivity Polymers, Wiley-VCH, Weinheim, 2000; t) J. Roncali, Acc. Chem.
tities related to a standard, which is measured at the same

conditions, for example [Eq. (37)], are recommended for


materials science applications.
brel

b0 compound molecular mass 4-nitroaniline



b0 4-nitroaniline molecular mass compound

37

Altogether, considerable deficits can be recognized for


the experimental determination of b and g values of oligomer
series. Numerous theoretical attempts have been made for
their linear (Section 2) and nonlinear optics (Sections 4 and
5).[138, 139] A new approach in the synthetic area is offered by
star-shaped compounds (Section 3.3)[140] and dipolar structures such as 101, in whichcontrary to the resonance
described in Scheme 3-the aromatic and dipolar resonance
structures are compatible (Scheme 30).[141] The preparation of
Angew. Chem. Int. Ed. 2005, 44, 2482 2506

Scheme 30. Resonance forms of a quinoid, electroneutral, and an


aromatic, zwitterionic resonance structure as an example that is
opposed to the usual resonance of an aromatic, electroneutral, and a
quinoid, zwitterionic limiting structure.

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2503

Reviews

[2]
[3]

[4]
[5]
[6]
[7]

[8]
[9]

[10]
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[12]
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[24]
[25]

[26]
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[30]

2504

H. Meier

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S. R. Marder, C. B. Gorman, F. Meyers, J. W. Perry, G. Bourhill,
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H. Meier, J. Gerold, H. Kolshorn, W. Baumann, M. Bletz,
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2505

Reviews

H. Meier

[112] G. Berkovic, Y. R. Shen, M. Shadt, Mol. Cryst. Liquid Cryst.


1987, 150, 607 616.
[113] M. Blanchard-Desce, J.-M. Lehn, M. Barzoukas, I. Ledoux, J.
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[125] G. P. Agrawal, C. Cojan, C. Flytzanis, Phys. Rev. B 1978, 17,
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[126] Ld is defined as the quotient (b22b21)b1
for oligoenes with
2
alternating double and single bonds and the corresponding
resonance integrals b1 < b2 ; b-carotene has for example with
n = 11 conjugated double bonds the value Ld = 7.5 < n. See also
G. P. Agrawal, C. Flytzanis, Chem. Phys. Lett. 1976, 44, 366
370.
[127] C. Bubeck, K. Koynov, B. Mhling, H. Meier, unpublished
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[128] D. Lu, G. Chen, J. W. Perry, W. A. Goddard III, J. Am. Chem.
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[131] The quantum mechanical calculations were performed with
dimethylamino groups.
[132] It depends on the donor and acceptor strength which of the two
groups D and A causes the greater polarization; see Scheme 30
and ref. [130].
[133] See, for example: J. Michl, V. Bonacic-Koutecky, Electronic
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[134] J. Michl, E. W. Thulstrup, Tetrahedron 1976, 32, 205 209.
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[137] A DAOPE series, which is of interest for this case, was studied
by Mllen and co-workers[48]: lmax(1) > lmax(2) < lmax(3). However, since additional hexyl side chains were introduced on
going from n = 1 to n = 2, the minimum of lmax for n = 2 could
result from other effects.
[138] This also includes analyses of obtained vibrational bands in IR
and Raman spectra.
[139] a) A. Bianco, M. Del Zoppo, G. Zerbi, Synth. Met. 2002, 125,
81 91; b) G. Zerbi, C. Castiglioni, M. Del Zoppo in ref. [1k],
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[141] A. Abbotto, L. Beverina, S. Bradamante, A. Facchetti, C. Klein,
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