J. Phys. Chem.

1994,98, 13513-13516 13513

Molecular Hyperpolarizabilities of Coumarin Dyes

Christopher R. Moylan
IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099
Received: August 25, 1994@

The molecular hyperpolarizabilities of 14 amine-substituted coumarins have been measured by electric-field-

induced second harmonic generation (EFISH). The results are compared with semiempirical calculations.
Conclusions are drawn with regard to preferability of the various electron donors and acceptors involved, as
well as to the utility of these compounds in the three major applications for nonlinear optical chromophores.

Introduction
Chromophore-doped polymers are being vigorously studied
for use in three nonlinear optical applications. The first is for
electrooptic materials,' which are the heart of the optoelectronic
devices that convert continuous-wave diode laser beams into
optical signals that can be switched or modulated at gigahertz
frequencies. The second application is frequency doubling of
diode laser light2 so that optical storage devices can operate
near 400 nm rather than 800 nm, leading to a factor of 4 increase
in storage densities. Photorefractive materials represent the third
application area3 and show promise for holographic storage and
intensity-dependent filters, among other things.
For each of these applications, nonlinear optical chromophores
of differing properties are required. There is only one class of
chromophores that has been successfully exploited for research
in all three areas, and that is the coumarins. Coumarin-
substituted methacrylate polymers have been shown by Mor-
tazavi et aL4to have reasonable electrooptic coefficients; a patent
on such materials has been issued.5 Yankelevich et a1.6 have
demonstrated frequency doubling of short 625-nm pulses with
a similar coumarin-based material. And Silence et al. have
shown7 that coumarin-doped polysilanes exhibit photorefrac- CF, n
tivity and excellent charge mobility. Because the nonlinear
optical properties of any polymer film are crucially dependent
upon the molecular hyperpolarizability and dipole moment of
its chromophore, it is clearly important to determine which Figure 1. Structures of the coumarins studied in this work.
particular substituted coumarins have higher nonlinearities. Yet
no coumarin hyperpolarizabilities have apparently ever been
measured. Accordingly, a series of 14 amine-substituted
coumarins has been characterized.

Experimental Section
The 14 compounds studied in this work are shown in Figure
1. All of them possess a trifluoromethyl acceptor group at the
4-position (compounds 1-6) or a julolidine donor group
(compounds 6-14) or both (the ring-numbering convention is
shown in Figure 2). All of the compounds possess an amino
donor of some kind attached to the 7-position of the fused ring
system. Coumarins are typically identified by numbers, and a
given compound may have more than one identifying number.
In the following source list, multiple identifiers are shown by a
slash between them. All coumarin compounds were obtained
commercially and used as delivered. Coumarins 490/151 (l),
500 (3), LD49016H (7), 519/343 ( l l ) , 504/314 (12), 523/337
(13), and 510 (14) were obtained from Exciton. Coumarins
152/485 (2), 106/478 (9),and 334/521 (10) were obtained from
@Abstractpublished in Advance ACS Abstracts, November 15, 1994.
0022-365419412098-13513$04.5010
5 4
Figure 2. Numbering convention for the coumarin ring system.
Eastman or Eastman Kodak. Coumarins 152A/481(4), 522 (5),
1531540A (a), and 1021480 (8) were obtained from Lambda-
Physik. All of these compounds will be referred to henceforth
by the identifying numbers 1-14 shown in Figure 1.
All hyperpolarizabilities were measured by electric-field-
induced second harmonic generation (EFISH)in chloroform
solution as previously described.8 The frequency-doubling
experiments yielded the product pb; separate dielectric measure-
ments were performed in order to determine the dipole moment
for each compound independently, allowing extraction of the
hyperpolarizability. p values were determined by using expres-
sions recommended for consistency in conventionsgand were
referenced to the currently preferred value for the nonlinearity
of quartz.lo*ll Both of these choices have so far led to
0 1994 American Chemical Society
13514 J. Phys. Chem., Vol. 98, No. 51, 1994 Moylan
TABLE 1: Nonlinear Optical Data for CoumarhW
coumarin A, U BloM BO

14 430 7.44 fO.O1 114f5 32.9 f 1.7

13 446 10.2 f 0 . 1 132 f 2 32.4 f 0.8
12 436 8.20 f 0.02 106 f 1 29.0 f 0.7
11 448 9.86 f 0.07 120 f 8 28.6 f 2.0
10
6
452
418
7.56 f 0.04
6.55 f 0.01
111 f 6
49.1 f 2.6
25.4 f 1.3
15.8 f 0.8
0.80 1
4 400 6.07 f 0.02 41.8 f 0.8 15.7 f 0.3 B 0.60
5 406 6.14 f 0.01 42.8 f 2.2 15.3 f 0.8
3 378 5.59 f0.04 29.0 f 1.2 12.6 f 0.5 0.40

7
2
8 388
392
392
6.98 f 0.01
6.76 f 0.05
5.71 f 0.01
30.6 f 5.1
27.9 f 1.3
27.0 f 0.8
12.4 f 2.1
11.0 f 0.5
10.6 f 0.3
0.20 1
9 382 6.39 f 0.05 22.1 f 1.7 9.4 f 0.7 0 . 0 0 ~ ~ ' ~ " ~I '
2.550 2.570 2.590 2.610 2.630 2.650
1 358 4.59 f 0.10 18.7 f 1.0 9.0 f 0.5
Log 1 max (nm)
Wavelengths given in nm, dipole moments in debye, and hyper- Figure 3. Nonlinearity-transparency plot for coumarins 1-14.
polarizabilities in esu.
dipole moment. The coumarins are somewhat more compli-
TABLE 2: Results of Semiempirical Calculations using the
MOPAC Program, the PM3 Hamiltonian, and the Dipole cated. The MOPAC calculations indicate that the carbon in
Moment Expansion the 3-position bears a partial negative charge in the ground state
for all of the coumarins, whereas the carbon in the 4-position
coumarin P BO coumarin P BO
has a very slight positive charge. These results suggest that
13 9.20 28.6 2 4.63 17.3 intramolecular charge transfer would be better facilitated by
14 6.01 25.2 3 4.66 17.0
12 6.59 24.5 1 4.43 13.2 attachment of an electron-withdrawing substituent at the 3-posi-
11 9.33 24.4 5 4.61 11.3 tion rather than the 4-position. Because the f i s t excited state
4 5.14 22.2 8 5.73 9.2 in nonlinear optical chromophores typically exhibits intramo-
10 6.81 21.7 7 5.40 8.2 lecular charge transfer in the same direction but to a greater
6 5.21 18.8 9 5.27 7.1 extent than in the ground state, one can infer that 3-substituted
coumarins might have larger hyperpolarizabilities than 4-sub-
predictions for electrooptic constants that have come closest to stituted coumarins. That prediction is generally borne out by
the experimental values.'* As part of each day's frequency- both the experimental results and the calculations; coumarins
doubling work, the pure solvent was referenced to a quartz 10-14 represent most of the higher entries in Tables 1 and 2.
crystal. The average 1064-nm susceptibility of CHC13 in this It must be noted, however, that no direct comparison between
work, 4.0 x esu, was in reasonable agreement with the two coumarins with identical electron acceptors in the 3- and
value of Burland et al.13 (corrected for the most recent value 4-positions was possible with these commercially available
for the quartz standard). compounds.
It has been shown that PO has an explicit second-order
Results dependence on d, and the transition dipole moment" or
Molecular hyperpolarizabilities, dipole moments, and absorp- (equivalently) an explicit third-order dependence on Amm
tion maxima for all compounds measured in this work are shown multiplied by the oscillator strength.18 The oscillator strength
in Table 1. In addition to the 1064-nm hyperpolarizability, the itself tends to increase with am=, so the wavelength dependence
extrapolated zero-frequency value, PO,was determined by means of the zero-frequency hyperpolarizability is often quite strong.
of the two-level model14 and is also included in the table. It has become customary to compare the two quantities for a
Uncertainty limits are provided for dipole moments and hyper- series of similar compounds on a log-log plot, whose slope
polarizabilities,based on the statistical uncertainties in the slopes gives some indication of the amount of transparency that must
of the least-squares lines used15 to determine p and P. be sacrificed to achieve an increase in nonlinearity within the
Therefore, they reflect the precision of the measurements rather set of chromophores. Such a plot for the coumarins is shown
than their accuracy. in Figure 3. The slope of the plot in Figure 3 is 6.1 & 0.7,
Although accurate values for the hyperpolarizabilities of approximately the same as for pyrazoles19 and tolanes.20
molecules of this size are difficult to calculate even with ab The relative order of nonlinearities of the 14 coumarins based
initio methods, it is a useful exercise to run simple calculations on the EFISH data is consistent (within experimental error) with
for comparison with experimental data. Accordingly, the that based on MOPAC calculations, except for coumarins 1,2,
nonlinear optical properties of each of the coumarins was and 5. The log-log plot shows that the absorption maxima
calculated semiempirically, using the MOPAC program.16 The for these three chromophores are consistent with their experi-
dipole moment expansion and the PM3 basis set were used. mental hyperpolarizabilities. The MOPAC calculations indicate
The results are shown in Table 2. that POfor 1 and 2 should have been relatively higher and that
PO for compound 5 should have been lower. Given the
Discussion consistency of the absorption spectra and the EFISH data for
these compounds, one must conclude that the semiempirical
Relative Order of Nonlinearities. Most nonlinear optical calculations are not optimized for distinguishing between
chromophores consist of a roughly linear n-conjugated system different amino donors (see below).
with an electron donor at one end and an electron acceptor at The relative order of dipole moments across the coumarin
the other. For such compounds, it is easy to determine sample set is also fairly consistent between the calculations and
resonance structures of charge-transfer excited states and to the experimental results. The absolute values of the calculated
make accurate predictions as to the effect of any given donor dipole moments are uniformly lower than the experimental
or acceptor substitution on the molecular hyperpolarizability and values, by an average of 1.1 D. Such discrepancies have been
Molecular Hyperpolarizabilities of Coumarin Dyes
seen before. For example, the PM3 dipole moment for
2-methyl-4-nitroaniline is 6.7 D, whereas an ab initio value of
8.2 D has been reported.13 Given the large discrepancies in
absolute values, the 0.3-D error limit on calculated dipole
moments that would be required for the calculated order to be
consistent with the experimental order seems reasonable.
Relative Strengths of Amine Donor Groups. Among the
4-trifluoromethyl coumarin derivatives, the order of relative
nonlinearities should reflect the order of electron-donating
abilities of the amine substituents. Since the amine moiety is
expected to bear the positive charge resulting from intramo-
lecular electron transfer, increasing the number of saturated
carbons bonded to the nitrogen should increase the hyperpo-
larizability. The julolidine derivative 6 (six carbons) would
therefore be expected to have the highest nonlinearity, followed
by the N-methylpiperidineand dimethylamino compounds 5 and
4 (four carbons), the ethylamino and dimethylamino derivatives
3 and 2 (two carbons), and finally the simple amino derivative
1. This is the exact order of the experimentally determined
1064-nm hyperpolarizabilities. 4 and 5 had the same value of
Up at 1064 nm within experimental error; when the two-level
model extrapolation is performed to yield 60, coumarin 6 also
becomes indistinguishable experimentally from the other two.
Although the relative donor strengths of compounds 1-6 (as
manifested experimentally by their molecular hyperpolarizabili-
ties) are in accord with simple physical organic chemistry
concepts, the semiempirical calculations indicate that the order
should have been different. The calculations correctly predict
that Up0 for 2 and 3 should be quite similar and that 1 should be
lower but incorrectly predict that 5 should have the lowest
nonlinearity and that 6 should not be the most nonlinear in the
series. One possible explanation is that these approximate
calculations underestimate the electron-donating abilities of
amino groups that contain saturated rings. As a consequence,
small donor groups without rings such as NHz and N(Me)2 will
be artificially improved in any comparison. This phenomenon
probably accounts for the noticeable difference between ex-
perimental ranking and ranking based on MOPAC calculations
for compounds 1, 2, and 5.
Relative Strengths of Electron-Acceptor Groups. The
predicted order of zero-frequency nonlinearities for 3-substituted
coumarins is consistent with the experimental results. Cyano
derivative 13 was calculated to have the highest PO;it actually
had the highest 6 at 1064 nm but when extrapolated to zero
frequency is experimentally indistinguishable from m-pyridyl
analogue 14, which was predicted to have the second highest
nonlinearity. Unsurprisingly, substitution of an electron donor
across the 3- and 4-positions yields a compound (9) that has a
lower hyperpolarizability than one with no substitution (7).
Choosing Chromophores for Specific Applications. Each
of the three applications for nonlinear optical chromophores
determines a unique set of criteria for choosing one compound
over another. For electrooptic applications, the product pUpIM
at the wavelength of interest needs to be maximized, because
not only must a chromophore have a large nonlinear response,
but it must also be easily alignable in an electric field, and one
must be able to achieve a large molecular concentration of it.
Among the 14 coumarins studied in this work, the best
chromophore for electrooptic applications at 1300 nm would
be 13, whose figure of merit is 1.53. Compounds 11 and 14
would be the second and third choices, respectively.
The coumarin used by Mortazavi et alS4in their electrooptic
polymer had a diethylamino donor and a carboxamide acceptor
in the 3-position. At a poling field of 100 Vlpm, poling
temperature of 150 "C, and chromophore concentration of 9.8
J. Phys. Chem., Vol. 98, No. 51, 1994 13515
x 1020~ m - that~ , methacrylate material was found to have an
electrooptic coefficient of 12 p m N at 477 nm and 2 p m N at
1115 nm. These values correspond to a two-level model
effective ,A of 396 nm (the actual absorption maximum was
410 nm). By use of the appropriate dispersion expression,l2
one can calculate that the EO coefficient at 1300 nm would be
1.9 pmN, and at 830 nm, it would be 2.4 pmN. A polymer
with the same concentration of coumarin 13, poled under the
same conditions, would have an EO coefficient of 3.3 p m N at
1300 nm and 4.7 p m N at 830 nm (using its actual Amm of 446
nm for the extrapolation).
Photorefractive materials must have respectable electrooptic
coefficients, and they must also be photoconductive. For
holographic storage applications, one would prefer to operate
at the bluest possible diode laser wavelength, which for the
purpose of this discussion will be assumed to be 700 nm. It
has been shown that if the chromophore is physically small
enough to retain some mobility within its polymer host, an
orientational enhancement of the photorefractive effect is
observed.z1 Therefore, low molecular weight is even more
important for photorefractive materials than for simple elec-
trooptic materials. If we arbitrarily define a figure of merit as
and evaluate it at 700 nm, coumarin 13 is shown to be
the best choice for photorefractive applications as well. Cou-
marins 11 and 10 would be the best alternatives for this purpose.
For frequency-doubling applications, transparency is vital.
The chromophore must have negligible absorption at the second
harmonic. The unusually sharp edges on the red side of
coumarin absorption bands make them particularly attractive
for second harmonic generation. For the standard 830-nm laser
sources, though, only compound 1 out of the chromophores
studied here meets the criterion of negligible absorption.
Depending upon the amount of absorption that could be tolerated
in a given device configuration, coumarin 3 might be usable. If
so, it would be clearly superior to 1 in nonlinear activity.
Predictions for Improved Nonlinearity. Although the
compounds studied in this work are just a sample of the
commercially available coumarins, the results suggest that
improved nonlinear performance is unlikely to be achieved
without custom synthesis. For the two applications that require
large electrooptic coefficients, incorporation of the strongest
available donor and acceptor groups Cjulolidine and cyano) has
yielded the best chromophore. Although substitution of increas-
ingly strong donors and acceptors ultimately can result in
decreased nonlinearities,22it is clear that the coumarin structure
is not in that regime. The modifications that are most likely to
result in better electrooptic chromophores are the use of
cyanovinyl acceptor groupsz3for improved hyperpolarizabilities
and diarylamino donor groups18for improved thermal stabilities
(and possibly improved nonlinearities as well). For frequency-
doubling purposes, use of fluorinated acceptor groups24is the
most effective way to tune molecular hyperpolarizabilities
without seriously red-shifting absorption maxima. It would be
interesting to measure the nonlinear properties of the 3-trifluo-
romethyl analogues of coumarins 1-6 in this study, but even
the 3-fluor0 derivatives of coumarins 1 and 3 should exhibit
improved hyperpolarizabilities.
Conclusions
The nonlinear optical properties of 14 coumarins have been
measured and correlated with semiempirical calculations. The
experimental and calculated orders of relative nonlinearities are
in reasonable agreement. Substitution of electron-withdrawing
groups appears to be more effective in the 3-position than in
the 4-position. The coumarin ring system lies in the regime
13516 J. Phys. Chem., Vol. 98, No. 51, 1994
where increasing donor or acceptor strength results in increased
hyperpolarizability. Coumarin 337 (13), also known as Cou-
marin 523, a julolidinekyano derivative, was shown to be the
best choice for electrooptic and photorefractive applications.
Coumarin 151 (l),also known as Coumarin 490, was the only
compound unambiguously transparent enough for frequency-
doubling applications at 830 nm. Improved electrooptic per-
formance is predicted for diarylaminokyanovinyl analogues of
13, and improved frequency-doubling performance is predicted
for fluorinated analogues of 1.
Acknowledgment. Partial support of this work by the Air
Force Office of Scientific Research, the National Institute of
Standards and Technology, and the Advanced Research Projects
Agency is gratefully acknowledged. I thank the following IBM
colleagues: R. D. Miller for help with the semiempirical
calculations, D. M. Burland for helpful discussions, and P. B.
Comita, H. Ito, J. Pacansky, C. T. Rettner, and R. M. Shelby
for samples of various coumarins.
References and Notes
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