Second-order nonlinearity (p) in a series of partially oxidized bisferrocenes linked through conducting -C=N- linkages has been measured and found to vary linearly with the redox potential difference between the ferrocene moiety and the oxidant

Alagesan, K.

Das, Puspendu Kumar

Ray, Paresh Chandra

Samuelson, Ashoka G.

English

Publications of the IAS Fellows

RESEARCH COMMUNICATIONS
Partially oxidized ferrocenyl
complexes for nonlinear optics
K. Alagesan, Paresh Chandra Ray, Puspendu Kumar
Das, and Ashoka G. Samuelson
Department of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore 560012, India
Second-order nonlinearity (p) in a series of partially
oxidized bisferrocenes linked through conducting -
C=N- linkages has been measured and found to vary
linearly with the redox potential difference between
the ferrocene moiety and the oxidant.
DESIGNING organic molecules having large optical non-
linearities has been the topic of much current research''2.
Organometallic complexes prepared along these lines
have been found to exhibit large second-order non-
linearities3^. Indeed, they offer a variety of tunable
parameters unmatched in the realm of organic chemistry
such as low energy electronic transitions, variable oxida-
tion states of the metal atom, and electronic and steric
properties of the ligand for optimizing molecular hy-
perpolarizabilities. The recent discovery of large second-
order nonlinearity (|3) in certain mixed valence
compounds6 with a tunable intervalence charge transfer
transition suggests that there may be considerable poten-
tial for the discovery of large optical nonlinearities in
mixed valent organometallic molecules. The largest
second harmonic generation efficiency (220 x U) to date
for an organometallic compound came from a series of
ferrocene-based conjugated salts7. But their microscopic
nonlinearities have not been measured. Here we report
first hyperpolarizability (p) in a series of oxidized bis-
ferrocenes linked through various conducting organic
spacers, measured by the recently developed hyper-
Rayleigh scattering technique (HRS)8~'°.
Ferrocene carboxaldehyde has been linked to aromatic
amines and diamines to generate mononuclear function-
alized ferrocenes and the corresponding bisferrocenes.
These molecules are then oxidized using I2, 2,3-dichloro-
5,6-dicyano-l,4-benzoquinone (DDQ) and 7,7',8,8'-
tetracyanoquinodimethane (TCNQ) to give the products
indicated in Figure 1. Compounds la-3d have been
characterized" by various spectroscopic and analytical
techniques and their (3 values measured in acetonitrile
with 1064 nm radiation at low solute concentrations
( lO^-lO^M) by the HRS technique (Table 1). Since
these molecules are ionic in nature, the HRS technique
is specially suited for P measurements on them. The
error on these hyperpolarizabilities is ± 8%. The
wavelength of peak absorption in these molecules in
the visible region is also shown in Table 1. For com-
pounds absorbing appreciably in the green (~ 532 nm)
corrections were made as suggested by Laidlaw et al.6
and corrected values of P are listed.
CURRENT SCIENCE, VOL. 70. NO. I, 10 JANUARY 1996 69
RESEARCH COMMUNICATIONS
The nonzero and small P value of ferrocene (la) is
probably due to octupolar contributions from the non-
centrosymmetric eclipsed form which exists along with
the staggered DM conformation in solution. However,
the size of the Ji system along which the electrons are
delocalized is small and results in a low P value.
Attaching a pendant acceptor to ferrocene results in a
donor-acceptor motif (2a) and (3 increases moderately
as expected. What is surprising is that P increases further
by a factor of ca 1.5 when another ferrocene is attached
to the benzene ring through a similar Schiff base linkage
resulting in a donor-acceptor-donor D-A-D motif (3a).
Considering that the -C=N- linkage acts as an acceptor12,
2a is in fact, a D-A-D and 3a, a donor-acceptor-donor-
acceptor-donor (D-A-D-A-D) system. Alternating the
D-A motif appears to be suitable for nonlinear optics
(NLO) in the neutral molecules, unlike alternating pen-
dant donors and acceptors on the jc framework.
X
1 a
b I3
c (DDQ)
d (TCNQ)
Fe
Fe
2 a
b 3
c (DDQ)2
d (TCNQ)
Fe
= N-Q-N = CH
Fe
3 a
b 4.5
c (DDQ)2
d (TCNQ),
Figure 1. Structures of the neutral and oxidized ferrocene.
Table 1. The second-order nonlinearity (x 10"30 esu), relative
redox potential, AE,/2 (V), the absorption maximum Xmax (nm), and
absorbance at 532 nm e532 (x 103 M"1 cm"1) of compounds la-3d
Compound
la
Ib
Ic
Id
2a
2b
2c
2d
3a
3b
3c
3d
P
0.8
2.8
4.6
5.9
14.2
111.2
121.6
132.0
20.8
161.0
201.0
246.0
AEln
_
0.30
0.20
-0.13
_
0.08
-0.03
-0.36
-
0.18
0.08
-0.25
\»
380
420
470
580
460
550
567
589
465
556
572
588
^_
-
1.2
0.8
_
1.2
2.6
0.6
-
1.6
1.1
0.8
On the basis of cyclic voltametry, Mossbauer and
other spectroscopic data", we believe that the bisfer-
rocene moiety (3a) is unique in the ability of the two
iron centres to interact electronically. A recent report12
on similar functionalized ferrocenes supports this view
that the -C=N- linkage, indeed, allows for greater
electronic conjugation. Extended Hueckel calculations
on these complexes show that the highest occupied
molecular orbital is delocalized over the two iron centres
in 3a. Oxidation of all the neutral compounds results
in a tremendous increase in the p values. The measured
P values for the partly oxidized complexes are an order
of magnitude greater than those for the corresponding
neutral molecules. Since the oxidizing ability varies in
the order TCNQ < DDQ < I2, and the measured hyper-
polarizabilities of the complexes follow the reverse order,
we have examined the electrode potentials (AEl/2) for
the redox reactions. A remarkable correlation is obtained
between the AE]/2 and P (Figure 2). As AE1/2 decreases
in the positive sense, the free energy for electron transfer
from the bisferrocene moiety to the acceptor decreases
and only a charge transfer complex is formed. But this
is accompanied by an increase in p. Since the ferrocene
donors have low hyperpolarizabilities, the origin of the
large P values must lie elsewhere in the partially oxidized
complexes. It appears that the nonlinearity in these
complexes results from differential electron transfer from
the bisferrocene moiety to the oxidant in the ground
and excited states, resulting in a significant change in
the dipole moment between the two states. In other
words, in the excited state the ability of the oxidized
bisferrocene donor to accept an electron leads to a
reversal in the direction of charge transfer leading to
300 -
240
3 180
120 ~
60-
0
-0-50 -0.25 0 0-25 0-50
AE1/2(V)
Figure 2. p (I(r30esii) vs AEl/2 (V) for compounds 2b-d and 3b-d.
70 CURRENT SCIENCE, VOL. 70, NO. 1,10 JANUARY 1996
RESEARCH COMMUNICATIONS
a large 8(J. and hence large second-order nonlinearities
result in these complexes.
The 460 nm band in the neutral ferrocenes is attributed
primarily to a d-d transition which shifts to ~ 550 nm
on oxidation. The absorption band extends up to + 50
nm around Xmax and this may contribute to the resonance
enhancement of p through a two-photon mechanism. In
the case of complexes containing TCNQ and DDQ, this
band may also originate from TCNCT or DDQ~ respec-
tively. Although the ^max correlates linearly with p, no
straightforward correlation between the absorbance at
532 nm (e53,) and the measured P is observed. These
molecules do not absorb at ~ 1064 nm unlike the mixed
valence ruthenium complex3 and, therefore, a single
photon dispersion in p is ruled out.
In summary, we have clearly demonstrated that par-
tially oxidized ferrocenes formed by matching the redox
potentials of neutral ferrocene moieties and an oxidant
represent an entirely new class of complexes which
exhibit large first-order hyperpolarizability. p for the
corresponding neutral ferrocenes is, at least, an order
of magnitude smaller than the ionic compounds and
comparable to other ferrocenyl compounds studied in
the past. Since a huge library of metallocenes and their
oxidation potentials exist it is possible to design better
partially ionic NLO materials based on the above
guidelines. We are currently investigating this.
1. Lehn, J. M., Materials for Nonlinear Optics (eds Marder, S. R.,
Sohn, J. E. and Stucky, G. D.), Am. Chem. Soc. Symp. Series,
American Chemical Society, Washington D.C., 1991, vol. 455.
2. Long, N. J., Angew. Chem. Int. Ed. Engl., 1995, 34, 21-38.
3. Di Bella, S., Fragala, 1., Ledoux, I., Diaz-Garcia, M. A., Lacroix,
P. G. and Marks, T. J., Chem. Mater., 1994, 6, 881-884.
4. Kanis, D. R., Ratner, M. A., and Marks, T. J., Chem. Rev., 1994,
94, 195-242.
5. Calabrese, J. C., Cheng, L.-T., Green, J. C., Marder, S. R. and
Tarn, W., J. Am. Chem. Soc., 1991, 113, 7227-7236.
6. Laidlaw, W. M., Denning, R. G., Verbiest, T., Chauchard, E. and
Persoons, A., Nature, 1993, 363, 58-60.
7. Green, M. L. H., Marder, S. R., Thompson, M. E., Bandy, J. E., Bloor,
D., Kolinsky, P. V. and Jones, R. }., Nature, 1987, 330, 360-362.
8. Clays, K. and Persoon, A., Phys. Rev. Lett., 1991, 66, 2980-2983.
9. Clays, K. and Persoon, A., Rev. Sci. Instrum., 63, 3285-3289.
10. Ray, P. C. and Das, P. K., J. Phys. Chem., 1995, 99, 14414-14417.
11. Alagesan, K., PhD Thesis, Indian Institute of Science, 1995.
12. Bosque, R., Font-Bardia, M., Lopez, C., Sales, J., Silver, J. and
Solarms, X., J. Chem. Soc. Dalton Trans., 1994, 747.
ACKNOWLEDGEMENTS. We thank Dr S. Ramakrishnan for en-
lightening discussions. Financial assistance provided by the Department
of Science and Technology, Govt of India is gratefully acknowledged.
Received 25 September 1995; revised accepted 16 December 1995
CURRENT SCIENCE, VOL. 70, NO. 1, 10 JANUARY 1996 71


Partially oxidized ferrocenyl complexes for nonlinear optics

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Partially oxidized ferrocenyl complexes for nonlinear optics

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