4
5
Nonlinear Optical Properties of Organic Molecules and Crystals,
Eds. D. S. Chemla and J. Zyss, Academic Press, Orlando, FL,
1987.
Inter alia (a) Molecular Nonlinear Optics – Materials, Physics and
Devices, Ed. J. Zyss, Academic Press, San Diego, CA, USA, 1994;
(b) D. R. Kanis, M. A. Ratner and T. J. Marks, Chem. Rev., 1994,
94, 195; (c) J. J. Wolff and R. Wortmann, in Advances in Physical
Chemistry, Ed. D. Bethell, Academic Press, London, UK, 1999,
Vol. 32, p 121.
(a) R. Marder, B. Kippelen, A. K.-Y. Jen and N. Peyghambarian,
Nature, 1997, 388, 845; (b) S. R. Marder, C. B. Gorman, F.
Mayers, J. W. Perry, G. Bourhill, J.-L. Bre´das and B. M. Pierce,
Science, 1994, 265, 632; (c) S. R. Marder, C. B. Gorman,
B. G. Tiemann and L.-T. Cheng, J. Am. Chem. Soc., 1993, 115,
3006; (d) I. D. L. Albert, T. J. Marks and M. A. Ratner, J. Phys.
Chem., 1996, 100, 9714.
Table 2 First hyperpolarizability (b) values for DBAs 1–6 in CHCl3 as
measured using ESM of HRS
b
DBA
lmax/nm
b
expt/10228 esu
b0a/10228 esu
(b0/M)rel
1
2
3
4
5
6
338
355
480
418
392
329
438
12.5
12.8
21.2
15.0
4.2
6.6
6.3
3.1
4.9
1.7
1.7
2.4
1.4
1.3
0.7
0.9
0.3
0.5
~1
6
3.8
16.0
DANSc
ab0 is the first hyperpolarizability after dispersion correction. b(b0/
M)rel is the normalized NLO figure of merit for the DBAs relative to
DANS where M is the molecular mass of the corresponding chromo-
c
phores. Reference 18.
7
8
(a) J. Zyss, I. Ledoux, M. Bertault and E. Toupet, Chem Phys.,
1991, 150, 125; (b) J. Zyss, J. Chem. Phys., 1993, 98, 6583; (c) J. Zyss
and I. Ledoux, Chem. Rev., 1994, 94, 77; (d) S. Brasselet and
J. Zyss, J. Opt. Soc. Am. B, 1998, 15, 257.
(a) I. Ledoux, J. Zyss, J. Siegel, J. Brienne and J.-M. Lehn, Chem.
Phys. Lett., 1990, 172, 440; (b) M. Joffre, D. Yaron, R. J. Silbey
and J. Zyss, J. Chem. Phys., 1992, 97, 5607; (c) C. Dhenaut,
I. Ledoux, I. D. W. Samuel, J. Zyss, M. Bourgault and H. L. Bozec,
Nature, 1995, 374, 339.
(a) T. Verbiest, K. Clays, C. Samyn, J. Wolff, D. Reinhoudt and
A. Persoons, J. Am. Chem. Soc., 1994, 116, 9320; (b) J. J. Wolff,
D. La¨ngle, D. Hillenbrand, R. Wortmann, R. Matschiner,
C. Glania and P. Kra¨mer, Adv. Mater., 1997, 9, 138;
(c) R. Wortmann, C. Glania, P. Kra¨mer, R. Matschiner,
J. J. Wolff, S. Kraft, B. Treptow, E. Barbu, D. Langle and
G. Go¨rlitz, Chem. Eur. J., 1997, 3, 1765; (d) R. Spreiter,
C. Bosshard, G. Kno¨pfle, P. Gu¨nter, R. R. Tykwinski,
M. Schreiber and F. Diederich, J. Phys. Chem. B, 1998, 102, 29;
(e) Y.-K. Lee, S.-J. Jeon and M. Cho, J. Am. Chem. Soc., 1998,
120, 10921; (f) J. J. Wolff, F. Siegler, R. Matschiner and
R. Wortmann, Angew. Chem., Int. Ed., 2000, 39, 1436;
(g) B. R. Cho, S. B. Park, S. J. Lee, K. H. Son, S. H. Lee,
M.-J. Lee, J. Yoo, M. Cho and S.-J. Jeon, J. Am. Chem. Soc., 2001,
123, 6421.
signals as compared to DANS solution. Table 2 gives the
experimental b values19 of the DBAs when the measurements
were carried out with 1026 M CHCl3 solutions. As compared
to DANS, the corrected b0 values of DBAs 1–5 are similar in
magnitude or even two to three times larger. The parent DBA
6, possessing no substituents and being totally transparent in
the visible region, also exhibits a commensurate b0 value. A
more interesting analysis is the optical transparency of the
DBA solutions versus NLO activity based on the figure of
merit. Compared to a variety of similarly active chromophor-
es,1d the transition wavelengths of the DBA macrocycles are
generally 25–50 nm higher in energy, which translates into
better overall optical transparency. Finally, it is noteworthy
that DBA 1, the most promising of the systems studied in
Table 2, packs in a noncentrosymmetric pattern in the solid
state.12 Such an arrangement will be obligatory if DBAs or
other organic systems are to find use as viable NLO materials
for incorporation in devices such as high-speed optical
switches.20
9
The large b values of the DBAs make these planar 2-D
chromophores very promising candidates for second-order
NLO applications. To our knowledge, these are among the
most active organic NLO chromophores reported to date, and
present a novel structural motif for designing NLO-active
molecules with greater optical transparency. Based on these
results, we are conducting an inclusive study of all other DBAs
available in our lab to probe the structure–property relation-
ship for second-order NLO properties. In addition, our ability
to tune easily the electronic properties of the DBA skeleton, as
well as to incorporate easily polarizable functionalities such as
thiophenes,21 will permit us to design even more active NLO
chromophores. These results will be detailed in future reports.
10 (a) M. M. Haley, Synlett, 1998, 557; (b) M. M. Haley, J. J. Pak and
S. C. Brand, in Topics in Current Chemistry (Carbon-Rich
Compounds II), Ed. A. de Meijere, Springer-Verlag, Berlin,
1999, Vol. 201, p 81.
11 (a) R. R. Tykwinski and F. Diederich, Liebigs Ann./Recl., 1997,
649; (b) F. Diederich, Chem. Commun., 2001, 219.
12 J. J. Pak, T. J. R. Weakley and M. M. Haley, J. Am. Chem. Soc.,
1999, 121, 8182.
13 (a) M. L. Bell, R. C. Chiechi, C. A. Johnson, D. B. Kimball,
A. J. Matzger, W. B. Wan, T. J. R. Weakley and M. M. Haley,
Tetrahedron, 2001, 57, 3507; (b) W. B. Wan, R. C. Chiechi,
T. J. R. Weakley and M. M. Haley, Eur. J. Org. Chem., 2001, 3485.
14 M. D. Senskey, J. D. Bradshaw, C. A. Tessier and W. J. Youngs,
Tetrahedron Lett., 1995, 36, 6217.
15 M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson and
T. J. R. Weakley, J. Am. Chem. Soc., 1997, 119, 2956.
16 W. B. Wan, S. C. Brand, J. J. Pak and M. M. Haley, Chem. Eur. J.,
2000, 6, 2044.
Acknowledgements
17 (a) K. Clays and A. Persoons, Phys. Rev. Lett., 1991, 66, 2980;
(b) P. D. Maker, Phys. Rev. A, 1970, 1, 923.
18 M. A. Pauley, H.-W. Guan, C. H. Wand and A. K.-Y. Jen,
J. Chem. Phys., 1996, 104, 7821.
19 Although several significant tensor elements of b are operational in
our macrocycles, we have not differentiated between these in this
communication.
This research was supported by the National Science Founda-
tion and The Camille and Henry Dreyfus Foundation
(Teacher-Scholar Award to M.M.H.). J.J.P. acknowledges
the ACS Division of Organic Chemistry for a Graduate
Fellowship, sponsored by Organic Syntheses.
20 (a) B. J. Coe, Chem. Eur. J., 1999, 5, 2464; (b) I. Ledoux and
J. Zyss, in Novel Optical Materials and Applications, Eds.
I. C. Khoo, F. Simoni and C. Umeton, Wiley, New York, 1997;
(c) D. G. Feitelson, Optical Computing, MIT Press, Cambridge,
MA, 1988.
Notes and references
1
Nonlinear Optics of Organic Molecules and Polymers, Eds.
H. S. Nalwa and S. Miyata, CRC Press, New York, 1997.
Chem. Rev., 1994, 94, issue 1; J. Opt. Soc. Am. B, 1998, 15, issue 2
P. N. Prasad and D. J. Williams, Introduction to Nonlinear Optical
Effects in Molecules and Polymers, Wiley, New York, 1991.
2
3
21 A. Sarkar and M. M. Haley, Chem. Commun., 2000, 1733.
J. Mater. Chem., 2001, 11, 2943–2945
2945