First organophosphorus nonlinear-optical media

Full text of DOI:10.1023/B:DOCH.0000017272.85421.34

Doklady Chemistry, Vol. 394, Part 2, 2004, pp. 34–35. Translated from Doklady Akademii Nauk, Vol. 394, No. 6, 2004, pp. 773–774.
Original Russian Text Copyright © 2004 by Sukhov, Malysheva, Martynovich, Illarionov, Tirskii, Starchenko, Dubrovina, Belogorlova, Gusarova, Trofimov.
CHEMISTRY
First Organophosphorus Nonlinear-Optical Media
B. G. Sukhov*, S. F. Malysheva*, E. F. Martynovich**, A. I. Illarionov***,
V. V. Tirskii**, A. A. Starchenko**, M. A. Dubrovina***, N. A. Belogorlova*,
N. K. Gusarova*, and Academician B. A. Trofimov*
Received September 17, 2003
Molecular crystals occupy a place among nonlinear-
The Z,Z,Z isomers 2a and 2b were synthesized
optical materials owing to their high nonlinear suscep- under mild temperature conditions (20–100°ë) by a
tibilities [1–4]. This feature depends directly on the known method [6] involving oxidation (or sulfonyla-
degree of charge transfer in the molecules that form the tion) of Z,Z,Z-tristyrylphosphine (3), readily available
crystal [1]. Systems with intramolecular charge transfer through the direct reaction between elemental phospho-
are usually heteroatomic and functional organic com- rus and phenylacetylene [7, 8]. The E,E,E isomers 1a
pounds with extended electron conjugation [2]. By and 1b were prepared by heating (100–150°ë) of phos-
varying the nature of the heteroatom or the function phine 3 in DMSO or in an elemental sulfur–toluene sys-
incorporating the heteroatom, it is possible to vary the tem, respectively.
degree of charge transfer and, thus, to perform con-
trolled synthesis of new highly efficient nonlinear-opti-
cal materials [2–4]. To the best of our knowledge, no
data on the use of organophosphorus compounds as
nonlinear-optical media have been published.
Thus, the discovery of nonlinear-optical properties
in compounds 1 and 2 is a real prerequisite for con-
trolled synthesis of their structural analogues with a
specified degree of intramolecular charge transfer, i.e.,
new classes of organophosphorus nonlinear-optical
materials with controlled characteristics.
Using the powder method [5], we found for the first
time that the crystals of the E,E,E and Z,Z,Z isomers of
tristyrylphosphine oxide (1a, 2a) and tristyrylphos-
phine sulfide (1b, 2b) generate the second harmonics of
the radiation from a neodymium laser with an effi-
ciency comparable to that for a classical nonlinear-opti-
cal material, lithium iodate. The intramolecular charge
transfer in compounds 1 and 2 is made possible by the
conjugation of the π-electron-donating benzene rings
with the electron-withdrawing phosphoryl (or thio-
phosphoryl) group through the double bonds of the
styryl fragments.
E,E,E-Tristyrylphosphine oxide (1a). Phosphine 3
was heated (100°ë, 50 h) in DMSO, and the solvent
was evaporated in a vacuum to give phosphine oxide 1a
(80%) as colorless crystals, mp 246–248°C (DMSO).
1
The spectroscopic characteristics (IR, ç NMR, 31P
NMR) of phosphine oxide 1a were identical to those for
an authentic sample [9].
E,E,E-Tristyrylphosphine sulfide (1b). Phosphine 3
was heated (145–150°C, 12 h) with an equimolar
amount of elemental sulfur in xylene, the solvent was
distilled off, and the residue was recrystallized from
hexane to give phosphine sulfide 1b (40%) as light yel-
1
low crystals, mp 226–228°C (DMSO). H NMR
X
(CDCl3, δ, ppm): 6.68 (dd, 3H, H–C-1, 3JHH = 16.8 Hz,
2JPH = 21.5 Hz), 7.35–7.37 (m, 9H, p,m-Ph), 7.51–7.52
(m, 6H, o-Ph), 7.53 (dd, 3H, H–C-2, 3JPH = 22.9 Hz). IR
(KBr, cm–1): 3061, 3022, 2983 (ν, C–H); 1610, 1573,
1494, 1447 (ν, C=C, Ph); 1320, 1290, 1232, 1191, 1174
(δ, C–H); 997, 977, 880 (δ, HC=CH); 845, 834
(ν, P=S); 798 (ν, P–C); 743, 689 (δ, C–H arom); 610
(δ, C–P–C).
2
P
X
1
P
1a, 1b
2a, 2b
X = O (‡), S (b)
For C24H21PS anal. calcd. (%): C, 77.42; H, 5.65; P,
8.33; S, 8.60.
* Favorsky Institute of Chemistry, Siberian Division,
Russian Academy of Sciences, ul. Favorskogo 1,
Irkutsk, 664033 Russia
** Institute of Laser Physics (Irkutsk Branch),
Siberian Division, Russian Academy of Sciences,
Irkutsk, Russia
Found (%): C, 77.80; H, 5.36; P, 8.74; S, 8.50.
Z,Z,Z-Tristyrylphosphine oxide (2a) and sulfide
(2b) were prepared by treating Z,Z,Z-tristyrylphos-
phine with aqueous hydrogen peroxide or elemental
sulfur according to a known procedure [6].
The generation of the second harmonics was studied
by the powder method using the radiation from a
*** Irkutsk State University of Communications,
Irkutsk, Russia
0012-5008/04/0002-0034 © 2004 åÄIä “Nauka /Interperiodica”

FIRST ORGANOPHOSPHORUS NONLINEAR-OPTICAL MEDIA
35
2. Heflin, J.R. and Garito, A.F., Electroresponsive Molecu-
lar and Polymeric Systems, New York: Marsel Dekker,
1988, vol. 2, pp. 1–48.
neodymium laser on an yttrium aluminum garnet (with
a wavelength of 1064 nm) operating in the Q-modula-
tion mode. The pulse power density for the exciting
radiation was ~108 W/cm2. The spectrum of the arising
emission of the samples contained a line at 532 nm with
a width of ~1 nm, corresponding to the error of mea-
surement for the spectrometer used.
3. Singer, K.D. and Sohn, J.E., Electroresponsive Molecu-
lar and Polymeric Systems. N.Y.; Basel; Hong Kong,
Marsel Dekker, 1988, vol. 2, pp. 49–112.
4. Günter, P., Nonlinear Optical Effects and Materials,
Springer Series in Optical Sciences 72, New York:
Springer, 2000.
ACKNOWLEDGMENTS
This work was supported by the program of the
President of the Russian Federation “Leading Scientific
Schools” (grant no. NSh-2241.2003.3), the Russian
Foundation for Basic Research (project nos. 02–03–
32648 and 03–02–17733), and the Program of Integra-
tion Studies of the Siberian Division of the RAS (grant
nos. 135 and 136).
5. Kurtz, S.K. and Perry, T.T., J. Appl. Phys., 1968, vol. 39,
no. 8, p. 3798.
6. Gusarova, N.K., Trofimov, B.A., Rakhmatulina, T.N., et al.,
Zh. Obshch. Khim., 1990, vol. 60, no. 2, pp. 300–303.
7. Trofimov, B.A., Gusarova, N.K., Rakhmatulina, T.N., et al.,
Zh. Obshch. Khim., 1991, vol. 61, no. 6, pp. 1310–1315.
8. Gusarova, N.K., Malysheva, S.F., Arbuzova, S.N., et al.,
Zh. Obshch. Khim., 1994, vol. 64, no. 12, p. 2062.
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DOKLADY CHEMISTRY Vol. 394 Part 2 2004