Nonlinear optical materials with reduced aromaticity and bond length alternation

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to materials which exhibit nonlinear optical (NLO) properties. More particularly, the present invention relates to materials which have high first molecular electronic hyperpolarizability (.beta.) and therefor display high second order nonlinear optical properties.
2. Description of Related Art
Organic materials that show second-order nonlinear optical responses are of interest for a variety of photonic and optoelectronic applications. See Marder, S. R., Sohn, J. E. & Smoky, G. D. eds. Materials for Nonlinear Optics: Chemical Perspectives, ACS Symposium Series, Vol. 455(American Chemical Society, Washington, 1991); Chemla, D. S. & Zyss, J. eds Nonlinear optical properties of Organic Molecules and Crystals, Vol. 1 and 2 (Academic Press, San Diego, 1987); and Williams, D. J. Agnew. Chem. Int. Ed. Engl. 23, 690-703 (1984).
Exemplary nonlinear optical materials and devices which utilize such materials are described in U.S. Pat. Nos. 5,062,693; 5,011,907; and 5,016,063. Nonlinear optical materials are also described in Japanese Patent Appln. No. 63-270834 filed Oct. 28, 1988, and published on May 2, 1990.
Compositions which have been investigated for second order nonlinear properties include barbituric acid derivatives and cyanine dyes. Investigations with respect to barbituric acid derivatives are set forth in a number of literature references. These references include: Chapter 12 of Materials for Nonlinear Optics: Chemical Perspectives (supra, pp.200-213); Kondo, K. et al., Nonlinear Optical Properties of p-Substituted Benzalbarbituric Acids,--Appl. Phys. Lett. 56, 718 (1990); Ikeda H., et al., Second Order Hyperpolarizabilities of Barbituric Acid Derivatives, Chemistry Letters, pp. 1803-1806(1989); and Kondo K., et al., Crystal Structure of Thermally Stable Non-Linear Benzalbarbituric Acid Derivatives, Chemical Physics Letters, Vol. 188, No. 3.4, (1992). Investigations with respect to cyanine dyes are set forth in Ikeda, H., et al., Nonlinear Optical Properties of Cyanine Dyes, Chemical Physics Letters, Vol. 179, No. 5.6(1991).
Nonlinear optical compositions are also disclosed in U.S. Pat. No. 5,256,784 which issued on Oct. 26, 1994. The disclosed double functional group compositions include a variety of donor groups which are connected together by linkages composed of from 1 to 2 carbon double bonds.
There is a continuing need to develop new materials which have sufficiently high second-order nonlinear optical properties when used in thin films and crystals to make them useful for applications such as telecommunications, optical data storage and optical information processing.
SUMMARY OF THE INVENTION
The present invention provides compositions of matter that have bond length alternations which are selected to provide a high degree of first molecular electronic hyperpolarizability (.beta.). The compositions of the present invention are useful for incorporation into polymers, Langmuir-Blodgett thin films, self-assembled monolayers or poled polymers. It was discovered in accordance with the present invention that molecules that have degenerate or more nearly degenerate .pi. (pi)-electron bridges and do not lose aromaticity upon charge transfer. This diminishes the bond length alternation for given donor-acceptor end groups and provides optimization of .beta.. Applicants' invention is further based upon the discovery that there is an optimal combination of donors and acceptors which leads to an optimal degree of bond length alternation and therefore optimized .beta.. In addition, it was discovered that when the number of carbon double bonds linking certain donor group is increased above 2, then an unexpected increase in second-order nonlinear optical properties is observed.
Compositions in accordance with the present invention have the formula ##STR1##
wherein A is ##STR2##
R is H, alkyl, aryl, (CH.sub.2).sub.x OH where x=1 to 8, or (CH.sub.2).sub.x SH where x=1 to 8;
R' is H, alkyl, aryl, (CH.sub.2).sub.y' OH where y'=1 to 8, or (CH.sub.2).sub.y' SH where y'=1 to 8; ML.sub.n is a lewis acid;
wherein B is ##STR3##
D is OR", NR"R"' or SR"; where
R" is H, alkyl, aryl or (CH.sub.2).sub.w OH where w=1 to 8;
R"' is H, alkyl, aryl or (CH.sub.2).sub.z OH where z=1 to 8;
or where NR"R"' is derived from a cyclic amine of the form N(CH.sub.2).sub.1 where 1=3-10, and
wherein m is 0 to 15, if B is (11), and A is (3), (4), (5), (6), (7), (8), (9) or (10) then, m is 2 to 15;
or if B is (11) and A is (1) or (2), then m=3 to 15
where the asterisk indicates the point of attachment on the acceptor and donor.
As a feature of the present invention, nonlinear optical devices are provided which include compositions of matter .which exhibit a high second-order nonlinear optical response. The compositions used in the optical devices are those set forth above and also include compositions having the formula ##STR4## wherein Z is CH.dbd.CH, O, N, S or Se;
A is ##STR5##
R is H, alkyl, aryl, (CH.sub.2).sub.x OH where x=1 to 8, or (CH.sub.2).sub.x SH where x=1 to 8;
R' is H, alkyl, aryl, (CH.sub.2).sub.y' OH where y'=1 to 8, or (CH.sub.2).sub.y' SH where y'=1 to 8; ML.sub.n is a lewis acid;
wherein B is ##STR6##
Y is CH.dbd.CH, O, N, S or Se;
D is OR", NR"R"' or SR" where
R" is H, alkyl, aryl or (CH.sub.2).sub.w OH where w=1 to 8;
R"' is H, alkyl, aryl or (CH.sub.2).sub.z OH where z=1 to 8;
or where NR"R"' is derived from a cyclic amine of the form N(CH.sub.2).sub.1 where 1=3-10, and
wherein m is 0 to 15, n=0 to 15 and p=1 to 15; except when A is (2) then Y is S, and B is (13) or (14), M=0 to 10, n=0 to 15 and p=1 to 15,
where the asterisk indicates the point of attachment on the acceptor and donor.
Further compositions in accordance with the present invention include those having the formula ##STR7##
wherein C is ##STR8##
wherein A is ##STR9##
R is H, alkyl, aryl, (CH.sub.2).sub.x OH where x=1 to 8, or (CH.sub.2).sub.x SH where x=1 to 8;
R' is H, alkyl, aryl, (CH.sub.2).sub.y' OH where y'=1 to 8, or (CH.sub.2).sub.y' SH where y'=1 to 8; ML.sub.n is a lewis acid;
wherein B is ##STR10##
Y is CH.dbd.CH, O, N, S or Se;
D is OR", NR"R"' or SR" where
R" is H, alkyl, aryl or (CH.sub.2).sub.w OH where w=1 to 8;
R"' is H, alkyl, aryl or (CH.sub.2).sub.z OH where z=1 to 8;
or where R"R"' is derived from a cyclic amine of the form N(CH.sub.2).sub.1 where 1=3-10; and
wherein m is 0 to 15.
where the asterisk indicates the point of attachment on the acceptor and donor.
Applicants' invention focuses on the importance of the conjugated .pi. (pi)-electron bridge in determining second-order non-linear optical responses. As a feature of the present invention, it was discovered that the aromaticity of the bridge in the ground state is an important aspect in determining the degree of bond length alternation and resultant second-order nonlinear optical responses. This is in contrast to previous teachings which typically focused on the aromaticity of molecules on either side of the .pi. (pi) electron bridge. The previous teachings focused on optimizing .beta. by changing the strength of the donor and acceptor moieties (i.e. A and B) with the philosophy being that large .beta. is obtained by using the strongest donors and acceptors.
The above-discussed and many other features and attendant advantages will become better understood by reference to the following detailed description whet taken in conjunction with the accompanying drawings.

DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of the synthesis of an exemplary composition in accordance with the present invention wherein B is dimethylaminophenyl (11).
FIG. 2 is a schematic representation of the synthesis of an exemplary composition wherein B is julolidinyl (12).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The compositions of the present invention are organic materials that show second-order non-linear optical responses. The compositions are incorporated into thin films and crystals in the same manner as other materials which exhibit non-linear optical properties. The compositions, themselves, may exist as crystals, liquids or gases. The compositions may be used alone or in combination with other materials which are conventionally used in non-linear optical devices.
The optical element in accordance with the invention may in some cases consist of a macroscopic crystal of the compound chosen, providing the compound can be made to form crystals in which the polar molecules are in noncentrosymmetric alignment. Such crystals may be grown at a slow rate under equilibrium with their mother liquor by a variety of methods practiced in the art. However, this procedure will not work for many polar molecules due in large part to dipole interactions. Another method of producing a useful optical element involves dissolving the compound in a solvent, which can be placed in a container having the desired shape. The solution can then be subjected to an electrical field which causes the dissolved dipoles to align themselves in the field. Electromagnetic radiation can then be passed through the solution and nonlinear optical effects, such as second harmonic generation, can be produced. Both the presence of an electric field and the need to utilize the compound in liquid solution form may be inconvenient or undesirable in some applications.
A particularly convenient and effective form of the optical element in accordance with the invention involves dispersing the polar molecules in a polymeric binder. The polar molecules can be mixed into the polymeric binder or grated onto the polymer. The mixture can be heated to a temperature at which the polymer becomes sufficiently soft so that upon application of an electrical field the polar molecules line up on the direction of the field. When the mixture cools, the polar molecules are locked into their aligned positions after which the electric field can be removed. Suitable binders include polymethacrylate, poly(methyl methacrylate), poly(vinyl alcohol), copolymers of methyl methacrylate and methacrylic acid, copolymers of styrene and maleic anhydride and half ester-acids of the latter, as well as many others. It is preferred that the polymerize binder of choice be highly transparent so that the transparency of the compounds utilized in the practice of this invention can be advantageously employed.
The poled polymer of this invention are considered particularly useful because of their high concentration of nonlinear optically active molecules, their capability of being formed into large area thin films, and their high orientational stability. Preferred film thickness can vary according to use. Typically film thickness is within the range of 0.5 .mu.m-2 .mu.m.
The poled polymer can also be provided in forms other than films (e.g., a solid block of polymer could be formed into an electrooptic modulator or a frequency converter using conventional techniques known in the art for single crystals) and poled polymer in various forms are included within this invention.
The poled polymers of this invention are preferably shaped to function as nonlinear optical elements for transforming electromagnetic radiation (e.g., by changing the frequency and/or polarization of the radiation). Generally, the nonlinear optical element of a poled polymer is used for transforming electromagnetic radiation by including it within an optical device. A device for transforming electromagnetic radiation using a nonlinear optical element is described in U.S. Pat. No. 4,909,964. The compounds of the present invention may be used in such a device.
A conventional nonlinear optical device disclosed in U.S. Pat. No. 4,909,964 comprises means to direct at least one incident beam of electromagnetic radiation into an element. The element has nonlinear optical properties whereby electromagnetic radiation emerging from the element contains at least one frequency different from the frequency of any incident beam of radiation. The different frequency is an even multiple of the frequency of one incident beam of electromagnetic radiation.
Preferably, the emerging radiation of a different frequency is doubled (second-order) (SHG). Preferably, the electromagnetic radiation is radiation from one of a number of common lasers, such as Nd-YAG, Raman-shifted Nd-YAG, Nd-YLF or Nd-glass, semiconductor diode, Er-Glass, Ti-Sapphire, dye, and Ar or Kr ion, or radiation shifted to other frequencies by nonlinear processes. For example, polarized light of wavelength 1.06 .mu.m from an Nd-YAG laser is incident on the optical element along the optical path. A lens focuses the light into the optical element. Light emerging from the optical element is collimated by a similar lens and passed through a filter adapted to remove light of wavelength 1.06 .mu.m while passing light of wavelength 0.53 .mu.m.
As disclosed in U.S. Pat. No. 4,909,964 (incorporated herein by reference), one conventional electro-optic modulator comprises means to direct a coherent beam into an optical element, and means to apply an electric field to the element in a direction to modify the transmission property of the beam. For example, in an electro-optic modulator comprising an optical element, a pair of electrodes is attached to the upper and lower surfaces of the element, across which a modulating electric field is applied from a conventional voltage source. The optical element is placed between two polarizers. A light beam (such as that from a Nd-YAG laser) is polarized by a polarizer, focused on the optical element and propagated therethrough, and subjected to modulation by the electric field. The modulate light beam is led out through an analyzer polarizer. Linearly polarized light traversing the optical element is rendered elliptically polarized by action of the applied modulating voltage. The analyzer polarizer renders the polarization linear again. Application of the modulating voltage alters the birefringence of the optical element and consequently the ellipticity impressed on the beam. The analyzer polarizer then passes a greater or lesser fraction of the light beam as more or less of the elliptically polarized light projects onto its nonblocking polarization direction.
It will be further apparent to those skilled in the art that the optical elements formed by the poled polymers of the present invention are useful in this and other devices utilizing their nonlinear properties, such as devices utilizing the electro-optic effect.
One common form the optical element can take is that of a Langmuir-Blodgett (LB) film. A small amount of a compound useful in the practice of this invention spread on the surface of a liquid forms a surface film of monomolecular thickness at the air/liquid interface. If the supporting liquid is a polar liquid, such as water, the hydrophilic moieties of the compound are drawn into the liquid, while the hydrophobic moieties of the compound are attracted to the non-polar, air side of the interface to hold the polar molecules at the surface of the supporting liquid body, resulting in polar alignment of the polar molecules on the surface of the supporting liquid. When the supporting substrate is slowly immersed in the film bearing liquid body or slowly withdrawn from it, an oriented monomolecular film is formed on the substrate.
The nonlinear optical device according to the invention comprises a means to direct at least one incident of electromagnetic radiation onto an optical dement having nonlinear optical properties whereby electromagnetic radiation emerging from the element contains at least one frequency different from the frequency of any incident beam of radiation, the different frequency being an even multiple of the frequency of one incident beam of electromagnetic radiation. The optical element is selected from one of the forms described above. Preferably, the emerging radiation of a different frequency is doubled, i.e. SHG.
The optical element of the invention can also be utilized in an electro-optic modulator, wherein an electric field is applied to the optical element in a direction to modify the transmission properties of the element.
Compositions of matter which are covered by the present invention have the formula: ##STR11##
wherein A is ##STR12##
R is H, alkyl, aryl, (CH.sub.2).sub.x OH where x=1 to 8, or (CH.sub.2).sub.x SH where x=1 to 8;
R' is H, alkyl, aryl, (CH.sub.2).sub.y' OH where y'=1 to 8, or (CH.sub.2).sub.y' SH where y'=1 to 8; ML.sub.n is a lewis acid;
wherein B is ##STR13##
D is OR", NR"R"' or SR" where
R" is H, alkyl, aryl or (CH.sub.2).sub.w OH where w=1 to 8;
R"' is H, alkyl, aryl or (CH.sub.2).sub.z OH where z=1 to 8;
or where NR"R"' is derived from a cyclic amine of the form N(CH.sub.2).sub.1 where 1=3-10, and
wherein m is 0 to 15, if B is (11), and A is (3), (4), (5), (6), (7), (8), (9) and (10) then, m is 2 to 15;
or if B is (12) and A is (1), then m is 1 to 15;
or if B is (11) and A is (1) or (2), then m=3 to 15;
where the asterisk indicates the point of attachment on the acceptor and donor.
The present invention is also directed to non-linear optical devices which incorporate compositions of matter having the formula: ##STR14##
wherein Z is CH.dbd.CH, O, N, S or Se;
A is ##STR15##
R is H, alkyl, aryl, (CH.sub.2).sub.x OH where x=1 to 8, or (CH.sub.2).sub.x SH where x=1 to 8;
R' is H, alkyl, aryl, (CH.sub.2).sub.y' OH where y'=1 to 8, or (CH.sub.2).sub.y' SH where y'=1 to 8; ML.sub.n is a lewis acid;
where the asterisk indicates the point of attachment on the acceptor and donor.
wherein B is ##STR16##
Y is CH.dbd.CH, O, N, S or Se;
D is OR", NR"R"' or SR" where
R" is H, alkyl, aryl or (CH.sub.2).sub.w OH where w=1 to 8;
R"' is H, alkyl, aryl or (CH.sub.2).sub.z OH where z=1 to 8;
or where NR"R"' is derived from a cyclic amine of the form N(CH.sub.2).sub.1 where 1=3-10, and
wherein m is 0 to 15, n=0 to 15 and p=1 to 15; except when A is (2) then Y is S, and B is (13) or (14), m=0 to 10, n=0 to 15 and p=1 to 15,
where the asterisk indicates the point of attachment on the acceptor and donor.
The present invention is also directed to non-linear optical devices which include compositions of matter having the formula: ##STR17##
wherein C is ##STR18##
wherein A is ##STR19##
R is H, alkyl, aryl, (CH.sub.2).sub.x OH where x=1 to 8, or (CH.sub.2).sub.x SH where x=1 to 8;
R' is H, alkyl, aryl, (CH.sub.2).sub.y' OH where y'=1 to 8, or (CH.sub.2).sub.y' SH where y'=1 to 8; ML.sub.n is a lewis acid;
wherein B is ##STR20##
Y is CH.dbd.CH, O, N, S or Se;
D is OR", NR"R"' or SR" where
R" is H, alkyl, aryl or (CH.sub.2).sub.w OH where w=1 to 8;
R"' is H, alkyl, aryl or (CH.sub.2).sub.z OH where z=1 to 8;
or where R"R"' is derived from a cyclic amine of the form N(CH.sub.2).sub.1 where 1=3-10, and
wherein m is 0 to 15.
where the asterisk indicates the point of attachment on the acceptor and donor.
Alkyl groups set forth in the above formulas include those groups having up to 10 carbon atoms and includes both branched and straight chain alkyl groups. Exemplary alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, in the normal, secondary, iso and neo attachment isomers. Aryl groups referred to in the preceding formulas include aromatic hydrocarbons having up to 10 carbon atoms. Exemplary aryl groups include phenyl, naphthyl, furanyl, thiophenyl, pyrrolyl, selenophenyl, tellurophenyl. The abbreviation ML.sub.n refer to Lewis acids. Exemplary Lewis acids include (CH.sub.3).sub.2 Zn, (CH.sub.3).sub.3 Al, (CH.sub.3).sub.3 Ga, (CH.sub.3).sub.3 B Cl.sub.3 Al, Cl.sub.3 Ga, and Cl.sub.3 B.
The compositions of the present invention are prepared by reacting an appropriate acceptor (A) with B--(CH.dbd.CH).sub.n CHO under standard Knoevenagel conditions. As schematically shown in FIG. 1 for the exemplary case where B is dimethylaminophenyl (11). FIG. 2 is a schematic representation of the synthesis where B is julolidinyl (12).
A compound in accordance with the present invention was prepared where A was diethylthiobarbimric add (2) and B was dimethylaminophenyl (11). The procedure which was used to prepare this composition was as follows:
Preparation of the product is carried out by a conventional Kuoevenagel reaction wherein (7-4-dimethylamino-phenyl)-hepta-2,4,6-triene-1-al (1.41 mmol) is completely dissolved in approximately 100 mls of ethanol. 10 mls of a warm ethanol solution of 1,3-diethyl thiobarbituric acid (1.11 mmol is added to the dissolved (7-4-dimethylamino-phenyl)-hepta-2,4,6-triene-1-al. This causes a gradual darkening of color. The mixture is then set in an oil bath at 90.degree. C. and 0.5 mls of piperidine is added with stirring. The color of the solution immediately darkens. The solution is then refluxed generally for one hour or until thin layer chromatography (TLC) indicates the reaction is complete. The mixture is cooled and diluted with petroleum ether and the product is filtered and washed with ethanol/petroleum ether and then with petroleum ether. The yield is 0.435 gram (1.06 mmol, 95%) of dark green fluffy powder. The powder may be recrystallized from mixtures of dichloromethane/petroleum ether or from ethanol/petroleum ether.
In an alternate procedure, the (7-4-dimethylamino-phenyl)-hepta-2,4,6-triene-1-al is combined in 10 mls of ethanol and 30 mls of chloroform with 1.0 gram of isophorone-thiobarbituric acid derivative C, where A=(2) and R.dbd.R'=ethyl (3.12 mmol and 1 g ammonium acetate) in a Schlenk flask. The flask is filled with argon twice and sealed. The mixture is then evacuated and left to sit one day at room temperature in the dark. The resulting dark blue solution is washed with water (2.times.30 mls) followed by drying with magnesium sulfate. Solvent is removed from the solution under vacuum. The remaining residue is chromatographed on silica gel using 3% ethyl acetate/97% hexane as an eluant. The first blue band gave after evaporation of solvent a materials corresponding to a composition having the formula of the present invention where A is 2 R.dbd.R' is ethyl, C is 16 and m is 4 and B is (14), where Y is CH.dbd.CH and D is (CH.sub.3).sub.2 N.
A number of exemplary compositions in accordance with the present invention were prepared following the above-described procedure. The results of spectroscopic and elemental analysis for the various compositions are as follows:
EXAMPLE 1
General Formula I
A=diethyl barbituric acid (1)
B=dimethylaminophenyl (11)
m=3
.sup.1 H NMR (CD.sub.3 COCD.sub.3) .delta. 7.98 (m, 2H), 7.43 (dm, J=8.8 Hz, 2H), 7.39 (m, 1H), 7.04 (dd, J=14.3, 10.5 Hz, 1H), 6.93 (m, 2H), 6 dd, J=14.2, 11.8 Hz, 1H), 3.93, 3.92 (each q, J=7.0 Hz, 2H), 3.01 (s, 6H), 1.16, 1.15 (each t, J=7.0 Hz, 3H). Anal. Calcd. for C.sub.23 H.sub.27 N.sub.3 O.sub.3 : C, 70.21; H, 6.92; N, 10.68. Found: C, 70.26; H, 6.95; N, 10.67. .lambda..sub.max (solvent, nanometers): cyclohexane, 522; toluene, 546; chloroform, 572; methylene chloride, 562; acetone, 542; methanol, 560; N-methyl-2-pyrrolidone, 569.
EXAMPLE 2
General Formula I
A=diethyl barbituric acid (1)
B=julolidinyl (12)
m=1
.sup.1 NMR (CD.sub.3 COCD.sub.3) .delta. 8.36 (dd, J=14.8, 12.4 Hz, 1H), 8.05 (dd, J=12.5, 0.6 Hz, 1H), 7.44 (d, J=14.8 Hz, 1H), 7.20 (s, 2H), 3.94, 3.92 (each q, J=7.0 Hz, 2H), 3.37 (apparent t, J=5.8 Hz, 4H), 2.76 (apparent t, J=6.8 Hz, 4H), 1.95 (m, 4H), 1.17, 1.15 (each t, J=7.0 Hz, 3H). .sup.13 C NMR .delta. 162.77, 162.24, 158.30, 157.87, 151.04, 147.13, 130.05, 122.55, 121.25, 119.58, 108.62, 50.19, 36.87, 36.28, 27.48, 21.20, 13.48, 13.43. .lambda..sub.max (solvent, nanometers): cyclohexane, 529; chloroform, 574. Anal. Calcd. for C.sub.23 H.sub.27 N.sub.3 O.sub.3 : N, 10.68. Found: N, 10.64.
EXAMPLE 3
General Formula I
A=diethyl barbituric acid (1)
B=julolidinyl (12)
m=2
.sup.1 H NMR (CD.sub.2 Cl.sub.2) .delta. 8.04 (d, J=12.5 Hz, 1H) 7.94 (dd, J=13.9, 12.6 Hz, 1H), 7.28 (apparent ddd, J=13.9, 7.9, 2.9 Hz, 1H), 6.99 (s, 2H), 6.92 (m, 2H), 3.96, 3.96 (each q, J=7.0 Hz, 2H), 3.27 (apparent t, J=5.8 Hz, 4H), 2.73 (apparent t, J=6.3 Hz, 4H), 1.94 (m, 4H), 1.19 (m, 6H). .lambda..sub.max (solvent, nanometers): cyclohexane, 540; chloroform, 616.
EXAMPLE 4
General Formula I
A=diethylthio barbituric acid (2)
B=dimethylaminophenyl (11)
m=3
.sup.1 H NMR .delta. 8.09 (d, J=12.6 Hz, 1H), 8.00 (apparent t, J=13.3 Hz, 1H), 7.39 (d, J=9.0 Hz, 2H), 7.25 (dd, J=14.0, 11.7 Hz, 1H), 6.96 (dd, J=14.4, 10.2 Hz, 1H), 6.85 (d, J=15.1 Hz, 1H), 6.81 (dd, J=15.1, 10.2 Hz, 1H), 6.67 (d, J=9.0 Hz, 2H), 6.59 (dd, J=14.3, 11.7 Hz, 1H ), 4.55, 4.54 (each q, J=7.0 Hz, 2H), 3.04 (s, 6H), 1.30 (m, 6H). .sup.13 C NMR .delta. 178.75, 160.87, 159.87, 157.99, 157.27, 151.19, 147.82, 142.07, 130.07, 129.28, 128.31, 124.30, 123.92, 112.10, 112.00, 43.58, 43.05, 40.15, 12.42 (coincident). Anal. Calcd. for C.sub.23 H.sub.27 N.sub.3 O.sub.2 S: C, 67.45; H, 6.65; N, 10.26. Found: C, 67.48; H, 6.71; N, 10.18. .lambda..sub.max (solvent, nanometers): cyclohexane, 556; toluene, 588; chloroform, 624; methylene chloride, 612; acetone, 592; methanol, 608; N-methyl-2-pyrrolidone, 634.
EXAMPLE 5
General Formula I
A=diethylthio barbituric acid (2)
B=julolidinyl (12)
m=1
.sup.1 H NMR (CD.sub.3 COCD.sub.3) .delta. 8.40 (dd, J=14.5, 12.7 Hz, 1H), 8.10 (dd, J=12.6, 0.5 Hz, 1H), 7.56 (d, J=14.5 Hz, 1H), 7.27 (br s, 2H), 4.52, 4.50 (each q, J=6.9 Hz, 2H), 3.43 (apparent t, J=5.8 Hz, 4H), 2.78 (apparent t, J=6.5 Hz, 4H), 1.96 (m, 4H), 1.25, 1.22 (each t, J=6.9 Hz, 3H). .sup.13 C NMR .delta. 178.60, 161.37, 160.46, 159.38, 159.18, 147.99, 130.78, 122.74, 121.46, 120.11, 108.46, 50.33, 43.41, 42.86, 27.40, 21.04, 12.49, 12.41. Anal. Calcd. for C.sub.23 H.sub.27 N.sub.3 O.sub.2 S: C, 67.45; H, 6.65; N, 10.26; S, 7.83. Found: C, 67.18; H, 6.67; N, 10.24; S, 7.77. .lambda..sub.max (solvent, nanometers): cyclohexane, 563; chloroform, 614 (log .epsilon., 5.08).
EXAMPLE 6
General Formula I
A=diethylthio barbituric acid (2)
B=julolidinyl (12)
m=2
.sup.1 H NMR .delta. (CD.sub.2 Cl.sub.2) 8.07 (d, J=12.8 Hz, 1H), 7.98 (apparent t, J=13.2 Hz, 1H), 7.37 (dd, J=14, 11.0 Hz, 1H), 7.03 (br s, 2H), 6.98 (m, 2H), 4.54 (m, 4H), 3.30 (apparent t, J=5.8 Hz, 4H), 2.73 (apparent t, J=6.3 Hz, 4H), 1.95 (m, 4H), 1.27, 1.25 (each t, J=7.0 Hz, 3H). Anal. Calcd. for C.sub.25 H.sub.29 N.sub.3 O.sub.2 S: C, 68.94; H, 6.71; N, 9.65; S, 7.36. Found: C, 69.03; H, 6.76; N, 9.63; S, 7.42. .lambda..sub.max (solvent, nanometers): cyclohexane, 580; chloroform, 684.
EXAMPLE 7
General Formula I
A=diethylthio barbituric acid (2)
B=julolidinyl (12)
m=3
.sup.1 H NMR .delta. 8.08 (d, J=12.7 Hz, 1H), 7.98 (apparent t, J=13.3 Hz, 1H), 7.25 (dd, J=13.8, J=11.9 Hz, 1H), 6.96, (bs, 2H), 6.95 (m, 1H), 6.55 (dd, J=14.1, J=11.8 Hz, 1H), 4.55, 4.54 (each q, J=6.9 Hz, 2H), 3.25 (apparent t, J=5.7 Hz, 4H), 2.74 (apparent t, J=6.3 Hz, 4H), 1.96 (m, 4H), 1.31, 1.29 (each t, J=7.3 Hz, 3H). .sup.13 C NMR .delta. 178.05, 161.05, 160.04, 157.97, 157.91, 148.80, 144.72, 143.22; 129.39, 127.81, 127.30, 123.39, 123.09, 121.28, 111.35, 50.02, 43.58, 43.04, 27.67, 21.53, 12.48, 12.44; EIMS, m/z 461(M, 2), 327(47), 199(54), 186(100), 170(32), 97(24), 69(34); EI HRMS m/z (calcd for C.sub.27 H.sub.31 N.sub.3 O.sub.2 S: 461.2150), 461.2137. Anal. Calcd. for C.sub.27 H.sub.31 N.sub.3 O.sub.2 S: C, 70.25; H, 6.77; N, 9.10; S, 6.95. Found: C, 70.03; It, 6.80; N, 9.00; S, 6.83.
EXAMPLE 8
General Formula I
A=indandione (3)
B=dimethylaminophenyl (11)
m=2
.lambda..sub.max (solvent, nanometers): toluene, 536; chloroform, 55,6; methylene chloride, 552; acetone, 542; methanol, 560; N-methyl-2-pyrrolidone, 570.
EXAMPLE 9
General Formula I
A=indandione (3)
B=dimethylaminophenyl (11)
m=3
.sup.1 H NMR .delta. 7.91 (m, 2H); 7.83 (dd, J=14.3, 12.5 Hz, 1H), 7.73 (m, 2H), 7.53 (d, J=8.9 Hz, 2H), 7.37 (dm, J=8.9 Hz, 2H), 7.10 (dd, J=14.5, 11.5 Hz, 1H), 6.80 (m, 3H), 6.67 (dm, J=8.9 Hz, 2H), 6.60 (dd, J.sub.1 +J.sub.2 =25.17 Hz, 1H), 3.02 (s, 6H). .lambda..sub.max (solvent, nanometers): cyclohexane, 524; toluene, 550; chloroform, 572; methylene chloride, 570; acetone, 552; methanol, 568; N-methyl-2-pyrrolidone, 580.
EXAMPLE 10
General Formula I
A=indandione (3)
B=julolidinyl (12)
m=1
.sup.1 H NMR .delta. 8.21 (dd, J=14.8, 12.4 Hz, 1H), 7.88, 7.70 (each m, 2H), 7.62 (d, J=12.3 Hz, 1H), 7.21 (d, J=14.9 Hz, 1H), 7.17 (br. s, 2H), 3.30 (apparent t, J=5.7 Hz, 4H), 2.76 (apparent t, J=6.2 Hz, 4H), 1.97 (m, 4H). .lambda..sub.max (solvent, nanometers): cyclohexane, 541.
EXAMPLE 11
General Formula I
A=indandione (3)
B=julolidinyl (12)
m=2
.sup.1 H NMR .delta. 7.89 (m, 2H), 7.82 (dd, J.sub.1 +J.sub.2 =26.75 Hz, 1H), 7.70 (m, 2H), 7.54 (d, J=12.6 Hz, 1H), 7.17 (dd, J=14.3, 10.8 Hz, 1H), 6.99 (br. s, 2H), 6.92 (dd, J=15.0, 10.7 Hz, 1H), 6.85 (d, J=15.1 Hz, 1H), 3.25 (apparent t, J=5.7 Hz, 4H), 2.74 (apparent t, J=6.3 Hz, 4H), 1.97 (m, 4H).
EXAMPLE 12
General Formula I
A=3-phenyl-5-isoxazolone (5)
B=dimethylaminophenyl (11)
m=2
.sup.1 H NMR .delta. (CD.sub.2 Cl.sub.2) 7.81 (dd, J=14.1, 12.3 Hz, 1H), 7.57 (m, 5H,), 7.43 (d m, J=9.0 Hz, 2H), 7.40 (dd, J=12.6, 0.5 Hz, 1H), 7.18 (apparent dddd, J=14.3, 7.4, 3.3, 0.4 Hz, 1H), 7.00 (m, 2H), 6.69 (d m, J=9.0 Hz, 2H), 3.04 (s, 6H); .sup.13 C NMR (125.8 MHz) .delta. 170.21, 162.40, 154.61, 151.92, 149.73, 145.57, 130.53, 130.02, 129.06, 128.31, 128.24, 124.72, 123.93, 123.72, 112.70, 112.09, 40.08; Anal. Calcd. for C.sub.22 H.sub.20 N.sub.2 O.sub.2 : C, 76.72; H, 5.85; N, 8.13. Found: C, 76.67; H, 5.90; N, 8.08. .lambda..sub.max (solvent, nanometers): cyclohexane, 508; toluene, 538; chloroform, 562; methylene chloride, 564; acetone, 553; methanol, 570; N-methyl-2-pyrrolidone, 580.
EXAMPLE 13
General Formula I
A=3-phenyl-5-isoxazolone (5)
B=dimethylaminophenyl (11)
m=3
.sup.1 H NMR .delta. (CD.sub.2 Cl.sub.2) 7.78 (dd, J=14.3, 12.3 Hz, 1H), 7.58 (m, 5H), 7.37 (m, 3H), 7.09 (dd, J=14.4, 11.6 Hz, 1H), 6.90 (apparent ddd, J=14.1, 7.0, 3.8 Hz, 1H), 6.82 (m, 2H), 6.67 (d m, J=9.0 Hz, 2H), 6.62 (dd, J=13.6, 11.6 Hz, 1H), 3.01 (s, 6H); .sup.13 C NMR (125.8 MHz) .delta. 170.01, 162.37, 153.50, 151.22, 149.35, 146.27, 141.14, 130.59, 129.81, 129.09, 129.07, 128.22, 128.17, 125.64, 124.48, 123.97, 113.40, 112.12, 40.15. Anal. Calcd. for C.sub.24 H.sub.22 N.sub.2 O.sub.2 : C, 77.81; H, 5.99; N, 7.56. Found: C, 77.89; H, 6.02; N, 7.53. .lambda..sub.max solvent, nanometers): cyclohexane, 534; toluene, 558; chloroform, 582; methylene chloride, 578; acetone, 566; methanol, 576; N-methyl-2-pyrrolidone, 592.
EXAMPLE 14
General Formula I
A=3-phenyl-5-isoxazolone (5)
B=julolidinyl (12)
m=0
.sup.1 H NMR (CD.sub.3 COCD.sub.3) .delta. 8.08 (v br s, 2H), 7.58 (m, 5H), 7.31 (s, 1H), 3.46 (apparent t, J=5.8 Hz, 4H), 2.73 (apparent t, J=6.2 Hz, 4H), 1.95 (m, 4H); .sup.13 C NMR .delta. 164.85, 150.89, 149.27, 135.55, 135.49, 129.96, 128.97, 128.79, 128.73, 121.05, 120.85, 107.03, 50.43, 27.32, 20.82; Anal. Calcd. for C.sub.22 H.sub.20 N.sub.2 O.sub.2 : C, 76.72; H, 5.85; N, 8.13. Found: C, 76.82; H, 5.87; N, 8.09. .lambda..sub.max (solvent, nanometers): cyclohexane, 476; chloroform, 504.
EXAMPLE 15
General Formula I
A=3-phenyl-5-isoxazolone (5)
B=julolidinyl (12)
m=1
.sup.1 H NMR (CD.sub.3 COCD.sub.3) .delta. 8.12 (dd J=14.7, 12.2 Hz, 1H), 7.66 (m, 2H), 7.61 (dd, J=12.2, 0.6 Hz, 1H), 7.56 (m, 3H), 7.42 (d, J=14.6 Hz, 1H), 7.17 (s, 2H), 3.38 (apparent t, J=5.8 Hz, 4H), 2.75 (apparent t, J=6.2 Hz, 4H), 1.94 (m, 4H). .sup.13 C NMR (125.8 MHz) .delta. 171.10, 162.47, 155.21, 150.82, 147.26, 130.16, 129.85, 128.86, 128.72, 128.13, 122.34, 121.37, 117.40, 108.89, 50.16, 27.42, 21.10; Anal. Calcd. for C.sub.24 H.sub.22 N.sub.2 O.sub.2 : C, 77.81; H, 5.99; N, 7.56. Found: C, 77.79; H, 6.00; N, 7.49. .lambda..sub.max (solvent, nanometers): cyclohexane, 517; chloroform, 586.
EXAMPLE 16
General Formula I
A=3-phenyl-5-isoxazolone (5)
B=julolidinyl (12)
m=2
.sup.1 H NMR (CD.sub.3 COCD.sub.3) .delta. 7.75 (dd J=14.1, 12.6 Hz, 1H), 7.66 (m, 2H), 7.58 (dd, J=12.6, 0.6 Hz, 1H), 7.57 (m, 3H), 7.42 (dd, J=14.2, J=11.1 Hz, 1H), 7.11 (s, 2H), 7.09 (dd J=13.9, 11.0 Hz, 1H), 7.01 (d, J=14.0 Hz, 1H), 3.30 (apparent t, J=5.7 Hz, 4H), 2.72 (apparent t, J=6.2 Hz, 4H), 1.92 (m, 4H). Anal. Calcd. for C.sub.26 H.sub.24 N.sub.2 O.sub.2 : C, 78.76; H, 6.10; N, 7.07. Found: C, 78.64; H, 6.16; N, 7.05. .lambda..sub.max (solvent, nanometers): cyclohexane, 554; chloroform, 620.
EXAMPLE 17
General Formula I
A=3-phenyl-5-isoxazolone (5)
B=julolidinyl (12)
m=3
.sup.1 H NMR .delta. 7.79 (dd J=14.1, 12.4 Hz, 1H), 7.59 (m, 2H), 7.52 (m, 3H), 7.32 (d, J=12.4 Hz, 1H), 7.04 (dd, J=14.3, J=11.7 Hz, 1H), 6.94 (s, 2H), 6.84 (apparent dd J=14.1, 9.8 Hz, 1H), 6.73 (m, 2H), 6.55 (dd J=14.0, 11.7 Hz, 1H), 3.24 (apparent t, J=5.7 Hz, 4H), 2.73 (apparent t, J=6.2 Hz, 4H), 1.96 (m, 4H). .sup.13 C NMR .delta. 21.51, 27.62, 49.91, 112.12, 121.19, 122.91, 123.25, 124.98, 126.97, 128.99, 130.45, 142.20, 144.46, 147.24, 149.44, 154.14, 163.06; Anal. Calcd. for C.sub.28 H.sub.26 N.sub.2 O.sub.2 : C, 79.59; H, 6.20; N, 6.63'. Found: C, 79.51; H, 6.15; N, 6.61.
EXAMPLE 18
General Formula III
A=diethylthio barbituric acid (2)
B=dimethylaminophenyl (11)
C=isophorone (16)
m=1
.sup.1 H NMR (CD.sub.3 COCD.sub.3) .delta. 8.38 (s, 1H), 7.59 (dm, J=8.8 Hz, 2H), 7.27 (d, J=15.9 Hz, 1H), 7.06 (dd, J=15.9, 0.5 Hz, 1H), 6.76 (dm, J=9.0 Hz, 2H), 4.48 (br, 4H), 3.09 (s, 2H), 3.04 (s, 6H), 2.54 (s, 2H) 1.23 (br m, 6H), 1.04 (s, 6H).
EXAMPLE 19
General Formula III
A=diethylthio barbituric acid (2)
B=dimethylaminophenyl (11)
C=isophorone (16)
m=2
.sup.1 H NMR .delta. 8.32 (s, 1H), 7.37 (dm, J=8.7 Hz, 2H), 6.98 (m, 1H), 6.79 (m, 2H), 6.70 (br, 2H), 6.60 (d, J=15.1 Hz, 1H), 4.54, 4.51 (each q, J=6.8 Hz, 2H), 3.08 (s, 2H), 3.03 (s, 6H), 2.40 (s, 2H) 1.31, 1.29 (each t, J=6.9 Hz, 3H), 1.04 (s, 6H).
EXAMPLE 20
General Formula III
A=diethylthio barbituric acid (2)
B=dimethylaminophenyl (11)
C=isophorone (16)
m=3
.sup.1 H NMR .delta. 8.31 (s, 1H), 7.35 (dm, J=8.6 Hz, 2H), 6.90 (dd, J=15.0, J=11.2, 1H), 6.77 (dd, J=15.2, 10.6 Hz, 1H), 6.70 (br, 2H), 6.68 (dd, J=14.2, 10.7 Hz, 1H), 6.66 (d, J=15.2 Hz, 1H), 6.56 (d, J=15.1 Hz, 1H), 6.43 (dd, J=14.1, 11.2 Hz, 1H), 4.55, 4.51 (each q, J=7.0 Hz, 2H), 3.07 (s, 2H), 3.01 (s, 6H), 2.38 (s, 2H) 1.31, 1.29 (each t, J=7.0 Hz, 3H), 1.04 (s, 6H).
EXAMPLE 21
General Formula III
A=diethylthio barbituric acid (2)
B=dimethylaminophenyl (11)
C=isophorone (16)
m=4
.sup.1 H NMR .delta. 8.30 (s, 1H), 7.32 (dm, J=8.6 Hz, 2H), 6.87 (dd, J=15.0, J=11.1, 1H), 6.72 (dd, J=15.2, 10.9 Hz, 1H), 6.67 (br d, J=8.0 Hz, 2H), 6.61 (dd, J=14.5, 11.3 Hz, 1H), 6.60 (d, J=15.6 Hz, 1H), 6.56 (dd, J=14.4, 10.7 Hz, 1H), 6.56 (d, J=15.2 Hz, 1H), 6.39 (dd, J=14.2, 11.5 Hz, 1H), 6.39 (dd, J=14.5, 11.2 Hz, 1H), 4.54, 4.51 (each q, J=6.9 Hz, 2H), 3.07 (s, 2H), 3.00 (s, 6H), 2.36 (s, 2H) 1.31, 1.29 (each t, J=7.0 Hz, 3H), 1.04 (s, 6H).
EXAMPLE 22
General Formula II
A=diethylthiobarbituric acid, (2)
B=(14) with Y=S, D=piperidinyl
m=n=p=0
Anal. Calcd. for C.sub.18 H.sub.23 N.sub.3 O.sub.2 S.sub.2 : C, 57.27; H, 6.14; N, 11.13; S, 16.99. Found: C, 57.10; H 6.20; N, 11.22; S, 16.82. High resolution MS calcd. for C.sub.18 H.sub.23 N.sub.3 O.sub.2 S.sub.2 : 377.1225. Found: 377.1232.
EXAMPLE 23
General Formula II
A=5-phenyl-3-isoxazolone, (5)
B=(14) with Y=S, D=piperidinyl,
m=1,
n=1, Z=S,
p=0
.sup.1 H NMR (CD.sub.2 Cl.sub.2) .delta. 7.78 (s, 1H), 7.60 (m, 6H), 7.38 (d, J=15.3 Hz, 1H), 7.08 (d, J=4.2 Hz, 1H), 6.98 (d, J=4.2 Hz, 1H), 6.65 (d, J=15.4 Hz, 1H), 5.98 (d, J=4.0 Hz, 1H), 3.27 (t, J=5.6 Hz, 4H), 1.71 (m, 4H), 1.62 (m, 2H). Anal. Calcd. for C.sub.25 H.sub.22 N.sub.2 O.sub.2 S.sub.2 : C, 67.24; H, 4.97; N, 6.27; S, 14.36. Found: C, 67.26; H, 4.99; N, 6.26; S, 14.29.
EXAMPLE 24
General Formula II
A=diethylthiobarbituric acid, (2)
B=(14) with Y=S, D=piperidinyl,
m=1,
n=1, Z=S,
p=1
.sup.1 H NMR (CD.sub.2 Cl.sub.2) .delta. 8.28 (dd, J=14.5, 2.2 Hz, 1H), 8.11 (d, J=12.2 Hz, 1H), 7.55 (d, J=14.5 Hz, 1H), 7.33 (d, J=4.1 Hz, 1H), 7.16 (d, J=15.3 Hz, 1H), 6.96 (d, J=4.0 Hz, 1H), 6.90 (d, J=4.1 Hz, 1H), 6.62 (d, J=15.4 Hz, 1H), 5.97 (d, J=4.20 Hz, 1H), 4.53 (m, 4H), 3.25 (t, 4H), J=5.7 Hz), 1.70 (m, 4H), 1.61 (m, 2H), 1.26 (m, 6H).
Four different compounds produced by the above-described procedure were analyzed to determine first molecular hyperpolarizabilities. The results of these determinations are set forth in Tables 1-4. Tables 1-3 show the measured .beta. for the three exemplary compounds in accordance with the present invention. Table 4 sets forth measurements for a compound not covered by the present invention wherein A.dbd.CH.dbd.CHC.sub.6 H.sub.4 NO.sub.2.
TABLE 1______________________________________General Formula IA = CH-diethylthiobarbituric acid (2)B = dimethylaminophenyl (11) .beta.(0)/ .mu..beta.(0)/ # of atoms .lambda.max .mu./10.sup.-18 .beta./10.sup.-30 10.sup.-30 .mu..beta./10.sup.-48 10.sup.-48m conjugated (nm) (esu) (esu) (esu) (esu) (esu)______________________________________0 9 (484) 5.4 68 48 370 2591 11 (572) 5.7 256 150 1457 8552 13 (604) 6.2 636 347 3945 21513 15 (624) 6.6 1490 772 9831 5095______________________________________
TABLE 2______________________________________General Formula IA = 3-phenyl-5-isoxazolone (5)B = dimethylaminophenyl (11) .beta.(0)/ .mu..beta.(0)/ # of atoms .lambda.max .mu./10.sup.-18 .beta./10.sup.-30 10.sup.-30 .mu..beta./10.sup.-48 10.sup.-48m conjugated (nm) (esu) (esu) (esu) (esu) (esu)______________________________________0 9 (478) 8.3 27 56 312 2211 11 (530) 8.6 140 90 1202 7712 13 (562) 8.7 362 218 3156 18953 15 (582) 8.9 918 528 8171 4696______________________________________
TABLE 3______________________________________Genral Formula IA = CHC.sub.6 H.sub.4 NO.sub.2B = dimethylaminophenyl (11) .beta.(0)/ .mu..beta./ .mu..beta.(0)/ # of atoms .lambda.max .mu./10.sup.-18 .beta./10.sup.-30 10.sup.-30 10.sup.-48 10.sup.-48m conjugated (nm) (esu) (esu) (esu) (esu) (esu)______________________________________0 13 (430) 6.6 73 55 482 3631 15 (442) 7.6 107 80 813 6082 17 (458) 8.2 131 95 1074 7793 19 (464) 9 .+-. 1 190 .+-. 133 .+-. 1700 .+-. 1197 .+-. 35 35 400 250______________________________________
TABLE 4______________________________________General Formula IA = CH-diethylthiobarbituric acid (2)B = julolidinyl (12) .beta.(0)/ .mu..beta.(0)/ # of atoms .lambda.max .mu./10.sup.-18 .beta./10.sup.-30 10.sup.-30 .mu..beta./10.sup.-48 10.sup.-48m conjugated (nm) (esu) (esu) (esu) (esu) (esu)______________________________________0 9 (522) 7.0 87 56 609 3941 11 (614) 6.6 355 186 2210 11592 13 (680) 6.3 1141 490 7152 30693 15 (686) 8.8 2169 911 19086 8019______________________________________
As can be seen from thee above Tables, compounds in accordance with the present invention (Table 1-3) have large first molecular hyperpolarizabilities (.beta.) in comparison with the compound set forth in Table 4. For example, the results in Table 2 show that this exemplary composition in accordance with the present invention has a .beta. (0) of 911.times.10.sup.-30 esu (after correcting for dispersion with a two state model). This is to be compared with the compound in Table 4 which has a .beta. (0) of 133.times.10.sup.-30 esu. The Tables show that when the number of carbon double bonds which link the two functional groups together is increased, the first hyperpolarizabilities unexpectedly increases.
Having thus described exemplary embodiments of the present invention, it should be noted by those skilled in the art that the within disclosures are exemplary only and that various other alternatives, adaptations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the specific embodiments as illustrated herein, but is only limited by the following claims.

Number	Name	Date
4166740	Webster et al.	Sep 1979
4714838	Harelstad et al.	Dec 1987
5256784	Francis et al.	Oct 1993
5312565	Beckerbauer et al.	May 1994
5334333	Goetz	Aug 1994
5534201	Summers et al.	Jul 1996

Nonlinear optical materials with reduced aromaticity and bond length alternation

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