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WO2008034272A1 - Sel de stilbazolium - Google Patents

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Publication number
WO2008034272A1
WO2008034272A1 PCT/CH2007/000453 CH2007000453W WO2008034272A1 WO 2008034272 A1 WO2008034272 A1 WO 2008034272A1 CH 2007000453 W CH2007000453 W CH 2007000453W WO 2008034272 A1 WO2008034272 A1 WO 2008034272A1
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Prior art keywords
group
nonlinear optical
salt according
stilbazolium
stilbazolium salt
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PCT/CH2007/000453
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English (en)
Inventor
Peter Günter
Mojca Jazbinsek
Zhou Yang
Lukas Mutter
Blanca Ruiz
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Publication of WO2008034272A1 publication Critical patent/WO2008034272A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3613—Organic materials containing Sulfur

Definitions

  • the present invention relates to a stilbazolium salt as claimed in claim 1 and to a nonlinear optical material comprising such a salt as claimed in claim 11.
  • the inventive salt has both high second-order nonlinear optical properties and very favorable crystal growth characteristics.
  • NLO nonlinear optical
  • organic crystals based on the charged chromophores and strong Coulomb interactions have several advantages over non- ionic species, such as a large molecular nonlinearity or first-order hyperpolarizability ( ⁇ ), a better long-term stability and a higher tendency to override the dipole-dipole interactions and thus form non-centrosymmetric macroscopic packing
  • ⁇ molecular nonlinearity or first-order hyperpolarizability
  • ⁇ first-order hyperpolarizability
  • ⁇ first-order hyperpolarizability
  • ⁇ first-order hyperpolarizability
  • DAST consists of a positively charged nonlinear optical chromophore stilbazolium and a negatively charged tosylate anion.
  • the counter- anion tosylate is used to override the preferred antiparallel crystallization of the chromophores.
  • DAST is also the only commercially available organic nonlinear optical crystal [3]
  • its growth is still a challenge and there are high efforts to investigate the growth of bulk and thin films of DAST
  • one of the challenges is to speed up the several weeks long growth time of high optical quality DAST crystals with dimensions exceeding lcm 3 [3].
  • DS ⁇ S A-N 1 N- dimethylamino-4'-N'-methyl-stilbazolium 2-naphthalenesulfonate
  • the Stilbazolium salt according to the invention is represented by formula (I).
  • At least one of the substituents Ri to R 4 is different from hydrogen or deuterium and represents an alkyl group, preferably with 1-4 carbon atoms.
  • a hydroxyl group, carboxylic group, and/or amino group may be included in said alkyl group, preferably as ending group.
  • the Rj groups different from H/D enhance the solubility of the compound which is beneficial for crystal growth.
  • Xi represents hydrogen atom, deuterium atom, halogen atom, alkyl, hydroxyl group, aldehyde group, amino group, nitro group, amide group or carboxylic group group.
  • X 1 represents an alkyl group with less than 4 carbon atoms, most preferably a methyl group.
  • X 2 and X 3 being identical or different, independently represent hydrogen atom, deuterium atom, alkyl group, aryl group, wherein hydroxyl group, amide group, carboxylic group, ether bond, double bond, or the like may be included in each group.
  • X 2 and/or X 3 represent an alkyl group with less than 4 carbon atoms, preferably methyl and/or -CH 2 D, -CHD 2 , or -CD 3 .
  • X 2 and/or X 3 represent phenyl, 2,4-dinitrophenyl, and/or 2-pyrimidyl.
  • n 1 or 2.
  • organic crystals with similar nonlinear optical properties as DAST are feasible with a considerably faster crystal growth rate.
  • the salts are prepared by metathesization of 4-JV,N-dimethylamino-4'-JV-methyl- stilbazolium iodide with water solution of sodium salt of 2-mesitylenesulfonic acid, for example.
  • the salts are suited for second-order nonlinear optical applications such as electro- optical modulation, deflection, switching, filtering, frequency conversion, optical parametric oscillation s and for THz generation and detection.
  • the salts retain high second-order nonlinearities, i.e. y ⁇ of 2000 pm/V at 1.3 ⁇ m.
  • Solubilities of the salts are high in methanol, i.e. comparable to or even about two times higher than the one of DAST (4-JV, N-dimethylamino-4'-JV-methyl- stilbazolium tosylate) at the same temperature. Since the crystal structure cannot be predicted in general, some of the claimed compounds may have an enhanced solubility but crystallize in a centrosymmetric structure and are thus less suited for second-order nonlinear optical applications. Generally, those compounds crystallizing in a non-centrosymmetric structure are chosen for second-order nonlinear optical applications.
  • the stilbazolium chromophore (cation) has preferably one of the following structures:
  • the counter anion has preferably one of the following structures
  • a preferred embodiment of the invention is the combination of cation (a) with anion (e), the novel stilbazolium salt 4-N, N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6- trimethylbenzenesulfonate (DSTMS).
  • DSTMS can be prepared from metathesis reaction. With a similar molecular structure and crystal packing, DSTMS shows a much higher solubility in methanol, and therefore much better growth characteristics than the known material DAST. Large bulk crystals and thin films with good optical quality without using seed crystals can be obtained by carefully controlling the crystal growth conditions.
  • Fig. 1 shows solubility/temperature curves of DSTMS and DAST in methanol.
  • Fig. 2 shows in the upper panel a) a DSTMS bulk crystal (size 33 x 33 x 2 mm 3 ), the large surface is the (001) face.
  • the lower panel b) shows a DSTMS thin film crystal (size 6 x 5 x 0.03 mm 3 ) grown by the capillary method.
  • Fig. 3a-c show crystal packing of DSTMS projected along the crystallographic axes a (Fig. 3a), b (Fig. 3b), and c (Fig. 3c).
  • the mirror symmetry plane is perpendicular to the b-axis.
  • the chromophores make an angle of approximately 23% with respect to the polar a-axis (c).
  • Fig. 4 shows a crystal packing diagram of DSTMS projected along the [110] crystallographic vector.
  • the molecules are linked by Coulombic interactions between the ionic parts and by hydrogen bonds that are indicated by dotted lines.
  • Fig. 5 shows transmission spectra of 0.77 mm thick DSTMS crystal for light polarized along the polar a-axis (solid curve) and along the crystal b-axis (dashed curve).
  • Fig. 6 shows the THz amplitude generated through optical rectification of 160 fs pulses at 1.45 ⁇ m wavelength in a 0.34 mm thick DSTMS crystal, as detected by electro-optic sampling in a 0.5 mm thick ZnTe crystal using a frequency doubled probe beam at 0.725 ⁇ m (left) and its Fourier transform (right).
  • the oscillations for t > 2 ps are due to ambient water vapor absorption.
  • Fig. 7 shows crystallographic and other data of DSDMS, DSTMS and DAST crystals.
  • ⁇ i 2 is the angle between the long axis of the cation chromophores and the polar axis of the crystal, T m the melting temperature and X 111 the element of the first order hyperpolarizability tensor for second harmonic generation at fundamental wavelength of 1.9 ⁇ m.
  • Fig. 8 shows two DSDMS bulk crystals (size 10 x 2 x 0.4 mm and 8 x 1 x 0.2 mm 3 ).
  • Fig. 9a-c show crystal packing of DSDMS projected along the crystallographic axes a (Fig. 9a), b (Fig. 9b) and c (Fig. 9c). Cations and anions from four unit cells are shown.
  • the chromophores are aligned perfectly parallel, which is an ideal configuration for achieving high diagonal electro-optic and nonlinear optical coefficients.
  • DTMS 4-N, N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6- trimethylbenzenesulfonate
  • DSC Differential Scanning Calorimetry
  • TGA Thermogravimetric Analysis
  • DSTMS can be well dissolved in some strong polar solvents such as methanol, DMF and DMSO etc.
  • DMF and DMSO are not well suited for crystal growth because of their high boiling points. Therefore methanol was chosen as the solvent for the growth of DSTMS crystals.
  • Fig.l shows the solubility curve of DSTMS in methanol solution compared with DAST. The solubility at a temperature T was measured by saturating the solution at a higher temperature (about 5 0 C above T), slowly cooling it in the presence of a precipitated solid to maintain equilibrium, and then analyzing the solution at the temperature T.
  • the solubility of DSTMS is in the temperature range of interest around two times as large as the one found in DAST in methanol at the same temperature.
  • the large difference in the solubility can mainly be attributed to the different structure of counter-anions - the solubility of 2,4,6-trimethyl-benzenesulfonate that possesses three methyl groups should be higher than that of tosylate that possesses only one methyl group.
  • the temperature dependence of the solubility of a dilute solution considering that the solute dissolves into two ions, can be described by
  • Supersaturation in our system is achieved by lowering the temperature of the saturated solution from T' to T.
  • DAST bulky size DSTMS crystal can be easily grown without a seed crystal because of the improved growth characteristics of the latter.
  • Slow cooling technique was adapted for the growth of bulk crystals.
  • a saturated solution of DSTMS in methanol at 35°C-40°C was prepared. Spontaneous nucleation could be observed after cooling down the saturated solution. Then, the temperature was increased to dissolve most of the nuclei. The solution was carefully cooled down again to make sure that only one or two nucleated crystals remained undissolved. After that, large crystals with very good optical quality for optical measurements could be grown by slowly cooling the solution at a rate of 0.2°C-0.3°C /day. Typically, the crystals first appear as red thin plates and continue to grow preferentially along the edges in all directions. DAST, on the other hand, prefers to grow along the direction of the polar axis [-100].
  • the crystallographic structure of DSTMS was determined via X-ray analysis of single crystals. The data obtained are listed in the table shown in Fig. 7 and compared to those of DAST.
  • Figure 4 shows the hydrogen-bonded network formed by two kinds of C-H... O hydrogen bonds between the cation layers and the anion layers with H... O distances of about 2.49 A and 2.44 A, respectively.
  • the refractive indices were measured at the telecommunication wavelength of 1.55 ⁇ m by an interferometric technique.
  • refractive index data we calculated the optical absorption from the transmission measurement of Figure 5 by considering Fresnel losses due to multiple reflections at the crystal surfaces.
  • the nonlinear optical properties were measured by the standard Maker Fringe technique.
  • the first Stokes line at 1907 nm generated in a high pressure Raman cell filled with H 2 and pumped with a Q switched Nd: YAG at 1064 nm (pulse length of 7 ns) was used as fundamental wavelength.
  • the nonlinear optical properties of DAST and DSTMS can be also compared by relating microscopic first-order hyperpolarizability tensor ⁇ x7Z with the macroscopic second order susceptibility tensor ⁇ ijk-
  • DAST and DSTMS can be also compared by relating microscopic first-order hyperpolarizability tensor ⁇ x7Z with the macroscopic second order susceptibility tensor ⁇ ijk-
  • ⁇ ni (-2 ⁇ , ⁇ , ⁇ ) Nfi 2 ⁇ (f 1 ⁇ ) 2 cos 3 ( ⁇ i2 ) ⁇ 2zz (-2 ⁇ , ⁇ , ⁇ ), (2)
  • N is the number of chromophores per unit volume
  • fi ⁇ ' 2 ⁇ are the local field corrections
  • DSDMS 4-N, N-dimethylamino-4'-N'-methyl-stilbazolium 2,4- dimethylbenzenesulfonate
  • methanol was chosen as the most suitable solvent for the growth of DSDMS crystals.
  • DSDMS the slow evaporation technique at a constant temperature was adapted because we its solubility is mainly sensitive to the amount of the solvent and almost independent of temperature. Bulk single crystals with dimensions of 10 x 2 x 0.2 mm 3 have been obtained in 2-3 weeks (see Fig. 8).
  • DSDMS is an effective second-order nonlinear optical material, as confirmed by the preliminary powder second-harmonic generation test at 1.9 ⁇ m, which gave the efficiency of about 0.7 relative to the powder efficiency of DAST.
  • the powder second-harmonic generation test is a well known test to determine whether a substance has nonlinear optical properties before growing single crystals. It comprises illuminating a powder sample with a basic wavelength and detecting the presence of the second harmonic of this wavelengths. Single crystal X-ray analysis was carried out for a DSDMS crystal. The crystallographic data are listed in Figure 7, where also DAST is added for comparison. The crystal packing diagram is presented in Figure 9.
  • the crystal structure of DSDMS is triclinic, having space group symmetry Pl with one ion-pair per unit cell.
  • the three-dimensional packing exhibits alternating acentric sheets of stilbazolium cations and counter anions.
  • a further example is 4-N, N-dimethylamino-4'-N'-phenyl-stilbazolium 2,4- dimethylbenzenesulfonate (DAPSD) salt, which is a derivative of trans-4'- (dimethylamino)-N- ⁇ henyl-4-stilbazolium hexafluorophosphate (DAPSH) [8,10].
  • DAPSD 4-N, N-dimethylamino-4'-N'-phenyl-stilbazolium 2,4- dimethylbenzenesulfonate
  • DAPSD (scheme 3) has been synthesized by combination of cation (b) with anion (f) as described above.
  • DAPSD was obtained by condensation reaction between 4-methyl-N-phenyl pyridinium chloride, which was prepared from 4-picoline and phenyl chloroform, and 4-N, N-dimethylamino-benzaldehyde in the presence of piperidine. It was then metathesized to 2,4-dimethylbenzenesulfonate by precipitation from water solution of sodium 2,4-dimethylbenzenesulfonate.
  • the powder second-harmonic generation test of DAPSD gave the efficiency of about 2.0 relative to the powder efficiency of DAST at 1.9 ⁇ m, which is also much higher than the one of the DAPSH (about 0.9 relative to the powder efficiency DAST at 1.9 ⁇ m).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Pyridine Compounds (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)

Abstract

L'invention concerne un sel de stilbazolium présentant à la fois des propriétés optiques non linéaires de second ordre élevées et des caractéristiques de croissance cristalline très favorables, ce qui convient particulièrement aux applications optiques non linéaires telles que la conversion de fréquence, la modulation électro-optique, l'oscillation paramétrique optique et la génération et la détection de térahertz (THz). Le sel est représenté par la formule générale (I) : dans laquelle au moins l'un des radicaux R1, R2, R3, R4, identiques ou différents, représente indépendamment un groupement alkyle pouvant inclure un groupement hydroxyle, un groupement carboxylique et un groupement amino, de préférence en tant que terminaison, et les radicaux R1, R2, R3, R4 restants représentent un atome d'hydrogène ou un atome de deutérium; X1 représente un atome d'hydrogène, un atome de deutérium, un atome d'halogène, un groupement alkyle, un groupement hydroxyle, un groupement aldéhyde, un groupement amino, un groupement nitro, un groupement amide ou un groupement carboxylique; X2 et X3, identiques ou différents, représentent indépendamment un atome d'hydrogène, un atome de deutérium, un groupement alkyle, un groupement aryle, un groupement hydroxyle, un groupement amide, un groupement carboxylique, une liaison éther, une double liaison ou analogue pouvant être inclus dans chaque groupe; et n = 1 ou 2.
PCT/CH2007/000453 2006-09-18 2007-09-17 Sel de stilbazolium Ceased WO2008034272A1 (fr)

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US60/845,566 2006-09-18

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011057229A3 (fr) * 2009-11-09 2011-09-22 University Of Miami Analogues de neurotransmetteurs fluorescents, compositions les contenant et procédés pour les utiliser
CN104341342A (zh) * 2014-10-23 2015-02-11 中国电子科技集团公司第四十六研究所 一种高产率、高纯度的dast源粉合成工艺
WO2016035702A1 (fr) * 2014-09-02 2016-03-10 浜松ホトニクス株式会社 Cristal optique non linéaire et son procédé de fabrication, ainsi que générateur d'ondes térahertz et appareil de mesure d'ondes térahertz

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5194984A (en) * 1991-06-10 1993-03-16 General Electric Company Stilbazolium salt and optically non-linear devices incorporating same
WO1996037639A2 (fr) * 1995-05-19 1996-11-28 The Trustees Of Princeton University Procede et appareil de depot chimique en phase vapeur organique permettant la croissance de pellicules fines organiques presentant d'importantes non-linearites optiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5194984A (en) * 1991-06-10 1993-03-16 General Electric Company Stilbazolium salt and optically non-linear devices incorporating same
WO1996037639A2 (fr) * 1995-05-19 1996-11-28 The Trustees Of Princeton University Procede et appareil de depot chimique en phase vapeur organique permettant la croissance de pellicules fines organiques presentant d'importantes non-linearites optiques

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011057229A3 (fr) * 2009-11-09 2011-09-22 University Of Miami Analogues de neurotransmetteurs fluorescents, compositions les contenant et procédés pour les utiliser
WO2016035702A1 (fr) * 2014-09-02 2016-03-10 浜松ホトニクス株式会社 Cristal optique non linéaire et son procédé de fabrication, ainsi que générateur d'ondes térahertz et appareil de mesure d'ondes térahertz
JP2016051148A (ja) * 2014-09-02 2016-04-11 浜松ホトニクス株式会社 非線形光学結晶及びその製造方法、テラヘルツ波発生装置並びにテラヘルツ波測定装置。
GB2546183A (en) * 2014-09-02 2017-07-12 Hamamatsu Photonics Kk Non-linear optical crystal and method for manufacturing same, and terahertz-wave generator and terahertz-wave measuring apparatus
US10248003B2 (en) 2014-09-02 2019-04-02 Hamamatsu Photonics K.K. Non-linear optical crystal and method for manufacturing same, and terahertz-wave generator and terahertz-wave measuring apparatus
GB2546183B (en) * 2014-09-02 2020-06-17 Hamamatsu Photonics Kk Non-linear optical crystal and method for manufacturing same, and terahertz-wave generator and terahertz-wave measuring apparatus
CN104341342A (zh) * 2014-10-23 2015-02-11 中国电子科技集团公司第四十六研究所 一种高产率、高纯度的dast源粉合成工艺
CN104341342B (zh) * 2014-10-23 2016-04-13 中国电子科技集团公司第四十六研究所 一种高产率、高纯度的dast源粉合成工艺

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