WO1993024859A1 - Optically non-linear materials - Google Patents
Optically non-linear materials Download PDFInfo
- Publication number
- WO1993024859A1 WO1993024859A1 PCT/GB1993/001083 GB9301083W WO9324859A1 WO 1993024859 A1 WO1993024859 A1 WO 1993024859A1 GB 9301083 W GB9301083 W GB 9301083W WO 9324859 A1 WO9324859 A1 WO 9324859A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- dye according
- dye
- anion
- carbon atoms
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
-
- 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
- G02F1/3611—Organic materials containing Nitrogen
- G02F1/3612—Heterocycles having N as heteroatom
-
- 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
- G02F1/3614—Heterocycles having S as heteroatom
Definitions
- the present invention relates to novel optically non-linear materials, to methods for their synthesis and to optical devices which incorporate such materials.
- Film-forming hemicyanines dyes of general formula D-C6H4-CH CH-C5H4N + -R X where D is an electron donating group, R is an al yl group and X ⁇ is a simple inorganic anion such as a halide ion have been extensively studied for second harmonic generation (SHG). Their properties are dependent in part upon the extent of aggregation within the Langmuir-Blodgett film structures and in part upon the position of the anion. Girling e al_. (Thin Solid Films 132, 101 1985) and Schildkraut et al_. (Opt. Lett 13, 134, 1988) have disclosed that the SHG may be enhanced by mixing the dye with a fatty acid.
- Preferred anions are a phiphiles of the formula R-Z ⁇ or R- ⁇ r-Z _ wherein R represents a hydrophobic group comprising from 8 to 30 carbon atoms, -a represents a conjugated or aromatic bridging group and Z represents a negatively charged group such as a carboxylate, sulphate or sulphonate.
- R represents a hydrophobic group comprising from 8 to 30 carbon atoms
- -a represents a conjugated or aromatic bridging group
- Z represents a negatively charged group such as a carboxylate, sulphate or sulphonate.
- anionic surfactants especially the monobasic anionic surfactants such as soaps, alkylbenzene sulphonates, olefin sulphonates, alcohol sulphates and alkoxylated alcohol sulphates, alkoxylated alkylphenol sulphates, sulphated acids, amides and esters and sulphated natural oils and fats.
- the preferred amphiphiles for use in the present invention are soaps, alkyl benzene sulphonates, alcohol sulphates and ethoxylated alcohol sulphates.
- the materials of this invention may comprise any amphiphilic cationic dye of general formula D- ⁇ r-A + X ⁇ wherein D represents an electron donating group; ir represents a conjugated bridging group; A + represents an electron accepting group and X " represents the amphiphilic anion.
- R represents a hydrophobic alkyl or alkenyl group comprising 8 to 30 carbon atoms
- a + represents a pyridinium, pyrimidinium, quinoliniu , isoquinoliniu , benzothiazolium or thiazolium cation
- D represents an amino, N-alkylamino (R'HN-), N,N-dialkylamino (R'R"N-), alkoxy (R'O-), carboxylate (R'C(O)O) or alkylthio (R'S-) group wherein R' and R" represent an aliphatic, alkyl or alkenyl group comprising 8 to 30 carbon atoms
- a + represents a pyridinium, pyr
- novel compounds of this invention may conveniently be prepared by a metathesis reaction between a simple inorganic salt of the cation, e.g. the halide and especially the iodide or bromide and a metallic salt of the amphiphilic anion, e.g. the alkali metal and especially the sodium salt.
- the product may be purified or may be used directly in the production of an optically non-linear Langmuir-Blodgett film. Alternatively the reactants can be mixed during the formation of the film.
- the inorganic salt produced by the metathesis reaction migrates into the aqueous subphase and the properties of the resulting film are not significantly affected.
- the novel dyes may be formed into optically non-linear films using conventional techniques.
- Non-centrosymmetric multi-layered films may be produced by alternate layer deposition in which every alternate layer comprises a spacer molecule.
- An example of a suitable spacer molecule is 4,4'-dioctadecyl- 3,5,3' ,5'-tetramethyldipyrrylmethene hydrobromide.
- 1 represents a Nd:YAG laser
- 2 is an attenuator
- 3 is an infrared mirror
- 4 is a beam splitter
- 5 are visible blocking filters
- 6 is a Y-cut quartz plate reference
- 7 is an infrared blocking filter
- 8 is a 532 nm narrow bandpass filter
- 9 is a photomultiplier tube
- 10 is an infrared mirror
- 11 is a Glan Thompson polariser
- 12 is a halfwave plate
- 13 is a lens
- 14 are visible blocking filters
- 15 is the Langmuir-Blodgett film
- 16 is an infrared blocking filter
- 17 is a lens
- 18 is a 532 nm narrow bandpass filter
- 19 is a photomultiplier tube.
- E-N-octadecyl-4-(2-(4-acetoxyphenyl)ethenyl)pyridinium iodide The dyes were synthesized by the reaction of N-octadecyl-4- methylpyridinium iodide, the appropriate para-substituted benzaldehyde, e.g. 4-methoxybenzaldehyde for (2), and piperidine in hot methanol.
- the dye was spread from dilute methanol/chloroform solution onto the pure water subphase of compartment A of a Nima Technology Langmuir-Blodgett trough, and the spacer from dilute chloroform solution onto the pure water subphase of compartment B.
- Non-centrosymmetric structures were obtained by the alternate-layer deposition of the dye (on the upstroke) and the spacer (on the downstroke) on slides initially coated with a bilayer of spacer. The SHG from such alternate-layer films increases quadratically with the number of bilayers.
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6500320A JPH07507338A (en) | 1992-05-27 | 1993-05-26 | optical nonlinear materials |
EP93910286A EP0642678A1 (en) | 1992-05-27 | 1993-05-26 | Optically non-linear materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB929211238A GB9211238D0 (en) | 1992-05-27 | 1992-05-27 | Optically non-linear materials |
GB9211238.2 | 1992-05-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993024859A1 true WO1993024859A1 (en) | 1993-12-09 |
Family
ID=10716107
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1993/001083 WO1993024859A1 (en) | 1992-05-27 | 1993-05-26 | Optically non-linear materials |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0642678A1 (en) |
JP (1) | JPH07507338A (en) |
GB (2) | GB9211238D0 (en) |
RU (1) | RU94046100A (en) |
WO (1) | WO1993024859A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2282606A (en) * | 1993-08-11 | 1995-04-12 | British Tech Group | Z-type films for second harmonic generation |
KR100370405B1 (en) * | 2000-05-17 | 2003-01-29 | 삼성전자 주식회사 | Hemicyanine dyes and optical recording medium using the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989005843A1 (en) * | 1987-12-23 | 1989-06-29 | MERCK Patent Gesellschaft mit beschränkter Haftung | Non-linear optical material containing a hemicyanine compound and process for producing it |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8513770D0 (en) * | 1985-05-31 | 1985-07-03 | Gen Electric Co Plc | Optically non-linear materials |
-
1992
- 1992-05-27 GB GB929211238A patent/GB9211238D0/en active Pending
-
1993
- 1993-05-26 RU RU94046100/04A patent/RU94046100A/en unknown
- 1993-05-26 GB GB9310843A patent/GB2267288B/en not_active Expired - Fee Related
- 1993-05-26 EP EP93910286A patent/EP0642678A1/en not_active Withdrawn
- 1993-05-26 WO PCT/GB1993/001083 patent/WO1993024859A1/en not_active Application Discontinuation
- 1993-05-26 JP JP6500320A patent/JPH07507338A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989005843A1 (en) * | 1987-12-23 | 1989-06-29 | MERCK Patent Gesellschaft mit beschränkter Haftung | Non-linear optical material containing a hemicyanine compound and process for producing it |
Non-Patent Citations (5)
Title |
---|
JAPANESE JOURNAL OF APPLIED PHYSICS vol. 29, no. 6, June 1990, TOKYO JP pages 1112 - 1115 S.OKADA ET AL. 'synthesis and crystal structure of a novel organic ion-complex crystal for second-order nonlinear optics' * |
JOURNAL OF APPLIED PHYSICS vol. 62, no. 5, 1 September 1987, NEW YORK US pages 2028 - 2032 T.YOSHIMURA 'characterization of the electro-optic effect in styrilpyridinium cyanine dye thin-film crystals by an ac modulation method' * |
JOURNAL OF THE OPTICAL SOCIETY OF AMERICA - B vol. 4, no. 6, June 1987, NEW YORK US pages 950 - 955 I.R.GIRLING ET AL. 'second-harmonic generation in mixed hemicyanine: fatty-acid Langmuir-blodgett monolayers' * |
NATURE vol. 357, 4 June 1992, LONDON GB pages 393 - 395 G.J.ASHWELL ET AL. 'Improved second-harmonic generation from langmuir-blodgett films of hemicyanine dyes' * |
THIN SOLID FILMS vol. 179, 1989, LAUSANNE CH pages 529 - 534 P.STROEVE ET AL. 'studies of orientation and order of interleaved langmuir-blodgett films of a hemicyanine dye' * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2282606A (en) * | 1993-08-11 | 1995-04-12 | British Tech Group | Z-type films for second harmonic generation |
GB2282606B (en) * | 1993-08-11 | 1998-03-25 | British Tech Group | Z-type films for second harmonic generation |
KR100370405B1 (en) * | 2000-05-17 | 2003-01-29 | 삼성전자 주식회사 | Hemicyanine dyes and optical recording medium using the same |
Also Published As
Publication number | Publication date |
---|---|
GB2267288B (en) | 1995-12-06 |
GB9211238D0 (en) | 1992-07-08 |
JPH07507338A (en) | 1995-08-10 |
GB2267288A (en) | 1993-12-01 |
RU94046100A (en) | 1996-09-27 |
EP0642678A1 (en) | 1995-03-15 |
GB9310843D0 (en) | 1993-07-14 |
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