DE10039903A1 - Novel transition metal co-ordination compounds with heterocyclic-substituted bis-(thien-3-yl)perfluorocyclopoentene photochromic ligands are useful in the solid state at room temperature in e.g. opto-magnetic switches - Google Patents
Novel transition metal co-ordination compounds with heterocyclic-substituted bis-(thien-3-yl)perfluorocyclopoentene photochromic ligands are useful in the solid state at room temperature in e.g. opto-magnetic switchesInfo
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- DE10039903A1 DE10039903A1 DE2000139903 DE10039903A DE10039903A1 DE 10039903 A1 DE10039903 A1 DE 10039903A1 DE 2000139903 DE2000139903 DE 2000139903 DE 10039903 A DE10039903 A DE 10039903A DE 10039903 A1 DE10039903 A1 DE 10039903A1
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- photochromic
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- thien
- photochromic ligands
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 239000003446 ligand Substances 0.000 title claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract 3
- 150000003624 transition metals Chemical class 0.000 title claims abstract 3
- 239000007787 solid Substances 0.000 title claims description 6
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000005291 magnetic effect Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003852 triazoles Chemical class 0.000 claims abstract description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000006698 induction Effects 0.000 claims abstract description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000008859 change Effects 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 8
- -1 2-methyl-3-bromo5-substituted thiophenes Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003636 chemical group Chemical group 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OKCBEPHXQAIBDY-UHFFFAOYSA-N lithium;thiophene Chemical class [Li].C=1C=CSC=1 OKCBEPHXQAIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YOPBRMITNUZOIC-UHFFFAOYSA-N (4-bromo-5-methylthiophen-2-yl)-trimethylsilane Chemical compound CC=1SC([Si](C)(C)C)=CC=1Br YOPBRMITNUZOIC-UHFFFAOYSA-N 0.000 description 1
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 1
- IMTVZZQOCBGFGT-UHFFFAOYSA-N 2-(3,3,4,4,5,5-hexafluoro-2-thiophen-2-ylcyclopenten-1-yl)thiophene Chemical class FC1(F)C(F)(F)C(F)(F)C(C=2SC=CC=2)=C1C1=CC=CS1 IMTVZZQOCBGFGT-UHFFFAOYSA-N 0.000 description 1
- FHQKLIHFKVAEEP-UHFFFAOYSA-N 3,3,4,4,5,5-hexafluorocyclopentene Chemical compound FC1(F)C=CC(F)(F)C1(F)F FHQKLIHFKVAEEP-UHFFFAOYSA-N 0.000 description 1
- OGAJGUIMFMRGRB-UHFFFAOYSA-N 3,5-dibromo-2-methylthiophene Chemical compound CC=1SC(Br)=CC=1Br OGAJGUIMFMRGRB-UHFFFAOYSA-N 0.000 description 1
- BSDGZUDFPKIYQG-UHFFFAOYSA-N 4-bromopyridine Chemical compound BrC1=CC=NC=C1 BSDGZUDFPKIYQG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KTBZGSAJWRMFCV-UHFFFAOYSA-N CC=1SC(=CC=1[Li])[Si](C)(C)C Chemical compound CC=1SC(=CC=1[Li])[Si](C)(C)C KTBZGSAJWRMFCV-UHFFFAOYSA-N 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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- 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
- G02F1/01—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 for the control of the intensity, phase, polarisation or colour
- G02F1/0126—Opto-optical modulation, i.e. control of one light beam by another light beam, not otherwise provided for in this subclass
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- 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
- G02F2202/00—Materials and properties
- G02F2202/14—Materials and properties photochromic
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- Optics & Photonics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
- - Bis(thien-3-yl)perfluorocyclopenten ist als ein organisches Molekül mit photochromen Eigenschaften bekannt, bei dem eine reversible und vollständige Photoreaktion in Lösung und ebenfalls im Festkörper von 1,3,4 Hexatrien nach Cyclohexadien stattfindet. Die Verbindung besitzt ausgezeichnete photochrome Eigenschaften wie: Hoher Ermüdungswiderstand (10 Verfärbungs- /Entfärbungszyklen), hohe Stabilität der Isomeren ("open" und "closed" Formen) und eine sehr schnelle Ansprechzeit (1 ps) (M. Irie, K. Uchida, Bull.Chem.Soc. Jpn. 1998, 71, 985).- Bis (thien-3-yl) perfluorocyclopentene is included as an organic molecule Photochromic properties known to be reversible and complete Photoreaction in solution and also in the solid state of 1,3,4 hexatriene Cyclohexadiene takes place. The compound has excellent photochromic Features such as: High fatigue resistance (10 discoloration / Decolorization cycles), high stability of the isomers ("open" and "closed" Forms) and a very fast response time (1 ps) (M. Irie, K. Uchida, Bull.Chem.Soc. Jpn. 1998, 71, 985).
- - 1,2-bis[6-(1-oxyl-3.oxide-4,4,5,5-tetramethylimidazolin-2-yl)-2- methylbenzo[b]-tiophen-3-yl]hexafluorocyclopenten ist ein organisches Nitronyl-nitroxid Radikal, das zusätzlich zu seinen photochromen Eigenschaften eine Änderung der Größe der antiferromagnetischen Wechselwirkung zwischen Spinträgern für die "closed" und "open" Formen zeigt. (K. Matsuda, M. Irie, Chem. Lett., 2000, 16). Allerdings ist keine wesentliche Änderung der magnetischen Suszeptibilität bei Raumtemperatur zu beobachten.- 1,2-bis [6- (1-oxyl-4,4,5,5-tetramethylimidazoline-3.oxide-2-yl) -2- methylbenzo [b] -tiophen-3-yl] hexafluorocyclopentene is an organic Nitronyl nitroxide radical, in addition to its photochromic Properties change the size of the antiferromagnetic Interaction between spin carriers for the "closed" and "open" forms shows. (K. Matsuda, M. Irie, Chem. Lett., 2000, 16). However, it is not significant change in magnetic susceptibility at room temperature observe.
Bei der gegenwärtigen Erfindung handelt es sich um neue Koordinationsverbindungen mit 4 bis 8 Elektronen in der d-Schale, die photochrome Liganden auf der Basis von bis(thien-3-yl)perfluorocyclopenten enthalten. Wir stellen hier insbesondere neue Eisen(II)-Verbindungen vor, die thermisch und optisch induzierten Spinübergang zeigen. Diese Materialien können also gleichzeitig eine Änderung ihres magnetischen (Suszeptibilität) und optischen Verhaltens (Reflektivität, Farbe) zeigen. Das besondere dabei ist, dass diese Eigenschaft bei Raumtemperatur vorliegt. Dieses Material gehört zu einer Klasse von Verbindungen, bei denen neben den oben genannten Eigenschaften ein thermischer Spinübergang meistens in Verbindung mit Thermochromismus (tritt dann auf, wenn die d-d Übergange nicht von Metall-Ligand- Ladungsübertragungsbanden überdeckt werden) erwartet wird. Die Farbe der Koordinationsverbindungen hängt von den elektronischen Eigenschaften der Liganden, insbesondere vom Vorhanden- oder Nichtvorhandensein von MLCT-Banden im sichtbaren Bereich des elektromagnetischen Spektrums.The current invention is new coordination links with 4 to 8 electrons in the d shell, the photochromic ligands based on bis (thien-3-yl) contain perfluorocyclopentene. We are particularly making new ones here Iron (II) compounds before, the thermally and optically induced spin transition demonstrate. So these materials can simultaneously change their magnetic (Susceptibility) and optical behavior (reflectivity, color). The special is that this property is at room temperature. This material belongs to a class of compounds in which in addition to the above properties a thermal spin transition mostly in connection with thermochromism (occurs then when the d-d transitions are not from metal ligand Charge transfer bands are covered) is expected. The color of the Coordination compounds depends on the electronic properties of the ligands, in particular, the presence or absence of MLCT bands in the visible range of the electromagnetic spectrum.
Ausgehend von bis(thien-3-yl)perfluorocyclopenten haben wir photochrome Liganden hergestellt, die mit Stickstoff-Heterozyklen (Pyridin, Triazol, Tetrazol, Isoxazol, Bipyridin, Phenanthrolin, u. a.) substituiert sind. Diese Liganden können in zahlreichen Eisen(II)koordinationsverbindungen thermischen Spinübergang hervorrufen.Starting with bis (thien-3-yl) perfluorocyclopentene, we have photochromic ligands manufactured with nitrogen heterocycles (pyridine, triazole, tetrazole, isoxazole, Bipyridine, phenanthroline, u. a.) are substituted. These ligands can be found in numerous Iron (II) coordination compounds cause thermal spin transition.
Die photochromen Liganden weisen folgende Struktur auf:
The photochromic ligands have the following structure:
wobei X die Elemente bzw. Gruppen H, F, Cl, Br, J, OH, NO2, CnH2n+1 oder CnH2n-X und ε ein stark elektroaktiver Substituent oder der Rest R sein kann.where X can be the elements or groups H, F, Cl, Br, J, OH, NO 2 , C n H 2n + 1 or C n H 2n -X and ε can be a strongly electroactive substituent or the radical R.
Die erste Verbindungsklasse trägt in Position 3 und 6 der photochromen Verbindung denselben Stickstoff-Heterozyklus. Mit Eisen(II) entstehen polymere Koordinationsverbindungen. The first class of compounds bears in positions 3 and 6 of the photochromic compound the same nitrogen heterocycle. With iron (II), polymers are formed Coordination compounds.
Die zweite Verbindungsklasse enthält in Position 3 einen Stickstoff-Heterozyklus und
in Position 6 einen stark elektroaktiven Substituenten (E). In diesem Fall werden mit
Eisen(II) mononukleare Verbindungen erhalten, die in verschiedenen Lösungsmitteln
löslich sind. Eine Liste von Substituenten R ist im folfgenden aufgeführt. Es ist zu
erwähnen, dass auch Kombinationen dieser Gruppen zu Spincrossoververhalten in den
Eisen(II)-Komplexverbindungen führen können.
The second class of compounds contains a nitrogen heterocycle in position 3 and a strongly electroactive substituent (E) in position 6. In this case, iron (II) gives mononuclear compounds which are soluble in various solvents. A list of substituents R is given in the following. It should be mentioned that combinations of these groups can also lead to spin crossover behavior in the iron (II) complex compounds.
Liste von Substitutenten R. Das Symbol Φ stellt eine chemische Gruppe dar, die im Liganden vorhanden sein kann. List of substituents R. The symbol Φ represents a chemical group that is in the Ligands can be present.
Das photochrome System kann infolge einer photochromen Reaktion von 1,3,5- Hexatrien zu Cyclohexadien, d. h. zwischen einer nicht-planaren, farblosen, "open" Form (O) und einer planaren, stark gefärbten Form (C) reversibel "geschaltet" werden. In der letzten Form tritt ausgedehnte Konjugation auf.Due to a photochromic reaction of 1,3,5- Hexatriene to cyclohexadiene, d. H. between a non-planar, colorless, "open" Form (O) and a planar, strongly colored form (C) are reversibly "switched". Extended conjugation occurs in the last form.
Durch Bestrahlung des Eisen(II)-Komplexes mit Licht kann diese Reaktion auch im Festkörper stattfinden. Jedoch ist der räumliche Anspruch bei Änderung der Geometrie der Koordinationssphäre (in den beiden Formen) verschieden; dies hat unmittelberen Einfluss auf das Spinübergangsverhalten.By irradiating the iron (II) complex with light, this reaction can also be Solid state take place. However, the spatial requirement when changing the geometry the coordination sphere (in the two forms) different; this has more immediate Influence on the spin transition behavior.
Die photochromen Liganden werden auf folgenden Wegen hergestellt: 2-Methyl 3-bromo 5-substituerte Thiophene werden mit n-BuLi in THF bei -80°C umgesetzt. Zu diesen Lithium Thiophenen wird ein halbes Äquivalent Perfluorocyclopenten bei -80°C hinzugefügt. Die Addition-Elimination-Reaktion ergeben die symmetrischen 1,2-Dithiophenylperfluorocyclopentene. Der Substituent in Position 5 kann die koordinierende Gruppe für Eisen(II) sein (Pyridin, Triazol, Tetrazol, u. a.) oder kann in andere Derivate umgewandelt werden (z. B. vom Formyl zum Imin des 4-Aminotraizols, u. a.).The photochromic ligands are produced in the following ways: 2-Methyl 3-bromo 5-substituted thiophenes are mixed with n-BuLi in THF at -80 ° C implemented. Half of this is equivalent to these lithium thiophenes Perfluorocyclopentene added at -80 ° C. The addition-elimination reaction give the symmetrical 1,2-dithiophenylperfluorocyclopentenes. The substituent in Position 5 can be the coordinating group for iron (II) (pyridine, triazole, Tetrazole, u. a.) or can be converted into other derivatives (e.g. from formyl to the imine of 4-aminotraizole, u. a.).
Die umgekehrte Addition von Lithium-Thiophen an zwei Äquivalente Perfuorocyclopenten führt hauptsächlich zu monosubstituierten Perfluorocyclopentenen, aus denen die dissymetrischen Verbindungen (mit Substituenten R und ε) durch Additions-Eliminationsreaktion von 2-Methyl 3-lithio 5- substituierten Thiophenen erhalten werden.The reverse addition of lithium thiophene to two equivalents Perfuorocyclopentene mainly leads to monosubstituted Perfluorocyclopentenes, from which the dissymetric compounds (with Substituents R and ε) by addition-elimination reaction of 2-methyl 3-lithio 5- substituted thiophenes can be obtained.
Der organische Ligand (L), 1,2-Bis[2'-methyl-5'-(pyrid-4"-yl]perfluorocyclopenten wird gemäß der Vorschrift von S. L. Gilat, S. H. Kawai, J.-M. Lehn, Chem. Eur. J 1995, 1, 275 erhalten.The organic ligand (L), 1,2-bis [2'-methyl-5 '- (pyrid-4 "-yl] perfluorocyclopentene is carried out according to the instructions of S.L. Gilat, S.H. Kawai, J.-M. Lehn, Chem. Eur. J 1995, 1, 275 obtained.
Die Koordinationsverbindung [FeL(NCS)] erhält man durch Reaktion einer Lösung des Liganden L in trockenem Methanol mit einer methanolischen Lösung von Eisen(II)chlorid Tetrahydrat und Ammoniumthiocyanat. Der intensiv orange gefärbte Niederschlag wird sofort filtriert, mit kleinen Portionen Methanol gewaschen und über PO getrocknet. Alle Handhabungen sind im Dunkeln und in Argon-Athmosphäre durchzuführen. The coordination compound [FeL (NCS)] is obtained by reacting a solution of ligand L in dry methanol with a methanolic solution of Iron (II) chloride tetrahydrate and ammonium thiocyanate. The intense orange colored Precipitate is filtered immediately, washed with small portions of methanol and over PO dried. All operations are in the dark and in an argon atmosphere perform.
Dieser organische Ligand 1,2-Bis[5'-(2"-para-pyridin äthynyl)-2'-methylthien-3'- yl]perfluorocyclopenten wird in einer siebenstufigen Synthese aus 2-Methylthiophen erhalten: Die Bromierung von 2-Methylthiophen mit Brom in Essigsäure ergibt 2- Methyl 3,5-dibromothiophen (R. Lantz, A.B. Hörnfeldt, Chem. Scripta 1972, 2, 9). Die Dibromo-Verbindung wird anschließend mit n-BuLi in EtO bei -78°C lithiiert und mit MeSiCI behandelt, um 2-Methyl 3-bromo 5-trimethylsilyl thiophen (T. Saika, M. Irie, T. Shimidzu, J. Chem. Soc., Chem. Comm. 1994, 2123) zu erhalten. 1,2-bis[5'- (trimethylsilyl)-2'-methylthien-3'-yl]perfluorocyclopenten erhält man durch Zugabe von einem halben Äquivalent Perfluorocyclopenten zu 2-Methyl 3-lithio 5-trimethylsilyl thiophen in THF bei -78°C (T. Saika, M. Irie, T. Shimidzu, J. Chem. Soc., Chem. Comm. 1994, 2123). Die Trimethylsilyl-Gruppen werden quantitativ durch Jod mit Hilfe von ICl in Methylenchlorid ersetzt. Eine Reaktion - vom Typ Sonogashira - mit Trimethylsilylacetylen liefert 1,2-Bis[5'-(2"-trimethylsilyläthynyl)-2'-methylthien-3'- yl]perfluorocyclopenten; dieses Material wird mit einer Lösung von 5% NaHCO desilyliert und anschließend in einer Sonogashira-Reaktion Pyridin mit 4-Bromopyridin eingeführt. (Im Hinblick auf die Sonogashira-Methode siehe z. B.: K. Sonogashira, Y. Tohba, N. Hagihara, Tetrahedron Letters 1975, 50, 4467)This organic ligand 1,2-bis [5 '- (2 "-para-pyridine ethynyl) -2'-methylthien-3'- yl] perfluorocyclopentene is produced in a seven-step synthesis from 2-methylthiophene obtained: The bromination of 2-methylthiophene with bromine in acetic acid gives 2- Methyl 3,5-dibromothiophene (R. Lantz, A.B. Hörnfeldt, Chem. Scripta 1972, 2, 9). The dibromo compound is then lithiated with n-BuLi in EtO at -78 ° C and treated with MeSiCI to give 2-methyl 3-bromo 5-trimethylsilyl thiophene (T. Saika, M. Irie, T. Shimidzu, J. Chem. Soc., Chem. Comm. 1994, 2123). 1,2-bis [5 ' (trimethylsilyl) -2'-methylthien-3'-yl] perfluorocyclopentene is obtained by adding half an equivalent of perfluorocyclopentene to 2-methyl 3-lithio 5-trimethylsilyl thiophene in THF at -78 ° C (T. Saika, M. Irie, T. Shimidzu, J. Chem. Soc., Chem. Comm. 1994, 2123). The trimethylsilyl groups are quantified by using iodine Help replaced by ICl in methylene chloride. A reaction - of the Sonogashira type - with Trimethylsilylacetylene provides 1,2-bis [5 '- (2 "-trimethylsilylethynyl) -2'-methylthien-3'- yl] perfluorocyclopentene; this material is made with a solution of 5% NaHCO desilylated and then in a Sonogashira reaction pyridine with 4-bromopyridine introduced. (With regard to the Sonogashira method, see for example: K. Sonogashira, Y. Tohba, N. Hagihara, Tetrahedron Letters 1975, 50, 4467)
Die Probe [FeL(NCS)] wird grünem Licht (= 365 nm) einer UV Lampe mit geeigneten Filtern ausgesetzt. Man beobachtet eine Farbänderung von intensiv orange zu dunkelblau (Bestrahlung mit weißem Licht führt zum gleichen Ergebnis). Die Farbänderung wird bei Bestrahlung mit rotem Licht (= 660 nm) rückgängig gemacht (blau nach orange).The sample [FeL (NCS)] is green light (= 365 nm) with a UV lamp exposed to suitable filters. A change in color from intense orange is observed too dark blue (exposure to white light leads to the same result). The Color change is reversed when irradiated with red light (= 660 nm) (blue to orange).
Die magnetische Suszeptibilität wurde für beide Formen gemessen: Bei Raumtemperatur wird eine kräftige Änderung im Signal beobachtet und zwar von = 2.3 cm3Kmol-1 für die "open" Form (orange) nach = 4.4 cm3Kmol-1 für die "closed" Form (blau); ist hierbei die molare magnetische Suszeptibilität.The magnetic susceptibility was measured for both forms: At room temperature a strong change in the signal is observed, namely from = 2.3 cm 3 kmol -1 for the "open" form (orange) to = 4.4 cm 3 kmol -1 for the "closed" Shape (blue); is the molar magnetic susceptibility.
- - Das Phänomen, die lichtinduzierte Schaltung zwischen "closed" und "open" Form, wird von einer gleichzeitigen Änderung von Farbe und magnetischer Suszeptibilität begleitet; dies erschließt die Nutzung auf dem Gebiet der Informationsspeicherung.- The phenomenon, the light-induced switching between "closed" and "open" Shape, is characterized by a simultaneous change of color and magnetic Accompanied susceptibility; this opens up the use in the field of Information storage.
- - Das Phänomen tritt bei Raumtemperatur auf und ist reversibel.- The phenomenon occurs at room temperature and is reversible.
- - Das Material ist bei Raumtemperatur stabil und zeigt keine Ermüdungserscheinung nach vielen Bestrahlungszyklen.- The material is stable at room temperature and shows none Fatigue after many radiation cycles.
- - Die Eigenschaften des photochromen Moleküls bleiben in der Koordinationsverbindung erhalten: sehr stabil, hoher Ermüdungswiderstand (10 Farbänderungszyklen) und sehr schnelle Schaltzeiten (1 ps). - The properties of the photochromic molecule remain in the Coordination connection maintained: very stable, high fatigue resistance (10 color change cycles) and very fast switching times (1 ps).
- - Die Verbindung ist in den üblichen Lösungsmitteln sehr gut löslich; sie ist dadurch gut geeignet, in optischen Medien verschiedenster Art, wie "bulk" und dünne Schichten eingebaut zu werden.- The compound is very soluble in the usual solvents; she is therefore very suitable in various types of optical media, such as "bulk" and to be installed thin layers.
- - Kooperative Effekte sind nicht erforderlich, d. h. der Prozess kann in einem einzigen Molekül erreicht werden.- Cooperative effects are not required, i. H. the process can be done in one single molecule can be achieved.
- - Eine hohe Informationsdichte kann gespeichert werden. Bei dem Volumen eines Moleküls von etwa 10-21 cm3 liegt die theoretische Grenze für die Informationsdichte bei ungefähr 1021 bit cm-3.- A high density of information can be saved. With the volume of a molecule of approximately 10-21 cm 3 , the theoretical limit for the information density is approximately 10 21 bit cm -3 .
- - Die Information kann mit Hilfe von optischen Methoden (z. B. Laser) oder magnetischen Sensoren geschrieben, gelesen und gelöscht werden.- The information can be obtained using optical methods (e.g. laser) or magnetic sensors can be written, read and deleted.
- - Die hier vorgestellte Erfindung bedeutet einen enormen Fortschritt im Hinblick auf die beiden in der Literatur beschriebenen Methoden, einen durch Licht induzierten Spinwechsel in Spincrossover-Verbindungen zu erreichen: zum einen das "Light Induced Excited Spin State Trapping (LIESST)", das bei tiefen Temperaturen erfolgt (Chem. Phys. Lett. 105 (1984)1) und zum anderen der "Ligand Driven Light Induced Spin Change (LD-LISC; EP 570292 1993), der in "soft liquid" oder polymeren Medien, aber nicht im Festkörper stattfindet. Die Verbindungen im letzteren Fall nutzen eine cis-trans Isomerisierung von 1,2-Diaryläthylen, das einen sehr geringen photochromen Effekt zeigt und zu einer unvollständigen Photokonversion führt. In unserem Fall findet der Effekt im Festkörper statt und zeigt sich durch eine kräftige Änderung der Farbe und der magnetischen Suszeptibilität des Materials.- The invention presented here means an enormous advance in terms to the two methods described in the literature, one by light to achieve induced spin changes in spin crossover connections: to the "Light Induced Excited Spin State Trapping (LIESST)", which at low temperatures (Chem. Phys. Lett. 105 (1984) 1) and the other the "Ligand Driven Light Induced Spin Change (LD-LISC; EP 570292 1993), that in "soft liquid" or polymeric media, but not in the solid state takes place. The compounds in the latter case use a cis-trans Isomerization of 1,2-diarylethylene, which is a very low photochromic Shows effect and leads to an incomplete photoconversion. In our In this case, the effect takes place in the solid and is shown by a strong one Change in color and magnetic susceptibility of the material.
- - Entwicklung von lichtempfindlichen logischen Schaltkreisen- Development of light sensitive logic circuits
- - opto-magnetische Speicherung und Aufnahme (magnetische Abbildung von optischen Objekten)- Opto-magnetic storage and recording (magnetic imaging of optical objects)
- - Speicherung von binären Informationen (Computerspeicher) Flexible Speichermedien- Storage of binary information (computer memory) Flexible storage media
- - organische elektrische Kreisläufe mit "distributed" Parametern- organic electrical circuits with "distributed" parameters
- - Möglichkeit holographische Informationen zu speichern- Possibility to save holographic information
Das unten skizzierte Schema zeigt einen lichtempfindlichen Schaltkreis, der die
Verbindung der hier vorgestellten Erfindung benutzt. Der Schwingkreis besteht aus
einer Induktion L, der Kapazität C und dem Widerstand R. Der Kern der
Resonanzspule enthält die Verbindung der Erfindung. Wird der Spulenkern mit Licht
bestrahlt, erfolgt eine Änderung der Suszeptibilität damit einher geht eine Änderung
der Resonanzfrequebz
The diagram outlined below shows a photosensitive circuit using the connection of the invention presented here. The resonant circuit consists of an induction L, the capacitance C and the resistor R. The core of the resonance coil contains the connection of the invention. If the coil core is irradiated with light, the susceptibility changes, which is accompanied by a change in the resonance frequency
und der Impedanz
and the impedance
bei einer Frequenz
des Kreises. Solch eine Einheit kann als Grundelement für Speichereinheiten oder
Lichtsensoren eingesetzt werden. Prinzipiell können alle Teile einer solchen Einheit auf
der molekularen Ebene verwirklicht werden.
at a frequency of the circle. Such a unit can be used as a basic element for storage units or light sensors. In principle, all parts of such a unit can be realized at the molecular level.
Die Synergie bei Spinübergängen wird Thema zukünftiger Forschung sein.The synergy in spin transitions will be the subject of future research.
Claims (5)
wobei X die Elemente bzw. Gruppen H, F, Cl, J, Br, OH, NO2, CnH2n+1 oder CnH2n-X und ε ein stark elektroaktiver Substituent E oder der Rest R sein kann, wobei R einer der nachfolgenden Substituenten bzw. Kombinationen derselben
sein können und Φ eine chemische Gruppe darstellt, die im Liganden selbst vorhanden sein kann. 2. Coordination compounds according to claim 1, characterized in that the photochromic ligands can have the following structure:
where X can be the elements or groups H, F, Cl, J, Br, OH, NO 2 , C n H 2n + 1 or C n H 2n -X and ε can be a strongly electroactive substituent E or the radical R, where R is one of the following substituents or combinations thereof
and Φ represents a chemical group that may be present in the ligand itself.
- - Umsetzung von 2-Methyl-3-bromo5-substituierten Thiophenen mit n-BuLi in THF bei minus 80°C
- - Zusatz von einem halben Äquivivalent Perfluorocyclopenten zu diesen Lithium Thiophenenen bei minus 80°C
- - Die Addition-Elimination-Reaktion ergeben die 1,2- Dithiophenylpertluorocyclopentene
- - Reaction of 2-methyl-3-bromo5-substituted thiophenes with n-BuLi in THF at minus 80 ° C
- - Add half an equivalent of perfluorocyclopentene to these lithium thiophenenes at minus 80 ° C
- - The addition-elimination reaction gives the 1,2-dithiophenylpertluorocyclopentenes
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| DE2000139903 DE10039903A1 (en) | 2000-08-16 | 2000-08-16 | Novel transition metal co-ordination compounds with heterocyclic-substituted bis-(thien-3-yl)perfluorocyclopoentene photochromic ligands are useful in the solid state at room temperature in e.g. opto-magnetic switches |
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| DE2000139903 DE10039903A1 (en) | 2000-08-16 | 2000-08-16 | Novel transition metal co-ordination compounds with heterocyclic-substituted bis-(thien-3-yl)perfluorocyclopoentene photochromic ligands are useful in the solid state at room temperature in e.g. opto-magnetic switches |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004003107A1 (en) * | 2002-06-28 | 2004-01-08 | Qinetiq Limited | Potochromic liquid crystals |
| DE10242435A1 (en) * | 2002-09-11 | 2004-03-25 | Heinrich-Heine-Universität Düsseldorf | Photochromic polymer compositions, useful e.g. as light protectants or data storage components, based on 1,2-bis-((hetero)aryl)-cycloalkene or bis-(cyclo(hetero)alkeno)-cyclohexa-2,6-diene derivatives |
| WO2012022299A1 (en) * | 2010-08-16 | 2012-02-23 | Christian-Albrechts-Universität Zu Kiel | Molecular switch |
| CN108102106A (en) * | 2017-12-06 | 2018-06-01 | 陕西科技大学 | A kind of photochromic fibre element and preparation method thereof |
-
2000
- 2000-08-16 DE DE2000139903 patent/DE10039903A1/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004003107A1 (en) * | 2002-06-28 | 2004-01-08 | Qinetiq Limited | Potochromic liquid crystals |
| US7416682B2 (en) | 2002-06-28 | 2008-08-26 | Chi Mei Optoelectronics Corporation | Photochromic liquid crystals |
| DE10242435A1 (en) * | 2002-09-11 | 2004-03-25 | Heinrich-Heine-Universität Düsseldorf | Photochromic polymer compositions, useful e.g. as light protectants or data storage components, based on 1,2-bis-((hetero)aryl)-cycloalkene or bis-(cyclo(hetero)alkeno)-cyclohexa-2,6-diene derivatives |
| WO2012022299A1 (en) * | 2010-08-16 | 2012-02-23 | Christian-Albrechts-Universität Zu Kiel | Molecular switch |
| US9786420B2 (en) | 2010-08-16 | 2017-10-10 | Christian-Albrechts-Universität Zu Kiel | Molecular switch |
| CN108102106A (en) * | 2017-12-06 | 2018-06-01 | 陕西科技大学 | A kind of photochromic fibre element and preparation method thereof |
| CN108102106B (en) * | 2017-12-06 | 2021-02-26 | 陕西科技大学 | Photochromic cellulose and preparation method thereof |
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