WO2015162026A1 - Matière pour le marquage d'objets, de substances ou de mélanges de substances - Google Patents

Matière pour le marquage d'objets, de substances ou de mélanges de substances Download PDF

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Publication number
WO2015162026A1
WO2015162026A1 PCT/EP2015/057953 EP2015057953W WO2015162026A1 WO 2015162026 A1 WO2015162026 A1 WO 2015162026A1 EP 2015057953 W EP2015057953 W EP 2015057953W WO 2015162026 A1 WO2015162026 A1 WO 2015162026A1
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Prior art keywords
compound
groups
spectrum
group
emission
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PCT/EP2015/057953
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German (de)
English (en)
Inventor
Mathias Mydlak
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Cynora Gmbh
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Priority to DE112015001925.1T priority Critical patent/DE112015001925B4/de
Publication of WO2015162026A1 publication Critical patent/WO2015162026A1/fr

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Definitions

  • the invention relates to the use of a material (a chemical substance or substance mixture) for marking objects, substances or substance mixtures, wherein the material has a first compound with a characteristic spectrum, and a method for marking objects substances or mixtures, comprising a first compound with a characteristic spectrum.
  • a forgery-proof identification of an object, substance or substance mixture is becoming more and more important. Particularly in the case of high-priced and security-relevant products, traceability and unambiguous identifiability are very important.
  • counterfeit-proof marking of value or security documents such as banknotes, shares, certificates, identity cards, etc. or contracts is important.
  • the forgery-proof marking of gases, liquids, powders, medicines or food, for example, for tracing has a high priority.
  • the invention relates to the use of a material for the counterfeit-proof marking of objects, substances and mixtures of substances.
  • the material has a first compound with a characteristic spectrum.
  • the spectrum is selected from the group consisting of emission, absorption, reflection and transmission spectrum.
  • the tagging is in one embodiment via a single one of these spectra.
  • the marking is made over or two or more (three, four, five, etc.) of these spectra.
  • the first compound is a first emitter that emits detectable light upon electronic excitation.
  • the material has a second connection in addition to the first connection.
  • the second compound is structurally different from the first compound and in particular has a different absorption and / or reflection and / or transmission and / or emission behavior than the first compound. This results in a suitable absorption of the material, a complex absorption and / or reflection and / or transmission and / or Emission spectrum from the combination of the absorption and / or reflection and / or transmission and / or emission spectrum of the first compound with the absorption and / or reflection and / or transmission and / or emission spectrum of the second compound.
  • the material comprises, in addition to the first compound and optionally a second compound, a third compound or further compounds (additive (s), host) which exhibit the absorption and / or reflection and / or transmission and / or emission behavior influence the first connection and / or the optional second connection.
  • a third compound or further compounds additive (s), host
  • Influences in the sense of the invention are: addition of a further emission band; Reducing the intensity of one or more emission bands; Lowering the photoluminescent quantum yield of one or more compounds of the material, lengthening and / or shortening the excited state lifetime of all compounds of the material, producing new absorption bands of the material; Reinforcement of individual absorption bands of the material; Generation or attenuation of reflection bands of the material; Attenuation and / or amplification of individual reflection bands of the material (in each case based on the meterial consisting of the first compound and possibly the second compound).
  • individual and forgery-proof photoluminescence spectra can be provided.
  • Suitable additives are organic materials that are used in OLEDs as HOST or transport materials, such as. Tris (4-carbazoyl-9-ylphenyl) amine (TCTA), 1,3,5-tri (1-phenyl-1H-benzo [d] imidazol-2-yl) -phenyl (TPBi), polymethyl methacrylate (PMMA ), Bathocuproine (BCPO), 2,6-dicarbazolo-1, 5-pyridine (PYD2).
  • the additives are characterized by a particular absorption spectrum and thus produce characteristic absorption (and / or reflection and / or transmission) and / or emission spectra in a mixture with an emitter for this individual mixture. In this way, by combining an emitter with further emitters and / or optionally an additive, it is possible to obtain characteristic and thus exclusive spectra for a large number of different users.
  • the first compound and / or the second compound is an emitter that emits detectable light upon electronic excitation.
  • the first compound and / or the second compound is a transition metal complex (emitter), in particular a complex which exhibits the singlet harvesting effect, in particular, a copper complex, for example a copper (I) complex, in particular comprising one or consisting of a structure according to formula A.
  • a transition metal complex emitter
  • a copper complex for example a copper (I) complex, in particular comprising one or consisting of a structure according to formula A.
  • ⁇ * is a chelating N-heterocyclic ligand which binds to the Cu 2 X 2 nuclei via a nitrogen atom and either a phosphorus, arsenic or antimony atom, and L independently represents a phosphane, arsine or Antimony ligands, wherein both ligands L may also be connected to each other, so that a divalent ligand results, or wherein a ligand L or both ligands L may also be connected to ⁇ *, so that there is a trivalent or diminufitiger ligand.
  • dinuclear copper (I) complexes of the formula A are represented by the complexes of the formulas I to IV and explained below.
  • X * or X CN, SCN, N 3 and / or in particular Cl, Br and / or I (ie independently of one another, so that the complex can have two identical or two different groups X * or X),
  • the imine function is part of an aromatic or heteroaromatic group (eg pyridyl, pyrimidyl, Pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole or thiatriazole, etc.) which is optionally further substituted or fused.
  • "N” is also part of this aromatic group. The carbon atom is located both directly adjacent to the imine nitrogen atom and to the E atom.
  • D independently P and / or As and / or Sb.
  • Each R independently represents hydrogen, halogen or substituents which are bonded via oxygen (-OR), nitrogen (-NR 2 ) or silicon atoms (-SiR 3 ) and also alkyl (also branched or cyclic), heteroalkyl, aryl , Heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), Heteroalkyl, aryl, heteroaryl and other well known donor and acceptor groups such as amines, carboxylates and their esters, and CF 3 groups.
  • the radicals R optionally also lead to annelated ring systems.
  • B is a bridge whereby a radical D is connected to another radical D, wherein the bridge B is in particular an alkylene or arylene group or a combination of both, or -O-, -NR- or -SiR 2 -.
  • ⁇ * ⁇ and / or L are optionally substituted, in particular with groups which increase the solubility of the copper (I) complex in common organic solvents.
  • Common organic solvents include, in addition to alcohols, ethers, alkanes and halogenated aliphatic and aromatic hydrocarbons and alkylated aromatic hydrocarbons, especially toluene, chlorobenzene, dichlorobenzene, mesitylene, xylene, tetrahydrofuran, phenetole, propiophenone.
  • the compound used in the process according to the invention is a copper (I) complex of the formula I or III.
  • the first compound present in the material and / or the optionally present second compound is an emitter comprising a compound according to formula V or consisting of a compound according to formula V:
  • LBL is a neutral, bidentate ligand.
  • R 1, R 2 can each independently be hydrogen, halogen or deuterium or substituents which are bonded via oxygen (--OR '''), nitrogen (-NR'' 2 ) or silicon atoms (-SiR'' 3 ) and alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups, such as for example, amines, carboxylates and their esters, and CF 3 groups, which is connected via a bridge B with another radical L and thus forms a bid
  • Z1-Z7 consists of N or the fragment CR
  • R organic radical which is selected from the group consisting of: hydrogen, halogen or deuterium or groups which have oxygen (-OR '''), nitrogen (-NR'' 2 ), silicon (-SiR') " 3 ) or phosphorus atoms (-PR '" 2) are bonded and alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), aryl , Heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups such as amines, carboxylates and their esters, and CF 3 groups,
  • X is either CR '" 2 or NR'".
  • Y is either O, S or NR '".
  • R " is a sterically demanding substituent, especially in the ortho position to the coordination site, which prevents a geometry change in the direction of planarization of the complex in the excited state
  • a complex according to the invention may also have no or only one radical R".
  • R '' organic radical which is selected from the group consisting of: hydrogen, halogen or deuterium, and also alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl or substituted alkyl radicals. (also branched or cyclic), aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups, such as amines, carboxylates and their esters , and CF 3 groups •
  • the complex optionally has a functional group (FG). It is another substituent that introduces an additional function into the complex that would otherwise not be present.
  • the functional groups FG are attached either directly or via suitable bridges (see below) to the NHL substituents.
  • It can either be a group with properties of an electron conductor.
  • It may be a group having properties of a hole conductor.
  • It can be a group that determines the solubility of the complex.
  • in formula V Z1 to Z3 is N.
  • the first compound present in the material and / or the optionally present second compound is a complex comprising a compound according to formula VI or consisting of a compound according to formula VI.
  • LHL is a singly negatively charged bidentate ligand.
  • the ligand ⁇ is a substituted diimine ligand, in particular substituted 2,2'-bipyridine derivatives (bpy) or 1, 10-phenanthroline derivatives (phen).
  • R is a sterically demanding substituent in the 3,3'-position (bpy) or 2,9-position (phen), which prevents a geometry change in the direction of planarization of the complex in the excited state.
  • alkyl and aryl radicals may also be substituted (eg with halogens, alkoxy or silane groups, etc.) or to lead annulated ring systems.
  • two radicals A are shown in formula A, in one embodiment of the invention a complex according to the invention may also have only one radical R.
  • FG functional group is another substituent that introduces an additional function into the complex that would otherwise not be present.
  • the functional groups FG are attached either directly or via suitable bridges to the diimine substituents.
  • It may be a group having properties of a hole conductor.
  • It can be a group that determines the solubility of the complex.
  • the first compound present in the material and / or the optionally present second compound is a purely organic emitter which has no metal atom or metal ion.
  • organic emitters such as anthracene and rhodamine-6 in particular organic molecules of formula VII are suitable as rei mitter.
  • (Het) Ar a conjugated organic group which is selected from the group consisting of unsubstituted and substituted aromatic, heteroaromatic and conjugated double bonds fixed against cis-trans isomerization,
  • A a chemically bonded acceptor group with electron-withdrawing property
  • D are bound to directly adjacent atoms of the conjugated organic group (Het) Ar.
  • donors are aromatics and heteroaromatics, which either show inherent electron-donating properties and / or are substituted with electron-donating groups, as well as other donors linked directly to the central pi system (aromatic or heteroaromatic).
  • acceptors are aromatics and heteroaromatics, which either show inherently electron-withdrawing properties and / or are substituted by electron-withdrawing groups, as well as other acceptors directly linked to the central pi system (aromatic or heteroaromatic).
  • Acceptors can be:
  • the organic emitter has a phenyl ring as a central ⁇ system (formula VIII).
  • At least one of the two substituents (ie donor and / or acceptor) of the central repeat unit comprises a heteroatom X via which the substituent is bonded to the central repeat unit (the pi system).
  • the heteroatom X is independently selected from the group consisting of N, S, P, O and Se.
  • both substituents are linked to the central repeat unit (the pi system) via a heteroatom X (each independently) selected from the group consisting of N, S, P, O, and Se.
  • the organic emitter is a molecule according to formula IX:
  • NRR 1 is a donor (corresponding to D from formula VII or formula VIII), wherein R, R 1 are independently selected from the group consisting of hydrogen, halogen or substituents which are directly or via oxygen (-OR), nitrogen (-) NR 2 ), silicon (-SiR 3 ) or via sulfur atoms (-SR) are bonded and alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl (linear, branched or cyclic), heteroalkyl, aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (linear, branched or cyclic), heteroalkyl, aryl, heteroaryl groups, and other generally known donor groups. and acceptor groups such as amines, alcohol and ether groups, carbonyl groups, carboxylates and their esters, nitriles, and CF 3 groups.
  • the radicals R optionally also lead to fused ring systems.
  • acceptors are SO 2 R, SO 2 (OR), S (O) R, P (O) RR ', P (O) (OR) (OR'), P (O) R (OR '), Se0 2 R and Se (0) R.
  • the radicals R optionally also lead to fused ring systems.
  • Ar and Ar 1 can also be fused together or linked together via a unit E (eg carbazole, phenoxazine);
  • E represents a direct bond or an organic bridge containing a substituted or unsubstituted alkylene, alkenylene, alkynylene or arylene group or a combination of these, or -O-, -NR-, -SiR 2 -S- , -S (O) -, -S (O) 2 -, interrupted by O alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl, alkenyl groups, phenyl and substituted phenyl moieties, each R is independently selected from the group consisting of hydrogen, halogen or substituents which are bonded directly or via oxygen (-OR), nitrogen (-NR 2 ) silicon (-SiR 3 ) or via sulfur atoms (-SR) and also al
  • the radicals R can optionally also lead to fused ring systems.
  • Ar may also be fused to other aryl and heteroaryl groups and thus give larger aromatic systems (eg, phenyl, naphthyl, antracenyl, tolyl, etc.).
  • the organic emitter is a molecule according to formula XI:
  • R 1 -R 17 each independently selected from the group consisting of hydrogen, halogen and substituents which are directly or via oxygen (-OR), nitrogen (-NR 2 ), silicon (-SiR 3 ) or sulfur ( -SR) and wherein for the radicals R corresponds to the definition given for the formula D for R, as well as alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl - (also branched or cyclic), heteroalkyl, aryl, heteroaryl and alkenyl groups (with substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), heteroalkyl, aryl, heteroaryl groups), and other well-known donor and acceptor groups, such as, for example, amines, alcohol and ether groups, carbonyl groups, carboxylates and their esters, nitriles, and CF 3 groups, which are optional
  • the first emitter is combined with further emitters and / or hole or electron conductors and / or host materials such as, for example
  • the present invention also relates to a method of marking substances / mixtures (such as gases, liquids, powders, foods) or articles using a material comprising a first compound having a characteristic spectrum.
  • the spectrum is selected from the group consisting of emission, absorption, reflection and transmission spectrum.
  • the first compound is a first emitter that emits detectable light upon electronic excitation.
  • the material has a second compound which is structurally different from the first compound and in particular has a different absorption and / or reflection and / or transmission and / or emission behavior than the first compound.
  • a complex absorption and / or reflection and / or transmission and / or emission spectrum results from the combination of the absorption and / or reflection and / or transmission and / or emission spectrum of the first compound with the absorption and / or or reflection and / or transmission and / or emission spectrum of the second compound.
  • the material in addition to the first compound and optionally a second compound, has a third compound or several further compounds which exhibit the absorption and / or reflection and / or transmission and / or emission behavior of the first compound and / or the optionally influence existing further connections.
  • Suitable additives include compounds having conjugated double bonds, in particular aromatic and heteroaromatic structures whose absorption and emission is in the range between 200 nm and 1200 nm, such as, for example, organic materials which are used in OLEDs as HOST or transport materials, such as tris (4 -carbazoyl-9-ylphenyl) amine (TCTA), 1, 3,5-tri (1-phenyl-1H-benzo [d] imidazol-2-yl) -phenyl (TPBi), polymethylmethacrylate (PMMA), BCPO, 2 , 6-dicarbazolo-1, 5-pyridine (PYD2).
  • the additives are characterized by a particular absorption spectrum and thus produce characteristic absorption and / or reflection and / or transmission and emission spectra in a mixture with a first or second compound for this individual mixture.
  • the second emitter can quench or attenuate the emission of the first emitter, so that the quantum yield (PL) does not add up, but is characteristic of the respective mixture.
  • PL quantum yield
  • Such mixture-characteristic quenching or attenuation may also occur with a mixture of an emitter with a host.
  • the method according to the invention comprises the step of applying the material comprising the first and / or second compound having a characteristic spectrum to an object to be marked.
  • This application can be carried out in particular as a coating (for example by means of slot casting (in particular planar), dip-coating (in particular flat), inkjet (in particular punctiform)), by means of common printing processes (eg by means of flexographic printing, screen printing, etc.). ), but also other techniques of application, such as dry coating with the powder by means of a brush and subsequent covering for protection, application as paste, etc. are possible.
  • a punctual application even as a pattern, such as a barcode or QR code, possible.
  • the object to be identified may be a value document or a security document.
  • Value documents and security documents are in particular official and governmental documents (eg identity cards, banknotes, stamps, visas, ballot papers, certificates, etc.) or bank and financial papers (eg shares, contracts, etc.) or all other papers or documents containing a material value that exceeds the mere material value or has security-relevant value.
  • the material applied to the object to be marked is protected by a, in particular transparent, protective layer from the outside, the absorption, Protected factors influencing reflection, transmission and emission behavior.
  • This layer serves, for example, to protect against oxygen, from UV degradation, from water, from reactive atmospheres, from solvents, from mechanical erosion, etc.
  • the protective layer can also be formed as a removable cover (cap or protective sticker).
  • the material comprising the first and / or second compound having a characteristic spectrum is surrounded by an encapsulation, which is transparent in particular at the top and is optionally self-adhesive at the bottom, so that the material according to the invention acts like a sticker on one can be applied to the object to be marked.
  • the material admixed to the substance or substance mixture to be marked is surrounded by a, in particular transparent, protective layer, for example in the form of a nanocapsule.
  • the nanocapsules consist in particular of metal oxides or polymers. Such nanometer sized capsules enclose only a few molecules of the first and / or second compound, providing shielding from electronic and environmental influences.
  • the nanocapsules and the marking materials contained therein are shaped to decompose at a particular temperature. If the decomposition takes place at high temperature (for example 75 ° C.), such nanocapsules would be destroyed during cooking of the foodstuffs and thus could, for example, also be an indicator for complete overheating of the food, in addition to the counterfeit-proof marking.
  • the use of nanocapsules which already decompose at a lower temperature is suitable, for example, for controlling the cold chain in foods or medicaments.
  • the inventive method also has the determination of at least one photophysical parameter as the reference parameter of the material.
  • the parameter can be compared, which was determined in particular by light detection of material applied to an object. If the measured parameter and the reference parameter are identical, this leads to the conclusion that the article is an original product. If the measured parameter and the reference parameter are not identical, this indicates that the item is not an original product.
  • This photophysical parameter is in particular selected from the group consisting of emitted wavelength, shape of the absorption and / or reflection and / or transmission spectrum, shape of the emission spectrum, Photoluminescence quantum efficiency, excited state lifetime and CIE coordinates (coordinates according to the CIE standard color system).
  • the method according to the invention may comprise the step of excitation of the material by means of an excitation unit and the detection of the emitted light with a detection unit.
  • the excitation takes place in particular by means of UV light, by heating, by X-radiation, by means of radioactive radiation or by means of an electric field, wherein the excitation unit and / or the detection unit is designed in particular portable.
  • the materials according to the invention are irradiated in the near UV (wavelength 380 to 315 nm).
  • the excitation unit and the detection unit are combined in one device, in particular accommodated in a common housing, so that only one device has to be used for excitation and detection.
  • encoding is by one spectrum and not by the use of two materials having two different luminescence decay times.
  • the identification of the marked object takes place via the emission spectrum.
  • the light source used is an LED (eg NanoLED) with an excitation wavelength in the UV range (250 to 350 nm) for blue emitters.
  • the excitation wavelength in the UV range (250 to 350 nm) for blue emitters.
  • longer-wave light up to the blue range is also possible.
  • a higher energy than the emission energy is used for the excitation (with the exception of potential upconversion in the layer or two-photon absorption in the case of high-power excitation, such as with lasers).
  • the identification takes place via the reflection spectrum.
  • a light source then serves a white light source such.
  • a spectrometer known in the art may be used.
  • the spectrometer measures the spectrum and compares it to a spectrum stored for the user for a given marked item (reference spectrum). If they match the reference spectrum, a positive signal is given (eg green LED lights up), if there is no match with the reference spectrum, a negative signal is given (eg red LED lights up on the device).
  • both types can be measured sequentially and / or optionally the intensities of the respective spectra (absorption vs. emission) can be used to determine a quantum yield and these can be used as a further characteristic.
  • the emitted light is analyzed for at least one, in particular two characteristic parameters, such. B. emitted wavelength, shape of the spectrum, quantum efficiency, lifetime of the excited state or CIE coordinates.
  • the method according to the invention comprises the comparison of at least one, in particular at least two, of the characteristic parameters of the emitted light determined by means of the detector with the respective previously determined reference parameters.
  • the comparison it is possible to infer whether the material whose parameters of the light emitted after excitation were determined by means of the detector is the same material as that for which the reference values were determined.
  • a program for comparing the measured parameters with predefined reference parameters can be integrated into the detector so that it is possible to read directly at the detector whether or not the measured values correspond to the respective predetermined reference parameter (s).
  • all possible compounds having a characteristic spectrum can be used in the process according to the invention, in particular emitters.
  • a low emission quantum yield or a long emission lifetime generally does not argue against use in the method according to the invention.
  • the method according to the invention is based solely on the absolute value of the parameters for comparison with the respective reference parameters and not on, for example the emission quantum yield is particularly high or a particularly short emission lifetime is present, as is the case with the suitability of the compounds as emitters in optoelectronic devices, for example in OLEDs.
  • the first and / or second compounds having a characteristic spectrum used in the method according to the invention are a transition metal complex, for example a complex in which the singlet harvesting Effect is present, in particular a copper complex, preferably a copper (I) complex, in particular having or consisting of a structure according to formula A.
  • a transition metal complex for example a complex in which the singlet harvesting Effect is present, in particular a copper complex, preferably a copper (I) complex, in particular having or consisting of a structure according to formula A.
  • ⁇ * represents a chelating N-heterocyclic ligand which binds to the Cu 2 X 2 nucleus via a nitrogen atom and either a phosphorus, arsenic or antimony atom
  • L independently represents a phosphane, arsine or antimony Ligands, where both ligands L may also be linked together to give a divalent ligand, or wherein a ligand L or both ligands L may also be connected to ⁇ * to give a trivalent or tetravalent ligand.
  • dinuclear copper (I) complexes of the formula A are represented by the complexes of the formulas I to IV and explained below.
  • X * or X CN, SCN, N 3 and / or in particular Cl, Br and / or I (ie independently of one another, so that the complex can have two identical or two different groups X * or X)
  • the imine function is part of an aromatic or heteroaromatic group (eg pyridyl, pyrimidyl, Pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole or thiatriazole, etc.) which is optionally further substituted or fused.
  • "N” is also part of this aromatic group. The carbon atom is located both directly adjacent to the imine nitrogen atom and to the E atom.
  • D independently P and / or As and / or Sb.
  • Each R independently represents hydrogen, halogen or substituents which are bonded via oxygen (-OR), nitrogen (-NR 2 ) or silicon atoms (-SiR 3 ) and also alkyl (also branched or cyclic), heteroalkyl, aryl , Heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), Heteroalkyl, aryl, heteroaryl and other well known donor and acceptor groups such as amines, carboxylates and their esters, and CF 3 groups.
  • the radicals R can optionally also lead to fused ring systems.
  • B is a bridge whereby a radical D is connected to another radical D, wherein the bridge B is in particular an alkylene or arylene group or a combination of both, or -O-, -NR- or -SiR 2 -.
  • ⁇ * ⁇ and / or L are optionally substituted, in particular with groups which increase the solubility of the copper (I) complex in common organic solvents.
  • Common organic solvents include, in addition to alcohols, ethers, alkanes and halogenated aliphatic and aromatic hydrocarbons and alkylated aromatic hydrocarbons, especially toluene, chlorobenzene, dichlorobenzene, mesitylene, xylene, tetrahydrofuran, phenetole, propiophenone.
  • the first and / or second compound used in the method according to the invention is a copper (I) complex of the formula I or III.
  • the first and / or second compound used in the process according to the invention is a complex comprising a compound according to formula V or consisting of a compound according to formula V:
  • LBL is a neutral, bidentate ligand.
  • R1, R2 are each independently hydrogen, halogen or deuterium, or may be substituents on oxygen (-OR ''), nitrogen (-NR ' "2) or silicon atoms (-SiR' '3) are attached as well as alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups with substituents such as halogens or deuterium, Alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups, such as amines, carboxylates and their esters, and CF 3 groups, which is connected via a bridge B with another radical L and thus a bidentate Ligand forms,
  • Z1-Z7 consists of N or the fragment CR
  • R organic radical which is selected from the group consisting of: hydrogen, halogen or deuterium or groups which have oxygen (-OR '''), nitrogen (-NR'' 2 ), silicon (-SiR') " 3 ) or phosphorus atoms (-PR '" 2) are bonded and alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), aryl , Heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups such as amines, carboxylates and their esters, and CF 3 groups,
  • X is either CR '" 2 or NR'".
  • Y is either O, S or NR '".
  • R " is a sterically demanding substituent, especially in the ortho position to the coordination site, which prevents a change in geometry in the direction of planarization of the complex in the excited state
  • the alkyl and aryl groups may also be substituted (eg. as halogens, deuterium, or alkoxy silane groups, etc.) or fused ring systems
  • two radicals R "are shown in formula A in one embodiment of the invention a complex according to the invention may also have no or only one
  • R '' organic radical which is selected from the group consisting of: hydrogen, halogen or deuterium, and also alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl or substituted alkyl radicals. (also branched or cyclic), aryl, heteroaryl and alkenyl groups with substituents such as halogens or deuterium, Alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups, such as amines, carboxylates and their esters, and CF 3 - groups
  • the complex can optionally have a functional group (FG). It is another substituent that introduces an additional function into the complex that would otherwise not be present.
  • the functional groups FG are attached either directly or via suitable bridges (see below) to the NHL substituents.
  • It can either be a group with properties of an electron conductor.
  • It may be a group having properties of a hole conductor.
  • It can be a group that determines the solubility of the complex.
  • in formula V Z1 to Z3 is N.
  • the first and / or second compound used in the process according to the invention is a complex of the formula VI
  • LHL is a singly negatively charged bidentate ligand.
  • the ligand ⁇ is a substituted diimine ligand, in particular substituted 2,2'-bipyridine derivatives (bpy) or 1, 10-phenanthroline derivatives (phen).
  • R is a sterically demanding substituent in the 3,3'-position (bpy) or 2,9-position (phen), which prevents a geometry change in the direction of planarization of the complex in the excited state.
  • alkyl and aryl radicals may also be substituted (eg with halogens, alkoxy or silane groups, etc.) or lead to fused ring systems.
  • two radicals A are shown in formula A, in one embodiment of the invention a complex according to the invention may also have only one radical R.
  • FG functional group is another substituent that introduces an additional function into the complex that would otherwise not be present.
  • the functional groups FG are attached either directly or via suitable bridges to the diimine substituents.
  • It may be a group having properties of a hole conductor.
  • It can be a group that determines the solubility of the complex.
  • the first and / or second compound used in the process is a purely organic emitter which has no metal atom or metal ion.
  • organic molecules of the formula VII are suitable as purely organic emitters.
  • (Het) Ar a conjugated organic group which is selected from the group consisting of unsubstituted and substituted aromatic, heteroaromatic and conjugated double bonds fixed against cis-trans isomerization,
  • A a chemically bonded acceptor group with electron-withdrawing property
  • D are bound to directly adjacent atoms of the conjugated organic group (Het) Ar.
  • donors are aromatics and heteroaromatics, which either show inherent electron-donating properties and / or are substituted with electron-donating groups, as well as other donors linked directly to the central pi system (aromatic or heteroaromatic).
  • Donors can be:
  • acceptors are aromatics and heteroaromatics, which either show in themselves already electron-withdrawing properties and / or are substituted by electron-withdrawing groups and other acceptors, which are linked directly to the central pi system (aromatic or heteroaromatic).
  • Acceptors can be:
  • the organic emitter used in the process has a phenyl ring as the central pi system (formula VIII).
  • At least one of the two substituents (ie donor and / or acceptor) of the central repeat unit comprises a heteroatom X via which the substituent is attached to the central repeat unit (the pi system).
  • the heteroatom X is independently selected from the group consisting of N, S, P, O and Se.
  • both substituents are linked to the central repeat unit (the pi system) via a heteroatom X (each independently) selected from the group consisting of N, S, P, O, and Se.
  • a heteroatom X selected from the group consisting of N, S, P, O, and Se.
  • the organic emitter used in the process according to the invention is a molecule according to formula IX:
  • NRR 1 is a donor (corresponding to D from formula VII or formula VIII), wherein R, R 1 are independently selected from the group consisting of hydrogen, halogen or substituents which are directly or via oxygen (-OR), nitrogen (-) NR 2 ), silicon (-SiR 3 ) or via sulfur atoms (-SR) are bonded and alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), heteroalkyl, aryl, heteroaryl groups, and other well-known donor and acceptor Groups such as amines, alcohol and ether groups, carbonyl groups, carboxylates and their esters, nitriles, and CF 3 groups.
  • the organic emitter used in the process according to the invention is a molecule according to formula X:
  • the radicals R can optionally also lead to fused ring systems.
  • Ar and Ar 1 can also be fused together or linked together via a unit E (eg carbazole, phenoxazine);
  • E represents a direct bond or an organic bridge containing a substituted or unsubstituted alkylene, alkenylene, alkynylene or arylene group or a combination of these, or -O-, -NR-, -SiR 2 -S- , -S (O) -, -S (O) 2 -, interrupted by O alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl, alkenyl groups, phenyl and substituted phenyl moieties, each R is independently selected from the group consisting of hydrogen, halogen or substituents which are bonded directly or via oxygen (-OR), nitrogen (-NR 2 ) silicon (-SiR 3 ) or via sulfur atoms (-SR) and also
  • the radicals R can optionally also lead to fused ring systems.
  • Ar may also be fused to other aryl and heteroaryl groups and thus give larger aromatic systems (eg, phenyl, naphthyl, antracenyl, tolyl, etc.).
  • the organic emitter used in the process according to the invention is a molecule according to formula XI:
  • R 1 -R 17 each independently selected from the group consisting of hydrogen, halogen and substituents which are directly or via oxygen (-OR), nitrogen (-NR 2 ), silicon (-SiR 3 ) or sulfur ( -SR) and wherein for the radicals R corresponds to the definition given for the formula D for R, as well as alkyl (also branched or cyclic), heteroalkyl, aryl, heteroaryl, alkenyl, alkynyl groups or substituted alkyl - (also branched or cyclic), heteroalkyl, aryl, heteroaryl and alkenyl groups (with substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), heteroalkyl, aryl, heteroaryl groups), and other well-known donor and acceptor groups, such as, for example, amines, alcohol and ether groups, carbonyl groups, carboxylates and their esters, nitriles, and CF 3 groups, which are optional
  • Figure 1 Emission spectrum of the emitter A applied as a film.
  • FIG. 2 Reflection spectrum of the pure emitter A.
  • FIG. 3 Absorption spectrum of the pure emitter A.
  • FIG. 4 Transmission spectrum of the pure emitter A.
  • FIG. 5 Emission spectrum of the emitter B applied as a film.
  • FIG. 6 Emission spectrum of the emitter C applied as a film.
  • FIG. 7 Emission spectrum of the emitter A applied as a film in the organic host I.
  • FIG. 8 Emission spectrum of the emitter B applied as a film in the organic host I.
  • FIG. 9 Emission spectrum of the emitter C applied as a film in the organic host II.
  • the emission spectrum of the emitter A applied as a film is shown in FIG.
  • the reflection spectrum of the pure emitter A is shown in FIG. 2, the absorption spectrum of the pure emitter A is shown in FIG. 3, and the transmission spectrum of the pure emitter A is shown in FIG.
  • the emission spectrum of the emitter B applied as a film is shown in FIG.
  • the emission spectrum of the emitter A as a film deposited in the organic host I is shown in FIG.
  • the emission spectrum of the emitter B as a film deposited in the organic host I is shown in FIG.
  • the emission spectrum of the emitter C as a film deposited in the organic host II is shown in FIG.

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Abstract

L'invention concerne l'utilisation d'une matière pour le marquage d'objets, de substances ou de mélanges de substances, la matière comportant un premier composé ayant un spectre caractéristique, ainsi qu'un procédé de marquage d'objets, de substances ou de mélanges de substances présentant l'application de la matière citée.
PCT/EP2015/057953 2014-04-24 2015-04-13 Matière pour le marquage d'objets, de substances ou de mélanges de substances WO2015162026A1 (fr)

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EP2993176A1 (fr) * 2014-09-02 2016-03-09 cynora GmbH Complexes metal(i) pour une meilleure conductivite
WO2023163533A1 (fr) * 2022-02-23 2023-08-31 삼성디스플레이주식회사 Molécule organique pour dispositif optoélectronique

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DE10322794A1 (de) * 2003-05-19 2004-12-23 Bundesdruckerei Gmbh Sensor für die Echtheitserkennung eines lumineszierenden Sicherheitselements eines Wertdokuments, Wertdokument sowie Verfahren zur Herstellung eines Wertdokuments
DE102007063051A1 (de) * 2007-12-28 2009-07-02 Heinz Prof. Dr. Langhals Fluoreszenzmarkierungen durch die "Click-Reaktion". Anwendung der 1,3-dipolaren Cycloaddition
CN101987931A (zh) * 2010-11-03 2011-03-23 北京赛腾工业标识系统有限公司 高固体份耐高温环保喷码打印油墨
EP2308929A1 (fr) * 2005-07-01 2011-04-13 3DTL, Inc. Systèmes et procédés pour créer des effets optiques sur des supports pour prévenir la contrefaçon
WO2013007710A1 (fr) * 2011-07-08 2013-01-17 Cynora Gmbh Procédé de liaison covalente d'un complexe organométallique à un polymère

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EP2540730A1 (fr) 2011-06-29 2013-01-02 cynora GmbH Complexe de cuivre(I), notamment pour composants optoélectroniques

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DE10322794A1 (de) * 2003-05-19 2004-12-23 Bundesdruckerei Gmbh Sensor für die Echtheitserkennung eines lumineszierenden Sicherheitselements eines Wertdokuments, Wertdokument sowie Verfahren zur Herstellung eines Wertdokuments
EP2308929A1 (fr) * 2005-07-01 2011-04-13 3DTL, Inc. Systèmes et procédés pour créer des effets optiques sur des supports pour prévenir la contrefaçon
DE102007063051A1 (de) * 2007-12-28 2009-07-02 Heinz Prof. Dr. Langhals Fluoreszenzmarkierungen durch die "Click-Reaktion". Anwendung der 1,3-dipolaren Cycloaddition
CN101987931A (zh) * 2010-11-03 2011-03-23 北京赛腾工业标识系统有限公司 高固体份耐高温环保喷码打印油墨
WO2013007710A1 (fr) * 2011-07-08 2013-01-17 Cynora Gmbh Procédé de liaison covalente d'un complexe organométallique à un polymère

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2993176A1 (fr) * 2014-09-02 2016-03-09 cynora GmbH Complexes metal(i) pour une meilleure conductivite
WO2023163533A1 (fr) * 2022-02-23 2023-08-31 삼성디스플레이주식회사 Molécule organique pour dispositif optoélectronique

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