CN101072842A - Fluorescent diketopyrrolopyrroles - Google Patents

Fluorescent diketopyrrolopyrroles Download PDF

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Publication number
CN101072842A
CN101072842A CN200580042191.7A CN200580042191A CN101072842A CN 101072842 A CN101072842 A CN 101072842A CN 200580042191 A CN200580042191 A CN 200580042191A CN 101072842 A CN101072842 A CN 101072842A
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Prior art keywords
alkyl
group
phenyl
replaces
aryl
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H·雅马莫托
H·奥卡
M·杜格利
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/004—Diketopyrrolopyrrole dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

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Abstract

The present invention relates to fluorescent diketopyrrolopyrroles of the formula (I), or (III), a process for their preparation and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, in solid dye lasers, EL lasers and electroluminescent devices. A luminescent device comprising a compound, or composition according to the present invention is high in the efficiency of electrical energy utilisation and high in luminance.

Description

Fluorescent diketopyrrolopyrroles
The present invention relates to the fluorescent diketopyrrolopyrroles (DPP) of following formula:
Figure A20058004219100221
Or
Figure A20058004219100222
Its preparation method, and at preparation printing ink, tinting material, coloured plastics, coating, non-back-strike print material, colour filter, makeup, polymkeric substance printing ink particle, toning agent (toner), as fluorescent tracer, the purposes in variable color medium, solid-state dye laser, EL laser apparatus and electroluminescent (EL) device.The luminescent device that comprises The compounds of this invention has high utilization rate of electrical and high radiance.
EP-A-648770 relates to the DPP that contains carbamate groups and as the purposes of fluorescence dye.Following compounds is disclosed respectively in embodiment 6 and 9:
Figure A20058004219100223
With
Figure A20058004219100224
Except other DPP compound, WO90/01480 relates to the material with at least two kinds of painted forms of difference, and wherein a kind of painted form can change into another kind of painted form by supplementing energy, and the application in storage media.Following DPP compound is disclosed respectively in embodiment 10 and 11:
Figure A20058004219100231
With
Figure A20058004219100232
Generally be to prepare electroluminescent (" the EL ") device that comprises organic fluorescent substance at present by vacuum evaporation method, for example at Appl.Phys.Lett., 51,913 (1987) the middle methods of describing.Usually,, adopt two kinds of such vacuum evaporation method: unimodule type method and two-component-type (or " Host-Guest type " or " binary system ") method (for example be described in J.Appl.Phys., 65,3610 (1989) in) according to the structure of luminescent material.
JP-A2 2,296, the claimed a kind of electroluminescent cell of 891 (Ricoh), it comprise positive electrode, negative potential and place positive electrode and negative potential between an organic compound layer or a plurality of organic compound layer, but do not have a hole transport material.One deck at least in the described organic compound layer is to contain formula II " shown in the layer of pyrrolopyrrole compound:
Figure A20058004219100233
Y wherein 1And Y 2Represent replacement or unsubstituted alkyl, cycloalkyl or aryl independently of one another, Y 3And Y 4Represent hydrogen atom or replacement or unsubstituted alkyl or aryl independently, and X represention oxygen atom or sulphur atom.Specifically mentioned four kinds of compounds, in all cases promptly, wherein X represents oxygen, and (a) Y wherein 3=Y 4=methyl, and Y 1=Y 2=p-methylphenyl, (b) Y 3=Y 4=methyl, Y 1=Y 2=hydrogen, (c) Y 3=Y 4=hydrogen, and Y 1=Y 2=p-methylphenyl and (d) Y 3=Y 4=Y 1=hydrogen, and Y 2=rubigan.If only use DPPII ", promptly do not add three (oxine) aluminium (" Alq 3"), do not observe luminous.
JP-A2 5,320, the claimed a kind of organic EL device of 633 (Sumitomo), and described device has luminescent layer, and described luminescent layer comprises the luminescent material of 0.005-15 weight part between pair of electrodes, i.e. DPP shown in the formula I '
Figure A20058004219100241
Wherein at least one electrode is transparent or semitransparent, wherein Y 1And Y 2Represent C independently of one another 6-C 14-aryl or C 6-C 12Heterocyclic radical, for example thienyl, 2-pyridyl, 3-pyridyl and 4-pyridyl, and Y 3And Y 4Represent hydrogen atom, C independently of one another 1-C 12-alkyl or C 6-C 14Aryl.Though mentioning, independent claim do not use Alq 3, but from specification sheets and embodiment, especially from comparing embodiment 2, can obviously find out Alq 3It is the essential features of EL element required for protection or device.
JP-A2 9003448 (Toyo) has described a kind of organic EL, described element has luminescent layer between pair of electrodes, luminescent layer contains the DPP compound as electron transport material, or organic compound thin film layer, this thin film layer comprises luminescent layer and electron injecting layer, and wherein electron injecting layer contains the DPP compound as electron transport material.Wherein clearly mentioned following three kinds of heteroaryl pyrrolopyrrole compounds:
Figure A20058004219100242
With
Figure A20058004219100243
Determining of El element required for protection is according to embodiment, always must use Alq 3With luxuriant and rich with fragrance diamines (as hole-injecting material).
EP-A-499,011 has described electroluminescent device, and this device comprises the DPP compound of following formula
Figure A20058004219100251
Y wherein 1And Y 2Can be to replace or unsubstituted phenyl, 3-pyridyl or 4-pyridyl, and Y 3And Y 4Represent hydrogen atom, C independently of one another 1-C 18-alkyl, C 3-C 18Alkenyl, and two key is in the 1-position.In embodiment 1 and 7, specifically mentioned following DPP compound
Figure A20058004219100252
With
Figure A20058004219100253
The DPP compound that WO98/33862 has described formula IV ' in electroluminescent device as the application of guest molecule
Figure A20058004219100254
The Diketopyrrolo-pyrrole compounds (" DPP ") that the fluorescence N-of relating to property of EP-A-1087005 formula I ' replaces
Figure A20058004219100261
It is characterized in that Y 1And Y 2Derived from following groups:
Figure A20058004219100262
Figure A20058004219100263
Or
Figure A20058004219100264
Described group can be that replace or unsubstituted.
EP-A-1087006 relates to electroluminescent device, it comprises by following order: (a) anode, (b) hole transmission layer, (c) luminescent layer, (d) optional electron transfer layer, (e) negative electrode and luminophore, wherein luminophore is the Diketopyrrolo-pyrrole compounds (" DPP ") by formula I ' representative.
WO 03/002672 relates to the diketopyrrolopyrrolecocrystals of formula I ', it is characterized in that Y 1And Y 2Derived from following 1-naphthyl:
Figure A20058004219100265
WO03/064558 discloses El element, and this device comprises the DPP object chromophoric group of formula IV and the DPP main body chromophoric group (seeing below) of formula II.
EP-A-1,253,151 disclose El element, described device comprises following at least a: (a) DPP derivative and fluorescence peak wavelength are the organic fluorescence materials of 580-720nm and (b) a pyrromethene metal complex (also referring to JP2001 257077, JP2001257078 and JP2001 297881 (Toray)).
WO03/048268 relates to the composition that is used for EL element, and described composition comprises the compound of Ju You perylene ring and has the compound of DPP skeleton.Wherein specifically mentioned following three kinds of heteroaryl pyrrolopyrrole compounds:
Figure A20058004219100271
With
Figure A20058004219100272
Surprisingly, have been found that,, can obtain except high utilization rate of electrical and high radiance, also to have the fluorescent device of high durability especially as luminophore if use the particular combinations of specific DPP compound or DPP compound.
Therefore, the present invention relates to the fluorescent diketopyrrolopyrroles of following formula:
Figure A20058004219100281
Or
Figure A20058004219100282
R wherein 1And R 2Can be identical or different, and be selected from C 1-C 25Alkyl can be by C 1-C 3Alkyl replaces 1-3 time allyl group, can choose wantonly by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time cycloalkyl, is condensed 1 or 2 time cycloalkyl by phenyl, and described phenyl can be by C 1-C 4-alkyl, halogen, nitro or cyano group replace 1-3 time, alkenyl, cycloalkenyl group, alkynyl, heterocyclic radical, haloalkyl, halogenated alkenyl, the halo alkynyl, ketone or aldehyde radical, ester group, formamyl, silyl, siloxy-, aryl, heteroaryl or-CR 3R 4-(CH 2) m-A 3, R wherein 3And R 4Represent hydrogen or C independently of one another 1-C 4Alkyl or phenyl, described phenyl can be by C 1-C 3Alkyl replaces 1-3 time, A 3Represent aryl or heteroaryl, particularly phenyl or 1-or 2-naphthyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, and m represents 0,1,2,3 or 4,
A 1Representative
Wherein
X is N or C-R 8,
R 5-R 11Can be identical or different, and be selected from hydrogen, C 1-C 25Alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether, aryl thioethers base, aryl, heteroaryl, heterocyclic radical, halogen, haloalkyl, halogenated alkenyl, halo alkynyl, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, group NR 27R 28, R wherein 27And R 28Represent hydrogen atom, alkyl, the optional cycloalkyl that replaces, the optional aryl that replaces, the optional heteroaryl that replaces, optional heterocyclic radical, the aralkyl that replaces, perhaps R independently of one another 27And R 28Nitrogen-atoms with their institute's bondings forms 5 or 6 yuan of rings, and described ring can be condensed nitro, silyl, siloxy-, replacement or unsubstituted vinyl, perhaps at least two adjacent substituent R by 1 or 2 optional phenyl that replaces 5-R 11Form aromatics, heteroaromatic or aliphatic series and condense ring system,
A 2Aryl that representative does not replace or replaces or the heteroaryl that does not replace or replace, condition is A 2And A 1Have different implications at same intramolecularly, especially
A 2Represent A 1, condition is A 2And A 1Have different implications, perhaps A at same intramolecularly 2Representative
Figure A20058004219100291
Figure A20058004219100292
Or
Figure A20058004219100293
R wherein 101-R 123Can be identical or different, and be selected from hydrogen, C 1-C 25Alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether, aryl thioethers base, aryl, heterocyclic radical, halogen, haloalkyl, halogenated alkenyl, halo alkynyl, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, group NR 27R 28, R wherein 27And R 28As defined above, nitro, silyl, siloxy-, replacement or unsubstituted vinyl, perhaps at least two adjacent substituent R 115-R 121Form aromatics, heteroaromatic or aliphatic series and condense ring system,
R 124And R 125Can be identical or different, and be selected from C 1-C 18Alkyl; C 1-C 18Alkoxyl group; C 6-C 18Aryl; C 7-C 18Aralkyl; Perhaps R 124And R 125Form ring, especially 5,6 or 7 yuan of rings together, described ring can be chosen wantonly by C 1-C 8Alkyl replaces, and perhaps can choose wantonly by phenyl to condense 1 or 2 time, and described phenyl can be by C 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group replace 1-3 time;
Perhaps A 2Represent heteroaryl, especially
Figure A20058004219100301
Figure A20058004219100302
Or
R wherein 131-R 152Can be identical or different, and be selected from hydrogen, C 1-C 25Alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether, aryl thioethers base, aryl, heterocyclic radical, halogen, haloalkyl, halogenated alkenyl, halo alkynyl, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, group NR 27R 28, R wherein 27And R 28As defined above, nitro, silyl, siloxy-, replacement or unsubstituted vinyl,
R 153The C that is hydrogen atom, can be interrupted by-O- 1-C 25Alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical,
A 4And A 5Has A independently of one another 2Implication, and
A 6Be cycloalkyl, arylidene or heteroarylidene, described group is optional by C 1-C 8-alkyl or C 1-C 8-alkoxyl group replaces 1-3 time, and condition is not comprise following compounds:
Figure A20058004219100311
Figure A20058004219100321
R 1And R 2Can be different, but preferably have identical meanings, and C preferably 1-C 18Alkyl.
In a preferred embodiment of the invention, A 1And A 2In the middle of have at least one to represent the fused aromatic ring system, described ring system contains at least 13 carbon atoms, can be substituted, and carbon atom part can be by heteroatoms, preferred nitrogen or oxo are replaced, for example
Figure A20058004219100331
Figure A20058004219100332
Or
Figure A20058004219100333
If A 1Represent group
Figure A20058004219100341
R wherein 9Be hydrogen, A then 2The preferred group of representing
Figure A20058004219100342
Figure A20058004219100343
Or
Figure A20058004219100344
Or heteroaryl, especially
Figure A20058004219100351
Or
In another preferred embodiment of the present invention, A 1Represent the group of following formula
Figure A20058004219100354
R wherein 25And R 26As defined above, and R 300Be C 1-C 8Alkyl, C 6-C 24Aryl or C 2-C 17Heteroaryl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces; Especially C 1-C 8Alkyl or phenyl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces.In especially preferred embodiment of the present invention, A 1Represent the group of following formula
Figure A20058004219100361
Or
Figure A20058004219100362
In described embodiment, for A 2Be not particularly limited, except itself and A 1Difference, and be
Figure A20058004219100363
Preferably
Figure A20058004219100371
Figure A20058004219100372
Or
Figure A20058004219100373
R wherein 251, R 252, R 254, R 254, R 255And R 256Be C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group, particularly hydrogen.
R 1And R 2Preferably represent C independently of one another 1-C 8Alkyl, C 5-C 12-cycloalkyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, phenyl or 1-or 2-naphthyl, and described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, or-CR 3R 4-(CH 2) m-A 3, R wherein 3And R 4Represent hydrogen or C 1-C 4Alkyl, A 3Represent phenyl or 1-or 2-naphthyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, and m represents 0 or 1, allyl group especially, C 1-C 8Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2 for example, 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl, three (Cr C 8Alkyl) silyl trimethyl silyl for example ,-CH 2-A 3' ,-CHCH 3-A 3Or-CH 2-CH 2-A 3, A wherein 3Represent phenyl, described phenyl can be by C 1-C 8Alkyl replaces 1,2 or 3 time.
Most preferred R 1And R 2Be identical, and represent C 1-C 8Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2 for example, 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl.
If A 1Representative
Figure A20058004219100381
Then for A 2, group
Figure A20058004219100383
Or
Figure A20058004219100384
Be more not preferred.
A 1Preferred representative
Figure A20058004219100391
R wherein 25' be C 6-C 12Aryl, especially phenyl or naphthyl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces,
R 300Be C 1-C 8Alkyl, C 6-C 24Aryl, C 2-C 17Heteroaryl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces,
R 21, R 22, R 23, R 25And R 26Be hydrogen, C independently of one another 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-,
R 27And R 28Be independently of one another
Figure A20058004219100401
Especially
Figure A20058004219100402
R wherein 29, R 30And R 31Be hydrogen, C independently of one another 1-C 8Alkyl, C 1-C 8Alkoxyl group or group-NR 32R 33, R wherein 32And R 33Be independently of one another
Figure A20058004219100403
R wherein 34Be hydrogen, C 1-C 8Alkyl or C 1-C 8Alkoxyl group, perhaps R 27And R 28Nitrogen-atoms with their institute's bondings forms 5 or 6 yuan of heterocycles, for example
Figure A20058004219100404
Figure A20058004219100411
Described group can be condensed by one or two optional phenyl that replaces, for example
Figure A20058004219100412
R wherein 216And R 217Represent hydrogen, C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group or phenyl, R 29' and R 30' represent hydrogen, C independently of one another 1-C 8-alkyl or C 1-C 8-alkoxyl group, and X 1Represent hydrogen or C 1-C 8-alkyl; And A 2Represent A 1, condition is A 2And A 1Have different implications at same intramolecularly, perhaps
A 2Representative
Figure A20058004219100413
Especially
Figure A20058004219100421
R wherein 27And R 28As defined above,
R 25And R 26Be hydrogen, C independently of one another as defined above, and preferably 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-, and
R 101, R 102, R 103, R 106, R 107, R 110, R 111, R 112, R 115, R 116, R 122, R 123, R 135, R 136, R 137, R 138, R 139, R 140, R 147And R 148Be hydrogen, C independently of one another 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-;
R 124And R 125Can be identical or different, and be selected from C 1-C 18Alkyl; Perhaps R 124And R 125Form ring, especially 5,6 or 7 yuan of rings together, described ring can be chosen wantonly by C 1-C 8Alkyl replaces, and perhaps can choose wantonly by phenyl to condense 1 or 2 time, and described phenyl can be by C 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group replace 1-3 time;
R 153Be C 1-C 25Alkyl, and
R 251, R 252, R 253, R 254, R 255And R 256Be C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group, particularly hydrogen.
If R 124And R 125Form ring together, they are preferably formed pentamethylene or cyclohexane ring, and described ring can be chosen wantonly by C 1-C 8Alkyl replaces 1-3 time, perhaps can choose wantonly by phenyl to condense 1 or 2 time, and described phenyl can be by C 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group replace 1-3 time.The example of condensed cycloalkyl and cyclohexyl is:
Figure A20058004219100431
R wherein 251, R 252, R 253, R 254, R 255And R 256Be C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group, particularly hydrogen.
In a preferred embodiment, A 2Representative
R wherein 25And R 26Be hydrogen, C independently of one another 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-.
In an especially preferred embodiment, A 1Representative
Figure A20058004219100442
R wherein 300Be C 1-C 8Alkyl, phenyl, described phenyl can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces,
R 9Be hydrogen, phenyl or 1-naphthyl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces; C 1-C 8Alkyl or C 1-C 8Alkoxyl group, and
R 21Be hydrogen, C 1-C 8Alkyl or C 1-C 8Alkoxyl group.
In another preferred embodiment, the present invention relates to the Diketopyrrolo-pyrrole compounds of formula I, wherein
A 1It is the group of following formula
Figure A20058004219100452
A 2Be A 1Or the group of following formula
Figure A20058004219100461
R wherein 27And R 28As defined above.
In another preferred embodiment, the present invention relates to the Diketopyrrolo-pyrrole compounds of formula I, wherein
A 1It is the group of following formula
And A 2It is the group of following formula
Figure A20058004219100471
R wherein 300, R 9, R 27And R 28As defined above.
In described embodiment, R 27And R 28Preferably be independently of one another
Figure A20058004219100472
Figure A20058004219100473
R wherein 29, R 30And R 31Be hydrogen, C independently of one another 1-C 8Alkyl or C 1-C 8Alkoxyl group.
Being used for the main body of El element/object composition, comprise group-NR 27R 28The Diketopyrrolo-pyrrole compounds of formula I be commonly used for object, wherein do not comprise group-NR 27R 28The Diketopyrrolo-pyrrole compounds of formula I usually as main body.
R 1And R 2Preferably be allyl group independently of one another, C 1-C 8Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2 for example, 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl, three (C 1-C 8Alkyl) silyl trimethyl silyl for example, phenyl or 1-or 2-naphthyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time ,-CH 2-A 3' ,-CHCH 3-A 3Or-CH 2-CH 2-A 3, A wherein 3Represent phenyl, described phenyl can be by C 1-C 8Alkyl replaces 1 or 2 time.Following Diketopyrrolo-pyrrole compounds is preferred:
Figure A20058004219100481
Figure A20058004219100501
Figure A20058004219100511
Figure A20058004219100521
Figure A20058004219100531
Figure A20058004219100541
R wherein 1Be allyl group, C 1-C 8Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2 for example, 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl, three (C 1-C 8Alkyl) silyl trimethyl silyl for example ,-CH 2-A 3' ,-CHCH 3-A 3Or-CH 2-CH 2-A 3, A wherein 3Represent phenyl, described phenyl can be by C 1-C 8Alkyl replaces 1,2 or 3 time.
Following Diketopyrrolo-pyrrole compounds is preferred:
Figure A20058004219100551
Figure A20058004219100552
Figure A20058004219100561
Figure A20058004219100571
Figure A20058004219100581
Figure A20058004219100591
Figure A20058004219100601
Figure A20058004219100622
The DPP compound of formula I of the present invention can according to or be similar to method well-known in the art and synthesize, these methods are described in for example following document: US4,579,949, EP-A353,184, EP-A-133,156, EP-A-1,087,005, EP-A-1,087,006, WO03/002672, WO03/022848, WO03/064558, WO04/090046, WO05/005571 and WO05/005430.
Formula I compound can for example obtain like this: in a first step, and with the DPP derivative of alkaline purification following formula
The reaction mixture that will obtain in a first step in second step is handled with a kind of alkylating agent commonly used or two kinds of alkylating agents then, wherein in a first step, described alkali is for example sodium hydride, lithium hydride or potassium hydride KH of hydride, alkali metal alcoholate is sodium tert-butoxide or potassium tert.-butoxide, sodium tert-amyl alcohol for example, or carbonate for example yellow soda ash or salt of wormwood, and formula (R 1) 1 or 2X 10And/or (R 2) 1 or 2X 10The alkylating agent halogen compounds, X wherein 10Be for example chlorine, bromine or iodine of halogen, preferred chlorine, bromine or iodine, preferred especially R 1X 10And R 2X 10, X wherein 10It is bromine or iodine (about describing referring to EP-A-1 087,005 in detail).
The compound of following formula
Figure A20058004219100642
Can make by the method that is described among the WO05/005430, described method comprises formula (XI) compound and nitrile A 2-CN reaction
Figure A20058004219100651
A wherein 1And A 2The implication that has and above provide, and R is C 1-C 18Alkyl, particularly C 1-C 4Alkyl, aryl, particularly phenyl, or aralkyl, particularly benzyl, described group can be by C 1-C 8Alkyl, C 1-C 8Alkoxy or halogen replaces 1-3 time.
In another embodiment, the present invention relates to the compound of following formula
R wherein 1And R 2As defined above,
A 4And A 5Has A independently of one another 2Contain, and
A 6Be cycloalkyl, arylidene or heteroarylidene, described group is optional by C 1-C 8-alkyl or C 1-C 8-alkoxyl group replaces 1-3 time.
A 4And A 5We can say or can be identical, and be the group of formula II perhaps have A different 2Implication.For A 4And A 5, following groups is preferred:
Figure A20058004219100661
R wherein 25, R 26, R 122-R 125, R 135-R 140, R 149And R 150As defined above.
R 1And R 2Can be different, and preferably have identical meanings.
A 6Example have:
Especially
Especially
Figure A20058004219100675
Or
Figure A20058004219100676
Figure A20058004219100677
Especially
Figure A20058004219100678
Figure A20058004219100679
Especially
Figure A200580042191006710
Or
Figure A200580042191006711
Figure A200580042191006712
Especially
Figure A200580042191006713
Figure A20058004219100681
Figure A20058004219100682
Especially
Figure A20058004219100683
Figure A20058004219100684
Figure A20058004219100685
Or
Figure A20058004219100686
Wherein n1, n2, n3, n4, n5, n6 and n7 are 1-10, the integer of 1-3 particularly, A 16And A 17Be H, C independently of one another 1-C 18Alkyl, by E ' replacement and/or by the C of D ' interruption 1-C 18Alkyl, C 6-C 24Aryl, by the C of G ' replacement 6-C 24Aryl, C 2-C 20Heteroaryl, by the C of G ' replacement 2-C 20Heteroaryl, C 2-C 18Alkenyl, C 2-C 18Alkynyl, C 1-C 18Alkoxyl group, by E ' replacement and/or by the C of D ' interruption 1-C 18Alkoxyl group, C 7-C 25Aralkyl or-CO-A 28,
A 8Be C 1-C 18Alkyl, by E ' replacement and/or by the C of D ' interruption 1-C 18Alkyl, C 6-C 24Aryl or C 7-C 25Aralkyl,
A 9And A 10Be C independently of one another 1-C 18Alkyl, by E ' replacement and/or by the C of D ' interruption 1-C 18Alkyl ' C 6-C 24Aryl, by the C of G ' replacement 6-C 24Aryl, C 2-C 20Heteroaryl, by the C of G ' replacement 2-C 20Heteroaryl, C 2-C 18Alkenyl, C 2-C 18Alkynyl, C 1-C 18Alkoxyl group, by E ' replacement and/or by the C of D ' interruption 1-C 18Alkoxyl group or C 7-C 25Aralkyl, perhaps
A 9And A 10Formation ring, especially 5 or 6 yuan of rings, described ring can be chosen wantonly by one or more C 1-C 18Alkyl replaces;
A 14And A 15Be H, C independently of one another 1-C 18Alkyl, by E ' replacement and/or by the C of D ' interruption 1-C 18Alkyl, C 6-C 24Aryl, by the C of G ' replacement 6-C 24Aryl, C 2-C 20Heteroaryl or by the C of G ' replacement 2-C 20Heteroaryl,
D ' is-CO-;-COO-;-S-;-SO-;-SO 2-;-O-;-NA 25-;-SiA 30A 31-;-POA 32-;-CA 23=CA 24-; Or-C ≡ C-; And
E ' is-OA 29-SA 29-NA 25A 26-COA 28-COOA 27-CONA 25A 26-CN;-OCOOA 27Or halogen; G ' is E ' or C 1-C 18Alkyl; A wherein 23, A 24, A 25And A 26Be H independently of one another; C 6-C 18Aryl; By C 1-C 18Alkyl or C 1-C 18The C that alkoxyl group replaces 6-C 18Aryl; C 1-C 18The C that alkyl or quilt-O-are interrupted 1-C 18Alkyl; Perhaps A 25And A 26Form 5 or 6 yuan of rings together,
Particularly
Figure A20058004219100691
Or
Figure A20058004219100692
A 27And A 28Be H independently of one another; C 6-C 18Aryl; By C 1-C 18Alkyl or C 1-C 18The C that alkoxyl group replaces 6-C 18Aryl; C 1-C 18The C that alkyl or quilt-O-are interrupted 1-C 18Alkyl, A 29Be H; C 6-C 18Aryl; By C 1-C 18Alkyl or C 1-C 18The C that alkoxyl group replaces 6-C 18Aryl; C 1-C 18Alkyl; Or the C of quilt-O-interruption 1-C 18Alkyl,
A 30And A 31Be C independently of one another 1-C 18Alkyl, C 6-C 18Aryl or by C 1-C 18The C that alkyl replaces 6-C 18Aryl, and
A 32Be C 1-C 18Alkyl, C 6-C 18Aryl or by C 1-C 18The C that alkyl replaces 6-C 18Aryl.
A 6The group of following formula preferably
Figure A20058004219100701
Or
Or
Figure A20058004219100703
Wherein
A 8Be C 1-C 18Alkyl,
A 9And A 10Be C independently of one another 1-C 18Alkyl, perhaps A 9And A 10Formation ring, especially 5 or 6 yuan of rings, described ring can be chosen wantonly by C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces, and A 16And A 17Be H, C independently of one another 1-C 8Alkyl or C 1-C 8Alkoxyl group.
Because (photic) luminous spectral position is for A 6, following groups is preferred:
Figure A20058004219100704
With
Figure A20058004219100705
A wherein 8, A 16And A 17As defined above.
Most preferably, A 6It is the group of following formula
Figure A20058004219100711
A wherein 8Be C 1-C 8Alkyl, and A is hydrogen or C 1-C 8Alkyl.
The formula III examples for compounds is:
Figure A20058004219100712
A wherein 6It is the group of following formula
Figure A20058004219100713
A wherein 8Be C 1-C 8Alkyl, and A 16Be hydrogen or C 1-C 8Alkyl.
Figure A20058004219100721
A wherein 16, R 2, A 4And A 5As defined above, and n be integer 1,2 or 3.
Preferred formula III examples for compounds is:
Figure A20058004219100731
The formula III compound can for example make by following reaction scheme:
Figure A20058004219100732
Wherein R, R 1, A 4And A 6As defined above, and X 10Be for example chlorine, bromine or iodine of halogen, preferred bromine or iodine.
In order to prepare the formula III compound, with halogenide, the bromide of bromide or muriate, especially following formula for example
Figure A20058004219100741
Second boric acid or the reaction of second boric acid ester with the following formula of equimolar amount
Figure A20058004219100742
X wherein 11When occurring be independently-B (OH) at every turn 2,-B (OY 1) 2Or the group of following formula
Y wherein 1When occurring, be C independently at every turn 1-C 10Alkyl, and Y 2When occurring, be C independently at every turn 2-C 10Alkylidene group, for example-CY 3Y 4-CY 5Y 6-or-CY 7Y 8-CY 9Y 10-CY 11Y 12-, Y wherein 3, Y 4, Y 5, Y 6, Y 7, Y 8, Y 9, Y 10, Y 11And Y 12Be hydrogen or C independently of one another 1-C 10Alkyl, especially-C (CH 3) 2C (CH 3) 2-, or-C (CH 3) 2CH 2C (CH 3) 2-, carry out under the katalysis of described Pd of being reflected at and triphenylphosphine, wherein Ar 2And Ar 3Form group A together 6This reaction is for example carried out in the toluene at aromatic solvent usually at about 70 ℃-180 ℃.Other solvent for example dimethyl formamide and tetrahydrofuran (THF) also can use separately or use as mixture with aromatic hydrocarbons.Use the aqueous solution of alkali, for example yellow soda ash or sodium bicarbonate aqueous solution are as the HBr scavenging agent.According to the reactivity of reactant, this reaction can be carried out 2-100 hour.Organic bases for example tetraalkylammonium hydroxide and phase-transfer catalyst for example TBAB can promote the activity of boron (referring to for example Leadbeater﹠amp; Marco; Angew.Chem.Int.Ed.Eng.42 (2003) 1407 and the document of wherein being quoted).Other modification of reaction conditions by T.I.Wallow and B.M.Novak at J.Org.Chem.59 (1994) 5034-5037; And M.Remmers, M.Schulze and G.Wegner provide in Macromol.Rapid Commun.17 (1996) 239-252.By using the Suzuki coupling, can make the formula III compound, wherein A 4And A 5Have different implications, and such compound, wherein
A 6Be formula-Ar 2-(Ar 3) N11-Ar 2-,
N11 is integer 1-10, especially 1,2 or 3,
Ar 2, Ar 2' and Ar 3Be the group of following formula independently of one another
Figure A20058004219100751
A wherein 8, A 9, A 16And A 17As defined above.
In another embodiment, the present invention relates to composition, described composition comprises object chromophoric group and main body chromophoric group, wherein chromophoric absorption spectrum of object and the chromophoric fluorescence emission spectrum of main body are overlapping, wherein said main body chromophoric group is a Diketopyrrolo-pyrrole compounds, and its photoluminescence emission peak is at 500-720nm, preferred 520-630nm, 540-600nm most preferably, wherein main body and/or object chromophoric group are the Diketopyrrolo-pyrrole compounds of formula I.
Therefore, composition comprises the diketopyrrolopyrrolecocrystals main body chromophoric group of formula I or III, or the diketopyrrolopyrrolecocrystals object chromophoric group of formula I or III; Or the diketopyrrolopyrrolecocrystals object chromophoric group of the diketopyrrolopyrrolecocrystals main body chromophoric group of formula I or III and formula I or III.
Can use the diketopyrrolopyrrolecocrystals object chromophoric group that is described among for example EP-A-1087006, WO03/002672, WO03/064558 or the WO04/090046 to replace the diketopyrrolopyrrolecocrystals object chromophoric group of formula I or III.
Can make the chromophoric preferred diketopyrrolopyrrolecocrystals object chromophoric group of diketopyrrolopyrrolecocrystals object that is used for replacing formula I or III is to be described among the WO03/064558 those:
Figure A20058004219100761
A wherein 4And A 5Representative independently of one another
Figure A20058004219100762
R 200And R 201Represent C independently of one another 1-C 25-alkyl, preferred C 1-C 8Alkyl, C 5-C 12Cycloalkyl or condensed 1 or 2 time C by phenyl 5-C 12-cycloalkyl, described phenyl can be by C 1-C 4-alkyl, halogen and cyano group replace 1-3 time, cyclohexyl particularly, and described cyclohexyl can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, particularly 2,6-two-isopropylcyclohexyl-or
Figure A20058004219100763
Silyl, particularly trimethyl silyl, A 6' or-CR 211R 212-(CH 2) m-A 6', R wherein 211And R 212Represent hydrogen or C independently of one another 1-C 4Alkyl or phenyl, described phenyl can be by C 1-C 3Alkyl replaces 1-3 time, A 6Represent phenyl or 1-or 2-naphthyl, described group can be replaced 1-3 time by following groups: C 1-C 8Alkyl, C 1-C 8Alkoxyl group, halogen, cyano group, phenyl, this phenyl can be by C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces 1-3 time, or-NR 213R 214, R wherein 213And R 214Represent C 1-C 25-alkyl, C 5-C 12-cycloalkyl or C 6-C 24-aryl, particularly phenyl or 1-or 2-naphthyl, described group can be replaced 1-3 time by following groups: C 1-C 8Alkyl, C 1-C 8Alkoxyl group, halogen or cyano group or phenyl, this phenyl can be by C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces 1-3 time, and particularly 3,5-3,5-dimethylphenyl, 3,5-two-tert-butyl-phenyl, 3-aminomethyl phenyl and 2,6-two-isopropyl phenyl, and m represents 0,1,2,3 or 4, particularly 0 or 1; R 205, R 206And R 207Represent hydrogen, C independently of one another 1-C 25-alkyl, C 1-C 25-alkoxyl group ,-OCR 211R 212-(CH 2) m-A 6', cyano group, halogen ,-OR 210, S (O) PR 213Or phenyl, this phenyl can be by C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces 1-3 time, wherein R 210Represent C 6-C 24-aryl or comprise the saturated or unsaturated heterocycle of 5-7 annular atoms, wherein said ring is formed R by carbon atom and 1-3 heteroatoms that is selected from nitrogen, oxygen and sulphur 213Represent C 1-C 25-alkyl, C 5-C 12-cycloalkyl ,-CR 211R 212-(CH 2) m-Ph, R 215Represent C 6-C 24-aryl, p represent 0,1,2 or 3, and n represents 0,1,2,3 or 4, wherein R 208And R 209Represent hydrogen, C independently of one another 1-C 25-alkyl, C 5-C 12-cycloalkyl ,-CR 211R 212-(CH 2) m-A 6', C 6-C 24-aryl is phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl, phenanthryl, terphenyl, pyrenyl, 2-or 9-fluorenyl or anthryl for example, preferred C 6-C 12Aryl is phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl for example, described group is not replace or replace, or saturated or unsaturated heterocycle base, and described heterocyclic radical comprises 5-7 annular atoms, wherein said ring is made up of carbon atom and 1-3 heteroatoms that is selected from nitrogen, oxygen and sulphur, and R 216And R 217Represent hydrogen and C independently of one another 6-C 24-aryl, particularly phenyl.
The group of following formula is particularly preferred
Figure A20058004219100771
R wherein 208And R 209Be the group of following formula independently of one another
Figure A20058004219100781
R wherein 221, R 222And R 223Be hydrogen, C independently of one another 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-.R 221, R 222And R 223Be hydrogen, C independently of one another 1-C 8Alkyl, C 1-C 8Alkoxyl group or C 1-C 8Alkylthio.
R 201And R 202Be C independently of one another 1-C 8Alkyl,
Figure A20058004219100782
Or-CR 211R 212-(CH 2) m-A 6',
R wherein 211Be hydrogen, R 212Be hydrogen, particularly methyl or phenyl, and A 6' be
Figure A20058004219100783
R wherein 205, R 206And R 207Be hydrogen, C independently of one another 1-C 4-alkyl or halogen, particularly Br.
The DPP compound of particularly preferred formula II is a following compounds:
Figure A20058004219100791
Figure A20058004219100792
Figure A20058004219100801
The particularly preferred present composition is as follows:
Figure A20058004219100802
Figure A20058004219100811
Figure A20058004219100821
Figure A20058004219100831
Figure A20058004219100841
The compound of in WO04/090046, describing as the following formula of guest compound
Figure A20058004219100842
Be preferred, R wherein 301And R 302Represent C independently of one another 1-C 8Alkyl, C 5-C 12-cycloalkyl, described cycloalkyl can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, phenyl or 1-or 2-naphthyl, and described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, A 6" or-CR 331R 332-(CH 2) m-A 6", R wherein 331And R 332Represent hydrogen, A 6" represent phenyl or 1-or 2-naphthyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, and m represents 0 or 1,
A 301And A 302Be independently from each other
Figure A20058004219100851
Wherein
R 315Be group-NR 308R 309, R wherein 308And R 309Represent C independently of one another 1-C 8-alkyl, A 301, for example
Figure A20058004219100852
Especially
Figure A20058004219100853
Perhaps R 308And R 309Nitrogen-atoms with their institute's bondings forms 5 or 6 yuan of heterocycles, and described heterocycle can be condensed by 1 or 2 optional phenyl that replaces, for example
Figure A20058004219100861
R wherein 315', R 316And R 317Represent hydrogen, C independently of one another 1-C 8-alkyl or C 1-C 8-alkoxyl group, R 305" and R 306Represent hydrogen, C independently of one another 1-C 8-alkyl or C 1-C 8-alkoxyl group, and X 1Represent hydrogen or C 1-C 8-alkyl.
The object chromophoric group of the DPP compound of particularly preferred formula II and III representative is a following compounds:
Figure A20058004219100881
Figure A20058004219100882
Figure A20058004219100891
Figure A20058004219100901
Can use the DPP guest compound of in WO03/048268, describing to replace above-mentioned DPP guest compound, for example:
Figure A20058004219100911
With
Figure A20058004219100912
Can use the diketopyrrolopyrrolecocrystals main body chromophoric group that is described among for example EP-A-1087006, WO03/002672, WO03/064558 or the WO04/090046 to replace the diketopyrrolopyrrolecocrystals main body chromophoric group of formula I.
In addition, formula I or III compound can use with other the known fluorescent chemicalses as main body or guest compound, for example aromatic hydrocarbons condense derivative for example rubrene with perylene; The fused-heterocycle thing is pyrido thiadiazoles, Pyrazolopyridine and Naphthalamide derivatives for example; Rare-earth complex is Eu, Ir or Pt complex compound for example; Zinc protoporphyrin, rhodamine, deazaflavin derivative, coumarin derivatives, fen _ azoles, quinacridone, dicyano vinyl-arene, Alq 3And derivative.
Except the DPP host compound of the present invention of formula I or III is thought, particularly preferred main body of the present invention/object composition can also comprise the quinacridone guest compound that is described among the PCT/EP2005/052841 for example:
Figure A20058004219100921
Figure A20058004219100931
Term " at least two adjacent substituting group form aromatics or aliphatic series condenses ring system " is expression, two adjacent substituting groups can form aromatic ring, phenyl or naphthyl ring for example, aliphatic series is encircled for example cyclohexyl ring, or heterocycle for example pyridine or pyrrole ring, wherein two or more such rings can form with the group of their institute's bondings and condense ring system.
Term " halogen " refers to fluorine, chlorine, bromine and iodine.
C 1-C 25Alkyl generally be straight chain or ramose (under possible situation) methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, the 2-amyl group, the 3-amyl group, 2, the 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl, preferably such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, the 2-amyl group, the 3-amyl group, 2, the 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3, the C of 3-tetramethyl butyl and 2-ethylhexyl 1-C 8Alkyl is more preferably such as the C that is generally methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl 1-C 4Alkyl.
Term " haloalkyl, halogenated alkenyl and halo alkynyl " refers to partly or entirely replace with halogen the base of abovementioned alkyl, alkenyl and alkynyl, for example trifluoromethyl etc." aldehyde radical, ketone group, ester group, formamyl and amino " comprises the base that is replaced by alkyl, cycloalkyl, aryl, aralkyl or heterocyclic radical, and wherein alkyl, cycloalkyl, aryl, aralkyl and heterocyclic radical can be unsubstituted or substituted.Term " silyl " refers to general formula-SiR 62R 63R 64Base, R wherein 62, R 63And R 64That separate is C 1-C 8Alkyl, especially C 1-C 4Alkyl; C 6-C 24Aryl or C 7-C 12Aralkyl, for example trimethyl silyl.Term " siloxy-" refers to general formula-O-SiR 62R 63R 64Base, R wherein 62, R 63And R 64Definition as above, trimethylsiloxy for example.
C 1-C 8The example of alkoxyl group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethyl propoxy-, positive hexyloxy, positive heptan oxygen base, n-octyloxy, 1,1,3,3-tetramethyl-butoxy and 2-ethyl hexyl oxy are preferably such as the C that is generally methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy 1-C 4Alkoxyl group.Term " alkylthio " refers to the base identical with alkoxyl group, but the Sauerstoffatom of ehter bond replaces with sulphur atom.
Term " aryl " generally is such as phenyl, pentalene base, indenyl, Azulene base, 1-naphthyl, 2-naphthyl, 4-xenyl, as-indacenyl, s-indacenyl, acenaphthenyl, phenanthryl, terphenyl, pyrenyl, 2-or 9-fluorenyl, fluoranthene base, acephenanthrylenyl, aceanthrylenyl, triphenylenyl, pyrenyl or anthryl, preferably such as the C of phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl 6-C 12Aryl, they can be unsubstituted or replace.
Term " aralkyl " refers generally to such as benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-Er Jiajibianji, ω-phenyl-butyl, ω, the C of ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl 7-C 24Aralkyl is preferably such as benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-Er Jiajibianji, ω-phenyl-butyl, ω, the C of ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl 7-C 18Aralkyl is especially preferably such as benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-Er Jiajibianji, ω-phenyl-butyl or ω, the C of ω-dimethyl-ω-phenyl-butyl 7-C 12Aralkyl, wherein aliphatic hydrocarbyl and aromatic hydrocarbyl can be unsubstituted or replace.
Term " aryl ether " refers generally to C 6-24Aryloxy is promptly such as the oxygen C of for example phenoxy group or 4-p-methoxy-phenyl 6-24Aryl.Term " aryl thioethers base " refers generally to C 6-24The aryl thio group is promptly such as the sulphur C of for example benzene sulfo-or 4-anisole sulfo- 6-24Aryl.Term " formamyl " refers generally to C 1-18Formamyl, preferred C 1-8Formamyl; they can be unsubstituted or replacement, for example formamyl, methylamino formyl radical, ethylamino formyl radical, normal-butyl formamyl, tertiary butyl formamyl, formyl-dimethylamino oxygen base, morpholino formamyl or pyrrolidino formamyl.
Term " cycloalkyl " refers generally to the C such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ring undecyl, cyclo-dodecyl 5-C 12Cycloalkyl, preferred cyclopentyl, cyclohexyl, suberyl or ring octyl group, they can be unsubstituted or replace.Term " cycloalkenyl group " refers to contain the unsaturated lipid cyclic hydrocarbon radical of one or more pairs key, for example cyclopentenyl, cyclopentadienyl, cyclohexenyl etc., and they can be unsubstituted or replace.Cycloalkyl, especially cyclohexyl can be by can be by C 1-C 4Alkyl, halogen and cyano group replace 1-3 time phenyl condensation 1 or 2 times.The example of this condensed ring hexyl is:
Or
Figure A20058004219100952
Particularly
Or
Figure A20058004219100954
R wherein 51, R 52, R 53, R 54, R 55And R 56That separate is C 1-C 8Alkyl, C 1-C 8Alkoxyl group, halogen and cyano group, especially hydrogen.
Term " comprises and contains heteroatomic 5 yuan of heterocyclic groups that 1-3 is selected from nitrogen, oxygen and sulphur " and is meant 5 yuan of heterocycles for example thienyl, furyl, furfuryl, 2H-pyranyl, pyrryl, imidazolyl or pyrazolyl, or as condensing 5 yuan of heterocycles of the part of ring system, described condense ring system by these 5 yuan of heterocycles with can choose substituted aryl, heteroaryl and/or Cycloalkylfused formation wantonly.Such examples of groups is included in relevant A 1And A 2The group guide look and the definition of heteroaryl or heterocyclic radical in.
Term " comprises and contains heteroatomic 6 yuan of heterocyclic groups that 1-3 is selected from nitrogen, oxygen and sulphur " and is meant 6 yuan of heterocycles for example pyridyl, triazinyl, pyrimidyl, pyrazinyl, pyridazinyl, or as condensing 6 yuan of heterocycles of the part of ring system, described condense ring system by these 6 yuan of heterocycles with can choose substituted aryl, heteroaryl and/or Cycloalkylfused formation wantonly.Such examples of groups is included in relevant A 1And A 2The group guide look and the definition of heteroaryl or heterocyclic radical in.
Term " heteroaryl or heterocyclic radical " is the ring with 5-7 annular atoms, nitrogen wherein, oxygen or sulphur are possible heteroatomss, generally be to have 5-18 unsaturated heterocycle base that has the atom of at least 6 conjugated pi-electronics, thienyl for example, benzo [b] thienyl, dibenzo [b, d] thienyl, thianthrenyl, furyl, furfuryl group, the 2H-pyranyl, benzofuryl, isobenzofuran-base, dibenzofuran group, the phenoxy group thienyl, pyrryl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidyl, pyrazinyl, pyridazinyl, the indolizine base, pseudoindoyl, indyl, indazolyl, purine radicals, quinolizinyl, quinolyl, isoquinolyl, 2, the 3-phthalazinyl, 1, the 5-phthalazinyl, the cinnolines base, quinazolyl, 1, the 2-phthalazinyl, pteridyl, carbazyl, carbolinyl, the benzotriazole base, benzo _ azoles base, phenanthridinyl, acridyl, perimidinyl, the phenanthroline base, phenazinyl, isothiazolyl, phenothiazinyl, different _ the azoles base, furazan base or fen _ piperazine base, preferred above-mentioned monocycle or bicyclic heterocyclic radical.
Term " aryl " and " alkyl " in alkylamino, dialkyl amido, alkaryl amino, arylamino and the diaryl generally refer to C respectively 1-C 25Alkyl and C 6-C 24Aryl.
Above-mentioned base can be by C 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carbonyl, ester group, formamyl, amino, nitro, silyl or siloxy-replace.
The invention still further relates to the fluorescent diketopyrrolopyrroles or the present composition that between anode and negative electrode, have formula I or III, and under the electric energy effect luminous electroluminescent device.
The typical structure of up-to-date organic electroluminescence device is:
(i) anode/hole transmission layer/electron transfer layer/negative electrode, wherein The compounds of this invention or composition or as hole transport compound or composition are used to form luminous and hole transmission layer, perhaps as electric transmission compound or composition, be used to form luminous and electron transfer layer
(ii) anode/hole transmission layer/luminescent layer/electron transfer layer/negative electrode, wherein this compound or composition form luminescent layer, and in this structure, show the hole with them or electronic transmission performance irrelevant,
(iii) anode/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/negative electrode,
(iv) anode/hole transmission layer/luminescent layer/hole suppresses layer/electron transfer layer/negative electrode,
(v) anode/hole injection layer/hole transmission layer/luminescent layer/hole suppresses layer/electron transfer layer/negative electrode,
(vi) anode/luminescent layer/electron transfer layer/negative electrode,
(vii) anode/luminescent layer/hole suppresses layer/electron transfer layer/negative electrode,
(viii) only contain luminescent material or contain luminescent material and the bonded individual layer of any material of hole transmission layer, hole block layer and/or electron transfer layer and
(ix) (ii) to (multilayered structure of describing vii), wherein luminescent layer is the (individual layer of definition viii).
Compound of the present invention and composition can be used for any organic layer such as for example hole transmission layer, luminescent layer or electron transfer layer in principle, but are preferably used as the luminescent material in the luminescent layer.
The chromophoric weight ratio of main body chromophoric group and object is generally 50: 50-99.99: 0.01, be preferably 90: 10-99.99: 0.01, more preferably 95: 5-99.9: and 0.1, most preferably be 98: 2-99.9: 0.1.
The film-type electroluminescent device mainly is made of pair of electrodes and interelectrode at least one charge transport layer usually.General two charge transport layers, hole transmission layer (adjacent) and the electron transfer layer (adjacent) of existing with negative electrode with anode.According to its performance as hole transport or electron transport material, in them one contain inorganic or organic fluorescent substance as luminescent material.Equally commonly luminescent material is as other layers between hole transport and the electron transfer layer.In above-mentioned device architecture, can constitute hole injection layer between anode and the hole transmission layer, and/or can constitute inhibition layer in hole between luminescent layer and the electron transfer layer, make hole and electron amount maximum in the luminescent layer, thereby reach high charge recombination efficient and luminous by force.
This device can prepare with several different methods.Usually prepare with vacuum-evaporation.Preferably organic layer is pressed in being purchased on indium-stannic oxide (" ITO ") glass baseplate of maintenance room temperature with above-mentioned sequential layer, this base material plays anodize in above structure.The preferred 1-10000nm of film thickness, more preferably 1-5000nm, more preferably 1-1000nm, more preferably 1-500nm.Cathodic metal, Mg/Ag/ alloy for example, the binary Li-Al of thickness 50-200nm or LiF-Al system are laminated to this above organic layer.Vacuum tightness between depositional stage preferably is lower than 0.1333Pa (1 * 10 -3Torr), more preferably less than 1.333 * 10 -3Pa (1 * 10 -5Torr), more preferably less than 1.333 * 10 -4Pa (1 * 10 -6Torr).
As anode, can adopt and have that as if height is selected merit all gold, silver, copper, aluminium, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, plumbous, manganese, the metal of tungsten etc., such as magnesium/copper, magnesium/silver, magnesium/aluminium, the metal alloy of aluminium/indium etc., such as Si, Ge, the semi-conductor of GaAs etc., such as indium-tin-oxide (" ITO "), the metal oxide of ZnO etc., metallic compound such as CuI etc., and such as polyacetylene, polyaniline, Polythiophene, polypyrrole, the anode material commonly used of the conductive polymers of poly(p-phenylene) etc., preferably ITO, the most preferably ITO on the glass baseplate.These electrode materialss, metal, metal alloy, metal oxide and metallic compound can be transformed in the electrode by for example sputtering method.Using under the situation of material as electrode with metal or metal alloy, electrode also can form by vacuum deposition method.Under with the situation of metal or metal alloy as the material that forms electrode, electrode also can form (referring to for example Handbook of Electrochemistry, pp383-387, Mazuren, 1985) by chemical plating method.Under the situation that adopts conductive polymers, electrode can prepare by forming film by the anodic oxidation polymerization process on the base material that conductive coating is provided in advance.The thickness that forms electrode on base material does not have concrete limit value, but when making luminescent screen with base material, thickness of electrode is preferably at 1-300nm, more preferably in the 5-200nm scope, to guarantee transparency.
In a preferred embodiment, the thickness of ITO film is 10nm (100_)-1 μ (10000_) on the base material, preferred 20nm (200_)-500nm (5000_).The sheet resistance of ITO film is chosen in and is no more than 100 Ω/cm 2, preferably be no more than 50 Ω/cm 2
This anode can be purchased from for example Japanese manufacturers of Geomatech Co.Ltd., Sanyo Vacuum Co.Ltd., Nippon Sbeet Glass Co.Ltd..
Base material can be with conducting electricity or electrically insulating material.With under the situation of conductive base, on base material, directly form luminescent layer or hole transmission layer, and under the situation of electricity consumption insulating substrate, on base material, form earlier electrode, superimposed luminescent layer or hole transmission layer then.
Base material can be transparent, translucent or opaque.Yet, to do with base material under the situation of indicator plate, base material must be transparent or semitransparent.
Transparent electrical isolation base material is for example such as the mineral compound of glass, quartz etc., such as the organic polymer compounds of polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate etc.Every kind of these base material all can convert the electrically conducting transparent base material to by electrode is provided according to one of aforesaid method.
The example of translucent electrical isolation base material is the mineral compound such as aluminum oxide, YSZ (zirconium white that yttrium is stable) etc., such as the organic polymer compounds of polyethylene, polypropylene, polystyrene, Resins, epoxy etc.Every kind of these base material all can convert translucent conductive base to by electrode is provided according to one of aforesaid method.
The example of opaque conductive base is the metal such as aluminium, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold, platinum etc., various plated metals, metal alloy such as bronze, stainless steel etc., such as the semi-conductor of Si, Ge, GaAs etc., such as the conductive polymers of polyaniline, Polythiophene, polypyrrole, polyacetylene, polyparaphenylene etc.
Base material can obtain by certain the above-mentioned base material that forms required specification.Preferred substrates has smooth surface.Even its surface irregularity can not bring any problem to practical application yet, as long as its circumference ununiformity curvature is not less than 20 μ m.Base material thickness is not limit, as long as can guarantee enough physical strengths.
Negative electrode can adopt such as basic metal, alkaline-earth metal, 13 family's elements, silver and copper, and their alloy or mixture, for example sodium, lithium, potassium, calcium, lithium fluoride (LiF), sodium-potassium-sodium alloy, magnesium, magnesium-silver alloys, magnesium-copper alloy, magnesium-aluminum alloy, magnesium-indium alloy, aluminium, aluminium-aluminium oxide alloy, aluminium-lithium alloy, indium, calcium, and the material of enumerating among the EP-A 499011, for example such as low merit cathode materials of selecting commonly used such as the conductive polymerss of polypyrrole, Polythiophene, polyaniline, polyacetylene etc., preferred Mg/Ag alloy, LiF-Al or Li-Al composition.
In a preferred embodiment, can adopt thickness is 10nm (100_)-1 μ m (10000_), the mixture of the magnesium-silver alloys of preferred 20nm (200_)-500nm (5000_) or magnesium and silver, or the mixture of lithium-aluminium alloy, lithium fluoride-aluminium alloy or lithium and aluminium.
This negative electrode can be deposited on the aforementioned electronic transport layer by above-mentioned known evaporating deposition technique.
In a preferred embodiment of the invention, hole transmission layer and electric transmission interlayer can adopt luminescent layer.Luminescent layer is generally by forming film preparation on hole transmission layer.
The method that forms described film has for example vacuum deposition method, spin-coating method, flow coat method, Langmuir-Blodgett (" LB ") method etc.Wherein easy to operate and angle cost is seen calmly, especially preferred vacuum deposition method, spin-coating method and flow coat method.
Using under the situation of composition forming film by vacuum deposition method, vacuum deposition conditions depends on performance, shape and the crystalline state of compound usually consumingly.Yet top condition generally is: cooking-vessel temperature: 100-400 ℃; Base material temperature :-100-350 ℃; Pressure: 1.33 * 10 4Pa (1 * 10 2Torr)-1.33 * 10 -4Pa (1 * 10 -6Torr), deposition: 1pm-6nm/ second.
In organic EL, light emitting layer thickness is one of factor of determining its luminescent properties.For example, if luminescent layer is thick inadequately, clips between two electrodes of described luminescent layer and just be easy to be short-circuited, thereby can not get the EL emission.On the other hand, if luminescent layer is too thick, because its resistance is very big, the pressure drop of luminescent layer inside is just very big, thereby the threshold voltage of EL emission is improved.Therefore, the organic light emission layer thickness is limited to 5nm-5 μ m, in the preferred 10nm-500nm scope.
Forming under the situation of luminescent layer with spin-coating method and flow coat method, ink-jet printing process, available by the concentration of said composition with 0.0001-90% weight is dissolved in such as benzene,toluene,xylene, tetrahydrofuran (THF), methyltetrahydrofuran, N, the solution for preparing in the suitable organic solvent of dinethylformamide, methylene dichloride, dimethyl sulfone etc. applies.If concentration surpasses 90% weight, solution is thickness too just often, no longer can form smooth and uniform film.On the other hand, if concentration is lower than 0.0001% weight, film forming efficiency is just too low, uneconomical.Therefore, preferred compositions concentration is 0.01-80% weight.
Under the situation that adopts above-mentioned spin coating or flow coat method,, can further improve the homogeneity and the physical strength of gained layer by in the solution that forms luminescent layer, adding polymer binder.Can adopt any polymer binder in principle, as long as it dissolves in the solvent of dissolved composition.The example of this polymer binder is polycarbonate, polyvinyl alcohol, polymethacrylate, polymethylmethacrylate, polyester, polyvinyl acetate, Resins, epoxy etc.Yet if the solids content that polymer binder and composition are formed surpasses 99% weight, the flowability of solution is often just too low, can not form the luminescent layer of excellent in uniformity.On the other hand, if composition levels in fact is lower than polymer-bonded agent content, the resistance of described layer is just very big, and making only could be luminous when applying high-voltage.Therefore, the ratio of preferred polymer binder and composition is chosen in 10: 1-1: in 50 weight ranges, and the solids content that these two kinds of one-tenth are grouped in the solution is preferably in 0.01-80% weight, more preferably in the 0.1-60% weight range.
Hole transmission layer can adopt such as Polyvinyl carbazole
Figure A20058004219101001
Known organic hole transport compound; J.Amer.Chem.Soc., disclosed TPD compound in 90 (1968), 3925:
Q wherein 1And Q 2Each represents hydrogen atom or methyl; J.Appl.Phys., disclosed compound in 65 (9) (1989) 3610:
Compound based on Stilbene
Figure A20058004219101013
Wherein T and T 1Represent organic radical;
Compound based on hydrazone
Figure A20058004219101014
Compound as hole mobile material is not limited to above-claimed cpd.Available any compound with performance of transporting holes all can be used as hole mobile material, for example triazole derivative, _ oxadiazole derivative, imdazole derivatives, polyaryl alkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, aryl amine derivatives, the amino chalcone derivative that replaces, _ multipolymer and the derivative thereof of oxazole derivatives, Stilbene base anthracene derivant, fluorenone derivatives, hydrazone derivative, stilbene derivative, aniline, PEDOT (poly-(3,4-ethylidene dioxy base-thiophene)); Conducting oligomers, especially thiophene oligomers; Porphyrin compound, aromatic uncle amine compound, Stilbene ylamine compounds etc.Especially can adopt such as N, N, N ', N '-tetraphenyl-4,4 '-benzidine, N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-4,4 '-benzidine (TPD), 2,2 '-two (di-p-tolyl aminophenyl) propane, 1,1 '-two (4-xylyl aminophenyl)-4-Santosol 360s, two (4-dimethylamino-2-aminomethyl phenyl) phenylmethane, two (4-di-p-tolyl aminophenyl) phenylmethane, N, N '-phenylbenzene-N, N '-two (4-p-methoxy-phenyl)-4,4 '-benzidine, N, N, N ', N '-tetraphenyl-4,4 '-diamino-diphenyl ether, 4,4 '-two (diphenyl amino) quaterphenyl, N, N, N-three (p-methylphenyl) amine, 4-(di-p-tolyl amino)-4 '-[4-(di-p-tolyl amino) stilyl] Stilbene, 4-N, N-diphenyl amino-(2-diphenylacetylene) benzene, 3-methoxyl group-4 '-N, N-diphenyl amino Stilbene, the aromatic uncle amine compound of N-phenyl carbazole etc.
In addition, can adopt among the US-B-5061569 disclosed compound in disclosed 4,4 '-two [N-(1-the naphthyl)-N-phenyl amino] biphenyl and EP-A508562, wherein there are 3 triphenylamine units to be connected with nitrogen-atoms, for example 4,4 ', 4 "-three [N-(3-aminomethyl phenyl)-N-phenyl amino] triphenylamine.
Hole transmission layer can form by prepare the organic membrane that contains at least a hole mobile material on anode.Hole transmission layer can pass through formation such as vacuum deposition method, spin-coating method, flow coat method, ink-jet printing process, LB method.In these methods, from complexity and cost consideration, especially preferred vacuum deposition method, spin-coating method and flow coat method.
Under the situation that adopts vacuum deposition method, mode of deposition can be selected (referring to above) at the described same way as of the formation of luminescent layer.Preferably form the hole transmission layer that contains more than one hole mobile materials, can adopt the coevaporation method when adopting desired compounds.
Forming under the situation of hole transmission layer by spin-coating method or flow coat method, this layer can form (referring to above) under at the described condition of the formation of luminescent layer.
As the situation that forms luminescent layer, contain the solution of tackiness agent and at least a hole mobile material by employing, can form more smooth, more uniform hole transmission layer.Adopt the coating of this solution to carry out at the described same way as of luminescent layer.Can adopt any polymer binder, as long as it dissolves at least a hole mobile material institute dissolved solvent.The example and the suitable and preferred concentration of suitable polymers tackiness agent in the description that above luminescent layer is formed, have been provided.
The thickness of hole transmission layer is preferably at 0.5-1000nm, and preferred 1-100nm more preferably selects in the 2-50nm scope.
Hole-injecting material can adopt known organic hole transport compound, the metal-free phthalocyanine (H that for example describes among the JP64-7635 2Pc), copper-phthalocyanine (Cu-Pc) and derivative thereof.In addition, also can adopt some aromatic amine that above is lower than hole transmission layer with the ionizing potential of hole mobile material definition.
Hole injection layer can form by the organic membrane that contains at least a hole-injecting material in the preparation of anode layer and hole transport interlayer.Hole injection layer can pass through formation such as vacuum deposition method, spin-coating method, flow coat method, LB method.The preferred 5nm-5 μ of the thickness of this layer m, more preferably 10nm-100nm.
Electron transport material should have high electronics input rate (from negative electrode) and high electric transmission rate.Electron transport material can be enumerated following material: three (oxine generation)-aluminium (III) and derivative thereof, two (10-hydroxy benzo [h] quino-generation) beryllium (II) and derivative thereof; _ oxadiazole derivative, 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3 for example, 4-_ diazole and dipolymer system thereof, for example 1, two (4-tert-butyl-phenyl-1,3,4-_ di azoly) the inferior biphenyl and 1 of 3-, two (4-tert-butyl-phenyl-1,3,4-_ di azoly) the inferior benzene of 3-; Disclosed Si Suo Suan perylene derivative among two _ oxazole derivatives, triazole derivative, withered derivative, Imidazopyridine derivatives, phenanthroline derivative or the Appl.Phys.Lett.48 (2) (1986) 183.
Electron transfer layer can contain the organic membrane formation of at least a electron transport material by preparation on hole transmission layer or luminescent layer.Electron transfer layer can pass through formation such as vacuum deposition method, spin-coating method, flow coat method, LB method.
Be preferred for hole that the hole suppresses layer and suppress material and have high electronics injections/transmission rate from the electron transfer layer to the luminescent layer, and the ionizing potential higher than luminescent layer, flow out from luminescent layer to avoid the hole, make the luminous efficiency reduction.
The hole suppresses material can adopt such as Balq, TAZ and phenanthroline derivative, for example bathocuproine (bathocuproine) well known materials (BCP):
Figure A20058004219101041
The hole suppresses layer can contain the organic membrane formation that at least a hole suppresses material by preparation between electron transfer layer and luminescent layer.The hole suppresses layer can pass through formation such as vacuum deposition method, spin-coating method, flow coat method, ink-jet printing process, LB method.The thickness of this layer is more preferably selected in the 10nm-100nm scope preferably at 5nm-2 μ m.
As the situation that forms luminescent layer or hole transmission layer, contain the solution of tackiness agent and at least a electron transport material by employing, can form more smooth, more uniform electron transfer layer.
The thickness of electron transfer layer is preferably at 0.5-1000nm, and preferred 1-100nm more preferably selects in the 2-50nm scope.
In a preferred embodiment, the main body chromophoric group be the photoluminescence emission peak at 500-720nm, preferred 520-630nm, the most preferably diketopyrrolopyrrolecocrystals at 540-600nm place.
Light emitting composition is at 500-780, and preferred 520-750 more preferably has maximum fluorescent emission in the 540-700nm scope.In addition, The compounds of this invention preferably shows maximum absorbance in the 450-600nm scope.
The fluorescence quantum yield of light emitting composition (" FQY ") (is measured in inflation toluene or DMF) in 1＞FQY 〉=0.3 scope usually.In addition, in general, the molar absorption coefficient of the present composition is 5000-100000.
Another embodiment of the invention relates to by means commonly known in the art, and (molecular weight is generally 10 at high molecular weight organic materials 3-10 7G/mol; Comprise biological polymer, and plastic material, comprise fiber) in mix compound of the present invention or composition, with to this material method of colouring.
Compound of the present invention and composition can be used to prepare printing ink as the DPP compound of describing among the EP-A-1087005 for example, the printing-ink that is used for printing treatment, be used for flexographic printing, silk screen printing, packages printing, safety ink printing, intaglio or glue roller printing, be used for precompressed stage and textile printing, the office, family expenses or the diagram that are used for such as paper product are used, and for example are used for ballpoint pen, malthoid point, fiber point, card, timber, (timber) tinting material, metal, inking sheet rubber or impact type printing-ink (with impacting ink band); Be used to prepare tinting material, be used for coating, be used for industry or commercial use, be used for that textiles is decorated and industrial mark, be used for roller coat or powder coating or be used for automobile finish, be used for high solid (low solvent), moisture or metallic paint or be used for the painted prescription of water-borne coatings; Be used to prepare coating, fiber, disc or mould coloured plastics; Be used to prepare digital printed, hot wax trans-printing method, ink-jet printing process or heat transfer printing method nonimpact printing material; And the visible light, liquid-crystal display (LCD) or the charge-coupled device (CCD) colour filter that are used to prepare colour filter, particularly 400-700nm; Or be used to prepare makeup; Or be used to prepare polymkeric substance printing ink particle, toning agent, dye laser, dry type duplicating toning agent, liquid duplicating toning agent or electrophotographic toner, and electroluminescent device.
Another preferred embodiment relates to compound of the present invention and the composition purposes as the variable color medium.Have 3 kinds of major techniques to realize the full color organic electroluminescence device:
(i) the three primary colours indigo plant of employing electroluminescent generation, green and red,
(ii) by means of absorbing above electroluminescent blueness, and the variable color medium (CCM) of the fluorescence in green and the redness, electroluminescent blueness or white are changed into photoluminescence green and red,
(iii) the white light emission is changed into blueness by colour filter.
Compound of the present invention or composition can be used for the EL material of above kind (i), also can be used for above-mentioned technology (ii).This is because compound of the present invention or composition can show the high light electroluminescent properties, and the forceful electric power electroluminescent properties.
Technology (ii) can be known from for example US-B-5126214, wherein use tonka bean camphor, 4-(dicyano methylene radical)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans, pyridine, rhodamine 6G, fen _ azoles or other dyestuffs, convert the EL blue light of the about 470-480nm of maximum wavelength to green glow and ruddiness.
The compounds of this invention or composition can be used for above catalogue EL material (iii), as white-light luminescent component, combine with other electroluminescence that replenish, and constitute white luminous.This is because this compound or composition can show strong photoluminescence, and electroluminescent.
The illustrative example of the suitable high molecular weight organic materials that the available present composition is painted is described among the EP-A-1087005.
Especially preferred high molecular weight organic materials is for example such as the ether of cellulose and the ester of ethyl cellulose, Nitrocellulose, cellulose acetate ester and cellulose butyrate especially for the high molecular weight organic materials of preparation coating system, printing-ink or printing ink; Such as aminoplastics, especially the natural resin of urea/formaldehyde and melamine/formaldehyde resin, Synolac, phenoplast, polycarbonate, polyolefine, polystyrene, polyvinyl chloride, polymeric amide, urethane, polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, siloxanes and silicone resin or synthetic resins (polymerization or condensation resins), and their possible mixtures each other.
Also the high molecular weight organic materials of available solubilized form is as membrane-forming agent, for example boiled linseed oil, Nitrocellulose, Synolac, resol, melamine/formaldehyde resin and urea/formaldehyde resin, and acrylic resin.
Described high molecular weight organic materials is particle, plastics, melt form for example, or the solution form is independent or as the mixture acquisition, especially can be used for preparing spin coating solution, paint, coating, printing ink or printing-ink.
In the especially preferred embodiment of the present invention, The compounds of this invention and composition can be used for polyvinyl chloride, polymeric amide, particularly painted such as polyethylene and polyacrylic polyolefinic raw material, and the preparation that comprises the coating system of powder coating, printing ink, printing-ink, colour filter and coating color lake (coatingcolors).
The illustrative example that is used for the preferred adhesive of coating system is alkyd/melamine resin coating, acrylic/melamine cold coating, cellulose acetate ester/cellulose butyrate ester paint, and based on can with the double pack lacquer of the crosslinked acrylic resin of polymeric polyisocyanate.
Therefore, another embodiment of the invention relates to a kind of composition, comprises
(a) 0.01-50%, preferred 0.01-5%, the formula I of especially preferred 0.01-2% weight (based on painted high molecular weight organic materials gross weight meter) or the compound of III or the present composition and
(b) 99.99-50%, preferred 99.99-95%, the high molecular weight organic materials of especially preferred 99.99-98% weight (based on painted high molecular weight organic materials gross weight meter) and
(c) randomly, typical additives such as the significant quantity of for example 0-50% weight (based on (a) and total restatement (b)), such as rheology improving agent, dispersion agent, filler, coatings additive(s), siccative, softening agent, ultra-violet stabilizer, and/or other pigment or corresponding precursor.
In order to obtain different tones, the fluorescence DPP compound of the present invention of formula I or III or the present composition can be valuably and the filler that requires consumption, transparent and opaque white color, colour and/or black pigment, and blast pigment commonly used mixes.
In order to prepare coating system, coating, colour filter, printing ink and printing-ink, usually will be such as the corresponding high molecular weight organic materials of tackiness agent, synthetic resin dispersion etc. with The compounds of this invention or composition, if necessary, with typical additives and/or other pigment or pigment precursor, be dispersed in common solvent or the solvent mixture again such as dispersion agent, filler, coatings additive(s), siccative, softening agent.This can be by dispersing or dissolving every kind of composition itself, or several composition together, then with all the components together, or realizes by once adding all the components.
Therefore, the invention still further relates to the high molecular weight organic materials method of colouring, described method comprises by means known in the art mixes The compounds of this invention or composition in this organic materials.
Therefore, another embodiment of the invention relates to dispersion and the corresponding dispersion that comprises the present composition with The compounds of this invention or preparation of compositions, and the method for coating system, coating, colour filter, printing ink and printing-ink.
Especially preferred embodiment relates to The compounds of this invention or preparation of compositions fluorescent tracer, for example is used for the fluidic leak detection such as lubricant, cooling system etc., and the fluorescent tracer or the lubricant that comprise the present composition.
Painted for high molecular weight organic materials can be with The compounds of this invention or composition, and be nonessential with master batch form, with roller mill, hybrid device or grind device and mix with this high molecular weight organic materials.Usually subsequently with coloured material by such as calendering, inferior mould, push, sprawl, casting or injection molding common method make the final form of expectation.
For varnish stain, coating and printing-ink, high molecular weight organic materials and compound of the present invention or composition itself or with the additive such as filler, other pigment, siccative (siccatives) or softening agent dissolve usually or are dispersed in organic solvent commonly used or the solvent mixture.In this case, can adopt every kind of composition is dispersed or dissolved separately, or two or more compositions disperse or dissolve together, then with all the components blended method.
The invention still further relates to the printing ink of the pigment dispersion of the present composition that comprises painted significant quantity.
The weight ratio of pigment dispersion and printing ink is generally the 0.001-75% weight of printing ink gross weight, preferred 0.01-50% weight.
The preparation and the purposes of colour filter or coloured polymer amount organic materials are well known in the art, for example among Displays 14/2,1151 (1993), EP-A-784085 or the GB-A 2310072 description are arranged.
Colour filter can be used for example printing ink, the printing-ink that particularly can comprise the pigment dispersion that contains the present composition applies, or the pigment dispersion by for example comprising the present composition with can be mixed with by the high molecular weight organic materials (so-called resist) of decomposition, pyrolysis or photodissociation formation.Subsequent preparation can be similar to for example method of EP-A-654711, and by being coated on the base material such as LCD (liquid-crystal display), photoetching and colour developing are carried out then.The preparation of colour filter especially recommends to contain anhydrous solvent or the polymkeric substance pigment dispersion that comprises The compounds of this invention or composition with dispersion medium.
The invention still further relates to comprise and contain The compounds of this invention or composition or with the toning agent of the pigment dispersion of the painted high molecular weight organic materials of the present composition of painted significant quantity.The invention still further relates to and comprise the present composition, the tinting material of the composition of preferred dispersions form, colored plastic, polymkeric substance printing ink particle or non-back-strike print material, or with the painted high molecular weight organic materials of the present composition of painted significant quantity.The painted significant quantity that comprises the color compositions of the present invention of the present composition refers generally to the 0.0001-99.99% weight with the gross weight of its painted material, and preferred 0.001-50% weight especially refers to 0.01-50% weight.The present composition can be used for polymeric amide painted, because they do not decompose in mixing polymeric amide the time.In addition, they also show the thermostability of good especially photostabilization, excellence, especially in plastics.
Organic EL device of the present invention has significant industrial value, because it is suitable for flat-panel monitor, plane luminescence device, duplicating machine or printer light source, liquid-crystal display or counter light source, display mark board and the signal lamp of wall-hanging TV equipment.Compound of the present invention and composition can be used for fields such as organic EL device, xerographic printer photoreceptor, photoelectric commutator, solar cell, image sensor.
Following examples only are used to purposes of the present invention is described, and do not limit the present invention in any way the scope of embodiment.In these embodiments, unless otherwise indicated, " part " refers to " weight part ", and " percentage ratio " refers to " weight percentage ".
Embodiment
Embodiment 1
A) with 70.56g sodium hydride (50-72% analytical pure) with toluene wash to go out to deoil.Sodium hydride, 207.7g diethyl carbonate and the anhydrous dioxane of 1L with washing under agitation is heated to 80 ℃ then.During 3 hours, drip 150g1-ethanoyl naphthalene, and stirred 15 hours at 80 ℃.Allow this reaction mixture be cooled to room temperature, and pour in the 1L ice.Isolate water layer, use 200ml ethyl acetate extraction 2 times.Organic layer is merged, use dried over sodium sulfate, filter, evaporation and dry has obtained 212.6g 1-naphthoyl ethyl acetate.This crude product need not be further purified and be directly used in next reactions steps.
B) with 121g 1-naphthoyl ethyl acetate, 67.4g ethyl chloroacetate, 75.9g salt of wormwood, 300ml acetone and 200ml 1, the 2-glycol dimethyl ether places container.This mixture was stirred 20 hours at 80 ℃.This mixture is cooled to room temperature, with its filtration and drying.Obtained 170g 1-naphthyl ethyl succinate.This crude product need not be further purified and be directly used in next reactions steps.
C) 231g 1-naphthyl ethyl succinate, 543g ammonium acetate and 680ml acetate were stirred 18 hours at 140 ℃.After this reaction mixture is cooled to room temperature, it is poured in the ice.Isolate the solid that is generated, and by this aqueous solution of 300ml dichloromethane extraction.With extraction liquid and common merging, drying.By this crude product of column chromatography purifying, obtained 40.2g 4-ethoxycarbonyl-5-(1-naphthyl) pyrrolidin-2-one.
D) with 56.8g 9-cyano group phenanthrene, 63.3g t-BuOK, 80ml dry toluene and 200ml tertiary amyl alcohol 120 ℃ of stirrings, with added 40.2g 4-ethoxycarbonyl-5-(1-naphthyl) pyrrolidin-2-one in 2 hours in batches.Allow this reaction mixture be cooled to room temperature, and pour in the ice.Collect product by filtering, use toluene wash, and dry.Obtained 72.3g 1,4-diketo-3-(1-naphthyl)-6-(9-phenanthryl)-pyrrolo-[3,4-c] pyrroles.This crude product contains impurity, but is directly used in next step without purifying.
E) with 60g 1,4-diketo-3-(1-naphthyl)-6-(9-phenanthryl)-pyrrolo-[3,4-c] pyrroles, 16.5g sodium hydride (50-72% analytical pure) and 300ml 1-Methyl-2-Pyrrolidone were stirring at room 2 hours.Dropwise 5 7.8g methyl-iodide in this reaction mixture is then with this mixture restir 2 hours.This mixture is poured in the 1L ice, filtered out yellow solid, and use methanol wash.After the drying, obtained 25.2g orange solids (mp.=338-340 ℃).
Figure A20058004219101091
Embodiment 2
Repeat embodiment 1, but be to use 1-cyano group-4-methylnaphthalene to replace 9-cyano group phenanthrene, wherein obtained orange solids (mp.=360-364 ℃).
Figure A20058004219101101
Embodiment 3
Repeat embodiment 1, but be to use 3-methyl-4-cyano group-biphenyl to replace 9-cyano group phenanthrene, wherein obtained orange solids (mp.=235-337 ℃).
Figure A20058004219101102
Embodiment 4
Repeat embodiment 1, but be to use 2-cyano group naphthalene to replace 9-cyano group phenanthrene, wherein obtained orange solids (mp.=239-242 ℃).
Embodiment 5
Repeat embodiment 1, but be to use the luxuriant and rich with fragrance and 4-methyl isophthalic acid-cyano group naphthalene of 9-ethanoyl to replace 1-ethanoyl naphthalene in the step a) and the 9-cyano group phenanthrene (mp.=359-360 ℃) in the step d) respectively.
Figure A20058004219101111
Embodiment 6
25g 2-fluorenes formaldehyde, 11.6g sodium acetate, 9.7g chloration hydro-oxidation ammonium and 150ml acetate were stirred 18 hours at 130 ℃.Allow this reaction mixture be cooled to room temperature, pour in the 200ml water, by filtering collecting precipitation.By column chromatography purifying crude product, obtained 15.57g (63%) 2-cyano group fluorenes.
With 14.29g 2-cyano group fluorenes, 8.9g sodium hydride (60% in oil dispersion) and 150mlNMP stirring at room 2.5 hours.In this reaction mixture, drip the 31.2g methyl-iodide then, and with this reaction mixture room temperature restir 2 hours.This reaction mixture is poured in the 200ml water, and filtered.By column chromatography purifying crude product, obtained 8.5g (60%) 2-cyano group-9, the 9-dimethyl fluorene.
Repeat embodiment 5 then, use 2-cyano group-9, the 9-dimethyl fluorene replaces 4-methyl isophthalic acid-cyano group naphthalene (mp.=209-210 ℃).
Embodiment 7
Specification and the etching that the glass baseplate (Geomatek Co. makes, by the product of electron beam vapor deposition method preparation) of the ITO nesa coating of the thick 120nm of reaching is cut into 30 * 40mm will have been deposited on it.Thus obtained base material is used acetone ultrasonic cleaning 15 minutes, cleaned 15 minutes with Semikoklin 56 then, wash with ultrapure water.Then with this base material with Virahol ultrasonic washing 15 minutes, be immersed in the hot methanol 15 minutes, and dry.Face this base material is processed into element before, the base material of such acquisition was carried out the UV-ozonize 1 hour, and places vacuum gas deposition device, this device is evacuated to internal pressure reaches 1 * 10 -5Pa or lower.According to electrical resistance heating, the thickest CuPc (CuPc) of 20nm that reaches of vapour deposition is to form hole injection layer successively then.Vapour deposition N afterwards, N '-two (1-naphthalene)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (α-NPD) as hole mobile material, the thickest 50nm that reaches, to form hole transmission layer.The thickest DPP compd A-10 (as luminescent material) that reaches 50nm of vapour deposition afterwards is to form luminescent layer.Vapour deposition thickness is that the Alq3 layer of 30nm and lithium fluoride (0.5nm) are to form electron transfer layer and anode respectively then.
The glow peak wavelength of thus obtained luminous element is 585nm, and its high-high brightness is 14210 Cd/m 2With the continuous drive pattern from 963 Cd/m 2Brightness begin luminously, after 70 hours, its brightness keeps 62% of initial intensity.Compare with the compound of reference embodiment 1, compd A-10 shows higher luminous intensity and persistence (table 1).
With reference to embodiment 1
Prepare El element according to the mode identical, except using compound 1 as luminescent layer with embodiment 5.The glow peak wavelength of thus obtained luminous element is 583nm, and its high-high brightness is up to 7225 Cd/m 2With the continuous drive pattern from 844 Cd/m 2Brightness begin luminously, after 70 hours, its brightness keeps 56% of initial intensity.
Figure A20058004219101121
Compound 1 (Cpd.1)
Table 1
Embodiment Compound Luminous (the Cd/m of EL initial performance maximum 2) EL persistence original intensity (Cd/m 2) The % that keeps original intensity *
Embodiment 7 A-10 ?14,210 ?963 ?62％
With reference to 1 Compound 1 ?7,225 ?844 ?56％
*With the continuous drive mode 7 after 0 hour
Embodiment 8
Repeat embodiment 7, but luminescent layer comprises embodiment 1 and embodiment 2 (wt%).Luminescent layer makes by the successive sedimentation method.
Figure A20058004219101131
Compound 2 (Cpd.2)
The glow peak wavelength of thus obtained luminous element is 608nm, and its high-high brightness is up to 16,740 Cd/m 2With the continuous drive pattern from 843 Cd/m 2Brightness begin luminously, after 280 hours, its brightness keeps 68% of initial intensity.Compare with reference embodiment 2, the luminescent layer of embodiment 8 shows higher luminous intensity and persistence (table 2).
With reference to embodiment 2
Prepare El element according to the mode identical, except using compound 1 and compound 2 (1.89%) as luminescent layer with embodiment 8.The glow peak wavelength of thus obtained luminous element is 606nm, and its high-high brightness is up to 14,010 Cd/m 2With the continuous drive pattern from 730Cd/m 2Brightness begin luminously, after 280 hours, its brightness keeps 60% of initial intensity.
Table 2
Embodiment Luminescent layer (H/G) Luminous (the Cd/m of EL initial performance maximum 2) EL persistence original intensity (Cd/m 2) The % that keeps original intensity **
Embodiment 8 A-10/ compound 2 ?16,740 ?843 ?68％
With reference to 2 Compound 1/ compound 2 ?14,010 ?730 ?60％
*With the continuous drive pattern after 280 hours
Embodiment 9
Repeat embodiment 1, but be to use 3,5-two-tertiary butyl benzonitrile replaces 9-cyano group phenanthrene, has wherein obtained orange solids (mp.=251-252 ℃).
Figure A20058004219101141
Embodiment 10
Repeat embodiment 1, but be to use the 2-cyanobiphenyl to replace 9-cyano group phenanthrene, wherein obtained orange solids (mp.=343 ℃).
Figure A20058004219101142
Embodiment 11
Repeat embodiment 1, but be to use the 4-cyanobiphenyl to replace 9-cyano group phenanthrene, wherein obtained orange solids (mp.=247-250 ℃).
Embodiment 12
Repeat embodiment 1, but be to use 1-pyrene formonitrile HCN to replace 9-cyano group phenanthrene, wherein obtained red solid (mp＞300 ℃).
Figure A20058004219101151
Embodiment 13
With 4.25g 4-cyano group fluorenes, 2.6g sodium hydride (60% in oil dispersion) and 50mlNMP stirring at room 2 hours.In this reaction mixture, drip the 9.3g methyl-iodide then, and stirring at room 2 hours.This reaction mixture is poured in the 100ml water, and filtered.By column chromatography purifying crude product, obtained 3.9g (80%) 4-cyano group-9, the 9-dimethyl fluorene.Repeat embodiment 1 then, but be to use 4-cyano group-9, the 9-dimethyl fluorene replaces 9-cyanogen phenanthrene, has wherein obtained orange solids.
Figure A20058004219101152
Embodiment 14
Repeat embodiment 1, but be to use 4-phenyl-1-cyano group naphthalene to replace 9-cyano group phenanthrene, wherein obtained red solid.
Figure A20058004219101153
Embodiment 15
Repeat embodiment 1, but be to use 4-(1-naphthyl)-1-cyano group naphthalene to replace 9-cyano group phenanthrene, wherein obtained red solid.
Embodiment 16
3.6g sodium is added in the 100ml tertiary amyl alcohol, adds spoonful sharp FeCl 3, be heated to 115 ℃ then and dissolve fully until sodium.In this solution, add the 3.7g 5-tertiary butyl-m-dicyanobenzene.7.0g 4-ethoxycarbonyl-5-(1-naphthyl) pyrrolidin-2-one is dissolved in the dioxane, during 2 hours, is added in the above-mentioned solution by dropping funnel., allow this reaction mixture be cooled to room temperature, and pour in 300ml methyl alcohol/300ml water/8ml vitriolic solution after 2 hours 115 ℃ of maintenances.Collect product by filtering, with the cold methanol washing, and dry.Obtained 7.6g dimerization DPP.Crude product contains impurity, but is directly used in next step without purifying.The alkanisation step is similar to EXAMPLE Example 1e) the middle alkanisation of describing, but the amount of sodium hydride and methyl-iodide has doubled.After the drying, orange solids (mp.＞300 ℃ have been obtained; Tg=187 ℃).
Figure A20058004219101162

Claims (10)

1. the fluorescent diketopyrrolopyrroles of following formula:
Figure A2005800421910002C1
R wherein 1And R 2Can be identical or different, and be selected from C 1-C 25Alkyl can be by C 1-C 3Alkyl replaces 1-3 time allyl group, can choose wantonly by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time cycloalkyl, is condensed 1 or 2 time cycloalkyl by phenyl, and described phenyl can be by C 1-C 4-alkyl, halogen, nitro or cyano group replace 1-3 time, alkenyl, cycloalkenyl group, alkynyl, heterocyclic radical, haloalkyl, halogenated alkenyl, the halo alkynyl, ketone or aldehyde radical, ester group, formamyl, silyl, siloxy-, aryl, heteroaryl or-CR 3R 4-(CH 2) m-A 3, R wherein 3And R 4Represent hydrogen or C independently of one another 1-C 4Alkyl or phenyl, described phenyl can be by C 1-C 3Alkyl replaces 1-3 time, A 3Represent aryl or heteroaryl, particularly phenyl or 1-or 2-naphthyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, and m represents 0,1,2,3 or 4,
A 1Representative
Figure A2005800421910002C2
Wherein
X is N or C-R 8,
R 5-R 11Can be identical or different, and be selected from hydrogen, C 1-C 25Alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether, aryl thioethers base, aryl, heteroaryl, heterocyclic radical, halogen, haloalkyl, halogenated alkenyl, halo alkynyl, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, group NR 27R 28, R wherein 27And R 28Represent hydrogen atom, alkyl, the optional cycloalkyl that replaces, the optional aryl that replaces, the optional heteroaryl that replaces, optional heterocyclic radical, the aralkyl that replaces, perhaps R independently of one another 27And R 28Nitrogen-atoms with their institute's bondings forms 5 or 6 yuan of rings, and described ring can be condensed nitro, silyl, siloxy-, replacement or unsubstituted vinyl, perhaps at least two adjacent substituent R by 1 or 2 optional phenyl that replaces 5-R 11Form aromatics, heteroaromatic or aliphatic series and condense ring system,
A 2Aryl that representative does not replace or replaces or the heteroaryl that does not replace or replace, condition is A 2And A 1Have different implications at same intramolecularly, especially
A 2Represent A 1, condition is A 2And A 1Have different implications at same intramolecularly, perhaps
A 2Representative
Figure A2005800421910003C1
R wherein 101-R 123Can be identical or different, and be selected from hydrogen, C 1-C 25Alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether, aryl thioethers base, aryl, heterocyclic radical, halogen, haloalkyl, halogenated alkenyl, halo alkynyl, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, group NR 27R 28, R wherein 27And R 28As defined above, nitro, silyl, siloxy-, replacement or unsubstituted vinyl, perhaps at least two adjacent substituent R 115-R 121Form aromatics, heteroaromatic or aliphatic series and condense ring system,
R 124And R 125Can be identical or different, and be selected from C 1-C 18Alkyl; C 1-C 18Alkoxyl group; C 6-C 18Aryl; C 7-C 18Aralkyl; Perhaps R 124And R 125Form ring, especially 5,6 or 7 yuan of rings together, described ring can be chosen wantonly by C 1-C 8Alkyl replaces, and perhaps can choose wantonly by phenyl to condense 1 or 2 time, and described phenyl can be by C 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group replace 1-3 time;
Perhaps A 2Represent heteroaryl, especially
Figure A2005800421910004C1
R wherein 131-R 152Can be identical or different, and be selected from hydrogen, C 1-C 25Alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether, aryl thioethers base, aryl, heterocyclic radical, halogen, haloalkyl, halogenated alkenyl, halo alkynyl, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, group NR 27R 28, R wherein 27And R 28As defined above, nitro, silyl, siloxy-, replacement or unsubstituted vinyl,
R 153The C that is hydrogen atom, can be interrupted by-O- 1-C 25Alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical,
A 4And A 5Has A independently of one another 2Implication, and
A 6Be cycloalkyl, arylidene or heteroarylidene, described group is optional by C 1-C 8-alkyl or C 1-C 8-alkoxyl group replaces 1-3 time, and condition is not comprise following compounds:
Figure A2005800421910005C1
Figure A2005800421910006C1
2. the fluorescent diketopyrrolopyrroles of claim 1, wherein R 1And R 2Represent C independently of one another 1-C 8Alkyl, C 5-C 12-cycloalkyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, phenyl or 1-or 2-naphthyl, and described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, or-CR 3R 4-(CH 2) m-A 3, R wherein 3And R 4Represent hydrogen or C 1-C 4Alkyl, A 3Represent phenyl or 1-or 2-naphthyl, described group can be by C 1-C 8Alkyl and/or C 1-C 8Alkoxyl group replaces 1-3 time, and m represents 0 or 1.
3. claim 1 or 2 fluorescent diketopyrrolopyrroles, wherein A 1Representative
Figure A2005800421910006C2
Figure A2005800421910007C1
R wherein 25' be C 6-C 12Aryl, especially phenyl or naphthyl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces,
R 300Be C 1-C 8Alkyl, C 6-C 24Aryl or C 2-C 17Heteroaryl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces,
R 21, R 22, R 23, R 25And R 26Be hydrogen, C independently of one another 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-,
R 27And R 28Be independently of one another
R wherein 29, R 30And R 31Be hydrogen, C independently of one another 1-C 8Alkyl, C 1-C 8Alkoxyl group or group-NR 32R 33, R wherein 32And R 33Be independently of one another
Figure A2005800421910007C3
Or
Figure A2005800421910007C4
R wherein 34Be hydrogen, C 1-C 8Alkyl or C 1-C 8Alkoxyl group, perhaps R 27And R 28Nitrogen-atoms with their institute's bondings forms 5 or 6 yuan of heterocycles, for example
Figure A2005800421910008C1
Described group can be condensed by one or two optional phenyl that replaces, for example
Figure A2005800421910008C2
R wherein 216And R 217Represent hydrogen, C independently of one another 1-C 8-alkyl, C 1-C 8-alkoxyl group or phenyl, R 29' and R 30' represent hydrogen, C independently of one another 1-C 8-alkyl or C 1-C 8-alkoxyl group, and X 1Represent hydrogen or C 1-C 8-alkyl; And A 2Represent A 1, condition is A 2And A 1Have different implications at same intramolecularly, perhaps
A 2Representative
Figure A2005800421910009C1
Figure A2005800421910010C1
Wherein
R 25, R 26, R 27And R 28As defined above, and
R 101, R 102, R 103, R 106, R 107, R 110, R 111, R 112, R 115, R 116, R 122, R 123, R 135, R 136, R 137, R 138, R 139, R 140, R 147And R 148Be hydrogen, C independently of one another 1-C 8Alkyl, hydroxyl, sulfydryl, C 1-C 8Alkoxyl group, C 1-C 8Alkylthio, halogen, halo-C 1-C 8Alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro, silyl or siloxy-;
R 124And R 125Can be identical or different, and be selected from C 1-C 18Alkyl; Perhaps R 124And R 125Form ring, especially 5 or 6 yuan of rings together, described ring can be chosen wantonly by C 1-C 8Alkyl replaces, and perhaps can choose wantonly by phenyl to condense 1 or 2 time, and described phenyl can be by C 1-C 8-alkyl, C 1-C 8-alkoxyl group, halogen and cyano group replace 1-3 time; And
R 153Be C 1-C 25Alkyl.
4. the Diketopyrrolo-pyrrole compounds of claim 3, wherein A 1Representative
Figure A2005800421910010C2
Figure A2005800421910011C1
R wherein 300Be C 1-C 8Alkyl, phenyl, described phenyl can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces, R 9Be hydrogen, phenyl, 1-naphthyl, described group can be by one or more C 1-C 8Alkyl or C 1-C 8Alkoxyl group replaces; C 1-C 8Alkyl or C 1-C 8Alkoxyl group, and R 21Be hydrogen, C 1-C 8Alkyl or C 1-C 8Alkoxyl group.
5. the fluorescent diketopyrrolopyrroles of claim 4, wherein said compound is selected from:
Figure A2005800421910012C1
Figure A2005800421910013C1
Figure A2005800421910014C1
Figure A2005800421910015C1
Figure A2005800421910016C1
Figure A2005800421910017C1
Figure A2005800421910018C1
Figure A2005800421910020C1
R wherein 1Be allyl group, C 1-C 8Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2 for example, 2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl, three (C 1-C 8Alkyl) silyl trimethyl silyl for example ,-CH 2-A 3' ,-CHCH 3-A 3Or-CH 2-CH 2-A 3, A wherein 3Represent phenyl, described phenyl can be by C 1-C 8Alkyl replaces 1,2 or 3 time.
6. fluorescent composition, described composition comprise according to claim 1-5 each formula I or the fluorescence host compound of III and/or according to claim 1-5 each formula I or the fluorescence guest compound of III.
7. the fluorescent composition of claim 6, wherein said composition comprise according to claim 1-5 each formula I or fluorescence host compound and the fluorescent quinacridones guest compound of III.
8. electroluminescent device, described device comprise each formula I or the fluorescent chemicals of III or the composition of claim 6 or 7 according to claim 1-5.
9. the composition of a high molecular weight organic materials, described composition comprises
(a) based on the gross weight meter of painted high molecular weight organic materials, 0.01-50% weight according to claim 1-5 each formula I or the composition of the fluorescent chemicals of III or claim 6 or 7 and
(b) based on the gross weight meter of painted high molecular weight organic materials, the high molecular weight organic materials of 99.99-50% weight and
(c) typical additives of optional significant quantity
Claim 1-5 each formula I or the composition of the fluorescent chemicals of III or claim 6 or 7 at preparation printing ink, tinting material, coloured plastics, coating, non-back-strike print material, colour filter, makeup, polymkeric substance printing ink particle, toning agent, as fluorescent tracer, the purposes in variable color medium, solid-state dye laser, EL laser apparatus and electroluminescent device.
CN200580042191.7A 2004-12-09 2005-11-30 Fluorescent diketopyrrolopyrroles Pending CN101072842A (en)

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CN103619855A (en) * 2011-06-22 2014-03-05 巴斯夫欧洲公司 Diketopyrrolopyrrole oligomers for use in organic semiconductor devices
CN104094435A (en) * 2011-09-02 2014-10-08 巴斯夫欧洲公司 Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers
TWI580681B (en) * 2011-09-02 2017-05-01 巴地斯顏料化工廠 Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers
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Publication number Priority date Publication date Assignee Title
CN103619855A (en) * 2011-06-22 2014-03-05 巴斯夫欧洲公司 Diketopyrrolopyrrole oligomers for use in organic semiconductor devices
CN103619855B (en) * 2011-06-22 2017-08-08 巴斯夫欧洲公司 Diketopyrrolopyrrolecocrystals oligomer for organic semiconductor device
CN104094435A (en) * 2011-09-02 2014-10-08 巴斯夫欧洲公司 Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers
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