CN1308414C - Pyrromethene metal complex and light emitting device composition and light emitting devices using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent dye capable of being utilized for light emitting device, etc., and the light emitting device having high luminance efficiency and high chromatic purity using the fluorescent. SOLUTION: This pyrromethene metal complex is represented by the general formula (1) [wherein R<1> , R<2> and L may be same or different and are each selected from a hydrogen atom and an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, hydroxy group, mercapto group, an alkoxy group, an alkylthio group, an aryl ether group, an aryl thioether group, an aryl group, a heterocyclic group, a halogen group, a haloalkane group, a haloalkene group, a haloalkyne group, cyano group, an aldehyde group, carbonyl group, carboxyl group, an ester group, carbamoyl group, an amino group, nitro group, silyl group and a siloxanyl group and fused aromatic and alicyclic rings each formed between adjacent substituents; M represents a metal having a valence of m and is at least one kind compound selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum; Ar<1> to Ar<5> represent each an aryl group].

Description

Methylene pyrrole metal complex compound, the light emitting element material that uses this complex compound and luminous element

The present patent application is that application number is the dividing an application of application for a patent for invention of CN02124569.X (applying date is on April 25th, 2002).

Technical field

The present invention relates to can be used as the methylene pyrrole metal complex compound of fluorescence dye and the luminous element that uses this complex compound.

Background technology

In recent years, for from the negative electrode injected electrons and from the anode injected holes in the organic fluorescent between the two poles of the earth again in conjunction with the time luminous organic laminated film luminous element research begin to enliven.That this element is characterised in that is slim, the high brightness luminescent under the low driving voltage, multicolor luminous by selecting fluorescent material to cause, is therefore more and more gazed at.

Since the ironed membrane element high brightness luminescents of discovery organic layer such as C.W.Tang of コ ダ Star Network company (Appl.Phys.Lett.51 (12) 21, p.913,1987), most research institutions are carrying out this research.The representativeness of organic laminated film luminous element that the research group of コ ダ Star Network company proposes constitute be on the ito glass substrate, set gradually the cavity conveying diamine compound, as the oxine aluminium of luminescent layer, then as the Mg:Ag of negative electrode, and under the driving voltage about 10V, might produce 1000cd/m ²Green emitting.Present organic laminated film luminous element also has the element that formation is changed that electron supplying layer etc. is set except said elements constitutes element.

The research of green luminescent material gets along with most in multicolor luminous, and in just waiting in expectation now red illuminating material and the blue emitting material, the luminescent material that weather resistance is good, have sufficient brightness and purity of color characteristic, and be that purpose is just being carried out concentrated research to improve characteristic.

As red illuminating material, perylene kinds, perinone class, porphyrin class, Eu complex compound (Chem.Lett., 1267 (1991)) etc. such as two (diisopropyl phenyl) perylene for example.

In addition, as the gimmick that obtains emitting red light, also studying and in main material, sneaking into the method for micro-red fluorescence material as doping agent.As main material, for example be metal complex, two (10-benzoquinoline alkylol cpd) beryllium complex, diaryl butadiene derivatives, diphenyl ethylene derivatives, benzoxazole derivative, benzothiazole derivant of the quinolinol derivative of representative etc. with three (8-quinolinol compound) aluminium complex, wherein, by containing 4-(dicyano methylene radical)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans, metal phthalocyanine (MgPc, AlPcCl etc.) compound, squarilium compound, violanthrone compound, can obtain emitting red light as doping agent.

But, in the luminescent material that uses in the prior art (main material, dopant material), most luminous efficiency low consumption electric power height, and weather resistance is low, and component life is short.And even most luminescent material has strong fluorescence intensity under solution state, owing to concentration delustring and formation exciplex or excimer, fluorescence intensity also work reduces, and can not obtain the luminous of high brightness when being applied to luminous element under filminess.Particularly for red illuminating material (main material and dopant material), the material that purity of color and brightness take into account is considerably less to be a big problem.

In addition, be the example that the following organic fluorescent substance of the above 720nm of 580nm obtains emitting red light as using diketone pyrrolo-[3,4-c] pyrrole derivative and fluorescence peak wavelength, there is the spy to open the 2000-208270 communique, but do not obtain the luminous of high brightness.

Disclosure of the Invention

The objective of the invention is to solve above-mentioned prior art problems, and the novel methylene pyrrole metal complex compound that can obtain luminous efficiency height, luminous element that purity of color is good is provided, and the luminous element that uses this complex compound.

The preferred plan that carries out an invention

Below, be elaborated at the methylene pyrrole metal complex compound of the present invention shown in the general formula (1).

Here, R ¹, R ²Can be the same or different with L, be selected from hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether group, fragrant thioether group, aryl, heterocyclic radical, halogen, haloalkane, haloalkene, acetylenic halide, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, amino, nitro, silyl, siloxanes, the condensed ring that between adjacent substituting group, forms and aliphatics ring.M represents the metal of m valency, is selected from least a in boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, the platinum.Ar ¹～Ar ⁵The expression aryl.

In these substituting groups, alkyl is representative examples of saturated aliphatic alkyl such as methyl, ethyl, propyl group, butyl for example.Cycloalkyl is saturated fat ring type alkyl such as cyclopropyl, cyclohexyl, norcamphyl, adamantyl for example.Aralkyl is the aromatic hydrocarbyl that connects by aliphatic alkyl such as benzyl, styroyl for example.Alkenyl for example vinyl, allyl group, butadienyl etc. contains the unsaturated fatty hydrocarbons base of two keys.Cycloalkenyl group for example cyclopentenyl, cyclopentadienyl, cyclohexenyl etc. contains the unsaturated lipid ring type alkyl of two keys.Alkynyl for example ethynyl etc. contains triple-linked unsaturated fatty hydrocarbons base.Alkoxyl group is the aliphatic alkyl that connects by ehter bond such as methoxyl group for example.Alkylthio for example the Sauerstoffatom of the ehter bond of alkoxyl group by sulphur atom metathetical compound.Aryl ether group is the aromatic hydrocarbyl that connects by ehter bond such as phenoxy group for example.The virtue thioether group for example the Sauerstoffatom of the ehter bond of aryl ether group by sulphur atom metathetical compound.In addition, aryl aromatic hydrocarbyls such as phenyl, naphthyl, xenyl, phenanthryl, terphenylyl, pyrenyl for example.Heterocyclic radical for example furyl, thienyl,  azoles base, pyridyl, quinolyl, carbazyl etc. has the ring texture group of atom beyond the carbon.Halogen is fluorine, chlorine, bromine, iodine for example.Haloalkane, haloalkene, acetylenic halide for example abovementioned alkyl, alkenyl, alkynyl part or all of of trifluoromethyl etc. are used above-mentioned halogen substituted compounds.Also comprise the compound that replaces with aliphatic hydrocarbon, ester ring type hydrocarbon, aromatic hydrocarbons, heterocycle etc. in aldehyde radical, carbonyl, ester group, formamyl, the amino.Silyl is silicon compound group such as trimethyl silyl for example.Siloxanes is the silicon compound group that connects by ehter bond such as trimethylammonium first siloxanes for example.Above-mentioned any substituting group can be unsubstituted or replace.Condensed ring that forms between adjacent substituting group or aliphatics ring also can be unsubstituted or replace in addition.

In addition, in the metal complex of general formula (1) expression, the fluorescent quantum yield height of the boron complex of following general formula (2).

Here, R ³～R ⁶Can be the same or different, be selected from hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether group, fragrant thioether group, aryl, heterocyclic radical, halogen, haloalkane, haloalkene, acetylenic halide, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, amino, nitro, silyl, siloxanes, the condensed ring that between adjacent substituting group, forms and aliphatics ring.Ar ⁶～Ar ¹⁰The expression aryl.These substituent explanations are identical with the explanation in the above-mentioned general formula (1).

If the Ar of above-mentioned general formula (1) ¹～Ar ⁴In at least one, the Ar of above-mentioned general formula (2) ⁶～Ar ⁹In at least one be that alkyl more than 4 replaces by carbonatoms, then can improve the dispersiveness in film, and obtain high brightness luminescent.If also have being easy to get property and the synthetic easness of considering material, the R of then preferred above-mentioned general formula (2) ⁵And R ⁶Be fluorine.As the object lesson of above-mentioned methylene pyrrole metal complex compound, compound for example shown below.

Methylene pyrrole metal complex compound of the present invention for example can be by following method preparation.

In the presence of Phosphorus Oxychloride, with the compound of the compound of following general formula (7) expression and general formula (8) expression 1, in the 2-ethylene dichloride after the heating, in the presence of triethylamine, with the compound of following general formula (9) expression 1, react in the 2-ethylene dichloride, obtain the metal complex of general formula (1).Here, Ar ¹～Ar ⁵, R ¹And R ², M, L, m be same as described above.J represents halogen.

Methylene pyrrole metal complex compound of the present invention is suitable as light emitting element material and uses.To be elaborated at luminous element of the present invention below.

For luminous, anode is if transparent words, preferred stannic oxide, Indium sesquioxide, indium tin oxide target conductive metal oxides such as (ITO), perhaps metal such as gold and silver, chromium, inorganic conductive such as cupric iodide, cupric sulfide material, electric conductive polymers such as Polythiophene, polypyrrole, polyaniline etc. especially preferably use ito glass and nesa glass.As long as the resistance of transparency electrode can provide enough electric current just passable to element is luminous, from the viewpoint of the consumption electric power of element, preferred low-resistance electrode.For example if the following ITO substrate of 300 Ω/ owing to bring into play function as element electrode, therefore especially preferably uses the low resistance goods.The thickness of ITO can at random be selected according to resistance value, usually between 100～300nm.In addition, glass substrate uses soda-lime glass, non-alkali glass etc., and in order to keep physical strength, and thickness is enough thickness for well, so if then be enough more than the 0.5mm.Glass material ion of stripping from glass few for well, therefore be preferably non-alkali glass, also can use the soda-lime glass of implementing insulation coatings such as SiO2 in addition.Also have, as long as the anodic stable performance, it is glass that substrate there is no need, and for example forms anode and also be fine on plastic substrate.ITO film formation method is not confined to electronic beam method, sputtering method, chemical reaction method etc. especially.

Negative electrode preferably can inject electronics the material of this organic matter layer effectively, and specifiable is platinum, gold and silver, copper, iron, tin, zinc, aluminium, indium, chromium, lithium, sodium, potassium, calcium, magnesium, caesium, strontium etc.For the injection efficiency that improves electronics and improve element characteristic, lithium, sodium, potassium, calcium, magnesium, caesium or the alloy that contains these low workfunction metal are effective.But, great majority in these low workfunction metal are unstable usually in atmosphere, for example, the method for the electrode that the lithium that is to use in organic layer the trace that mixes that can enumerate as preferred example and magnesium, caesium (with the film thickness gauge of vacuum evaporation, below 1nm) and stability are high.Also can use the inorganic salt of lithium fluoride and so in addition.Also have for guard electrode metals such as preferred platinum, gold and silver, copper, iron, tin, aluminium, indium, or use the alloy of these metals, and inorganicss such as lamination silicon-dioxide, titanium dioxide, silicon nitride, polyvinyl alcohol, vinylchlorid, hydro carbons polymer etc.The making method of these electrodes also can be the method that resistive heating, electron beam, sputter, ion plating, coating etc. can obtain conducting.

Luminophore can be 1) hole transporting layer/luminescent layer, 2) hole transporting layer/luminescent layer/electron supplying layer, 3) luminescent layer/electron supplying layer, 4) hole transporting layer/luminescent layer/hole trapping layer, 5) hole transporting layer/luminescent layer/hole trapping layer/electron supplying layer, 6) luminescent layer/hole trapping layer/electron supplying layer, and 7) the aforesaid combination material is mixed in the form of one deck any.That is, constitute as element, except above-mentioned 1)～6) the laminated multi-layer structure, also can resemble 7) one deck luminous material layer only is set or contains luminescent material and the layer of hole transporting material, hole trapping layer and electron transport materials.Also have, luminophore is equivalent to self luminous material or helps in its luminous material any among the present invention, and refers to and luminous relevant compound, layer etc.

Containing diketone pyrrolo-[3,4-c] pyrrole derivative and fluorescence peak wavelength with ad hoc structure in the luminophore of the present invention is following organic fluorescent substance or methylene pyrrole metal complex compound of the above 720nm of 580nm.These materials can be included in above-mentioned arbitrary layer, but because all have fluorescence, so preferably be contained in the luminescent layer.

So-called hole transporting layer is meant from the anode injected hole and then carries the layer in hole.As hole transporting material, concrete specifiable is N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-4,4 '-phenylbenzene-1,1 '-diamines, N, N '-two (1-naphthyl)-N, N '-phenylbenzene-4,4 '-phenylbenzene-1, triphenyl amines such as 1 '-diamines, two (N-allyl group carbazoles) or two (N-alkyl carbazole) class, pyrazoline derivative, stilbene compound, diphenyl ethylene derivatives, hydrazone compounds,  oxadiazole derivative and phthalocyanine derivates, with the derivatives of porphyrin is the heterogeneous ring compound of representative, have above-mentioned monomeric polycarbonate and styrene derivatives at side chain in the polymer class, polyvinyl carbazole, polysilane etc., but preferably can form element necessary film and can be in making, and then can carry the compound in hole from the anode injected hole.These compounds can use separately, also can mix use with multiple derivative.

In fact so-called luminescent layer is meant the layer that luminescent material forms, and luminous element of the present invention utilizes electric energy in regional luminous below the above 720nm for 580nm of spike length.If less than 580nm, can not obtain the good emitting red light of purity of color although peak width is narrow, if greater than 720nm,, can not obtain the high brightness emitting red light of excellent in efficiency owing to visual impression response variation.In addition, luminescent material of the present invention contain following (a) or (b) shown in compound at least a.

(a) [3,4-c] pyrrole derivative of the diketone pyrrolo-shown in the general formula (3) and fluorescence peak wavelength are the following organic fluorescent substance of the above 720nm of 580nm.

R ⁷And R ⁸Can be the same or different, be selected from carbonatoms and be 1～25 alkyl, or following general formula (4).

(R ⁹And R ¹⁰Can be the same or different, be selected from hydrogen, carbonatoms and be 1～4 alkyl, do not replace or be the phenyl that 1～3 alkyl replaces, Ar by carbonatoms ¹³Be selected from and have substituent phenyl, the naphthyl that is selected from alkyl, alkoxyl group, halogen, the phenyl.N represents 0～4 integer)

Ar ¹¹And Ar ¹²Can be the same or different, be selected from phenyl, naphthyl, styryl, carbazyl.

(b) contain the light emitting element material of the methylene pyrrole metal complex compound shown in the above-mentioned general formula (1).

(a) in, diketone pyrrolo-[3 shown in the general formula (3), 4-c] pyrrole derivative and fluorescence peak wavelength be that the following organic fluorescent substance of the above 720nm of 580nm all can be used as dopant material or uses as main material, but preferably use diketone pyrrolo-[3,4-c] pyrrole derivative is as main material, and the use organic fluorescent substance is as the adulterating method of dopant material.

Below, be elaborated for the substituting group of the compound of general formula (3) and (4) expression.In these substituting groups, R ⁷And R ⁸Carbonatoms be that 1～25 alkyl can be that straight chain also can be a side chain, concrete specifiable is 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 3-tetramethyl butyl, the 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl, pentacosyl etc.Preferably carbonatoms is 1～8 methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2,2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl, 2-ethylhexyl, more preferably carbonatoms is 1～4 methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl and butyl, the tertiary butyl.

R ⁹And R ¹⁰Carbonatoms be that 1～4 alkyl is represented methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, same R ³And R ⁴The carbonatoms that is replaced by phenyl be that 1～3 alkyl is represented methyl, ethyl, n-propyl, sec.-propyl.Ar ¹³When being phenyl, this phenyl is replaced position at least by in alkyl, alkoxyl group, halogen, the phenyl any, but also can have 3 positions to be replaced by identical or different substituting group.In these substituting groups, the preferred carbonatoms of alkyl is 1～8.Concrete specifiable is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2,2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl, 2-ethylhexyl.Equally, the preferred carbonatoms of alkoxyl group is 1～8, concrete specifiable 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, 2-ethyl hexyl oxy.Halogen is represented fluorine, chlorine, bromine, iodine.Phenyl in the substituting group can also be 1～8 alkyl, alkoxyl group replacement by carbonatoms.These object lessons are same as described above.Ar ¹³When being naphthyl, 1-naphthyl, 2-naphthyl all can, when they had substituting group, substituting group can both be suitable for arbitrarily in addition, but preferably identical with the substituting group of above-mentioned phenyl substituting group.

Ar ¹¹And Ar ¹²Be selected from phenyl, naphthyl, styryl, carbazyl, when being naphthyl, styryl, carbazyl, can these groups any in conjunction with the position on diketone pyrrolo-[3,4-c] pyrrole skeleton combination.At phenyl, naphthyl, styryl, when carbazyl contains substituting group, substituting group is selected from hydrogen, cyano group, halogen, alkyl, cycloalkyl, aralkyl, alkoxyl group, alkylthio, aryloxy, fragrant thioether group, aryl, heterocyclic radical, amino, silyl, the condensed ring that forms and aliphatics ring between adjacent substituting group.In these substituting groups, halogen is same as described above.Alkyl can be that straight chain also can be a side chain, and preferred carbonatoms is 1～25, and more preferably carbonatoms is 1～8.Concrete example is same as described above.The preferred carbonatoms of cycloalkyl is 5～12, and concrete specifiable is cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ring undecyl, cyclo-dodecyl, more preferably cyclopentyl, cyclohexyl, suberyl, ring octyl group.Aralkyl has no particular limits for carbonatoms, but preferred 7～24, concrete specifiable is benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-Er Jiajibianji, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl, ω-phenyl-docosyl, benzyl more preferably, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-Er Jiajibianji, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, and then benzyl preferably, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-Er Jiajibianji, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl.The preferred carbonatoms of alkoxyl group is 1～8, and concrete example is same as described above.Alkylthio is that the Sauerstoffatom of ehter bond of alkoxyl group is by sulphur atom metathetical compound.The aromatic hydrocarbyl that the aryloxy ordinary representation connects by ehter bond, but in the present invention, also comprising carbonatoms is the compound that 6～24 aromatic hydrocarbons, saturated or undersaturated heterocycle connect by ehter bond.These aromatic hydrocarbonss or heterocycle can not be substituted, and can are 1～8 alkyl and/or alkoxyl group replacement by carbonatoms yet.The virtue thioether group is meant that the Sauerstoffatom of ehter bond of aryloxy is by sulphur atom metathetical compound.The preferred carbonatoms of aryl is 6～24, and concrete specifiable is phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl, phenanthryl, 2-fluorenyl, 9-fluorenyl, 2-anthryl, 9-anthryl, more preferably phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl.These aryl also can further be 1～8 alkyl and/or alkoxyl group replacement by carbonatoms.Heterocyclic radical represents to have nitrogen, oxygen, the ring texture group of atom beyond the carbon such as sulphur, can be saturated also can be undersaturated group, preferred unsaturated heterocycle base, concrete specifiable is thienyl, 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, porphyrin (プ リ ニ Le) base, quinolizinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridines (Na Off チ リ ジ ニ Le) base, quinoline  quinoline base, quinazolyl, quinolyl, phthalein pyridine base, carbazyl, carbolinyl, the benzotriazole base, the benzoxazol base, phenanthridinyl, acridyl, pool pyridine base, the phenanthroline base, phenazinyl, isothiazolyl, phenothiazinyl, different  azoles base, the furazan base, fen  piperazine base.These heterocyclic radicals can also further be 1～8 alkyl and/or alkoxyl group replacement by carbonatoms.Amino also comprise in two hydrogen at least one be that 1～25 alkyl, carbonatoms are 5～12 cycloalkyl, to contain carbonatoms be that aryloxy, the carbonatoms of 6～24 aromatic hydrocarbons is the compound that 6～24 aryl, heterocyclic radical etc. replace by carbonatoms, and carbonatoms be 6～24 aryl, heterocyclic radical can be that 1～8 alkyl and/or alkoxyl group replace by carbonatoms also.Silyl comprises that also in three hydrogen at least one is that 1～25 alkyl, carbonatoms are 5～12 cycloalkyl, to contain carbonatoms be that aryloxy, the carbonatoms of 6～24 aromatic hydrocarbons is the compound that 6～24 aryl, heterocyclic radical etc. replace by carbonatoms, and carbonatoms be 6～24 aryl, heterocyclic radical can be that 1～8 alkyl and/or alkoxyl group replace by carbonatoms also.Condensed ring that forms between adjacent substituting group or aliphatics ring can not be substituted also and can be substituted.

As the preferred example of above-mentioned diketone pyrrolo-[3,4-c] pyrrole derivative, the structure shown in can being listed below.

Diketone pyrrolo-of the present invention [3,4-c] pyrrole derivative synthetic, specifiable as a reference is the embodiment etc. of No. 0133156, No. 0094911, the open communique of EP and the open communique of EP.In the presence of potassium tert.-butoxide, aromatic nitrile and ni-isopropyl succinate are heated the diketopyrrolo-pyrrole precursor that obtains in tertiary amyl alcohol, in the presence of potassium tert.-butoxide, in dimethyl formamide, heat with haloalkyl or halogeno-benzyl, handle by ordinary method, can obtain diketone pyrrolo-[3,4-c] pyrrole derivative.

Diketone pyrrolo-of the present invention [3,4-c] pyrrole derivative has fluorescence, and the fluorescent quantum yield of most of derivative is (among toluene or the DMF) or to have molar absorptivity be value more than 5000 more than 0.3.

Among the present invention in order to obtain emitting red light, use the fluorescence peak wavelength to be the organic fluorescent substance below the above 720nm of 580nm, specifically, can use the fused-ring derivatives of aromatic hydrocarbonss such as terylene, pyrido thiadiazoles and Pyrazolopyridine, condensed heterocyclic derivates such as diketopyrrolo-pyrrole, Naphthalamide derivatives such as two (diisopropyl phenyl) perylene tetracarboxylic acid imide, the perinone derivative, with rare earth complexes such as Eu complex compound such as methyl ethyl diketone and benzoyl acetone and phenanthroline etc. as part, 4-(dicyano methylene radical)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans and analogue thereof, the magnesium phthalocyanine, metal phthalocyanine derivatives such as aluminium chlorine phthalocyanine, metal porphyrin derivatives such as zinc protoporphyrin, thiophene derivant, pyrrole derivative, the rhodamine compound, denitrogenation flavine (the デ ア ザ Off ラ PVC Application) derivative of mixing, coumarin derivatives oxazine compound phenoxazine derivative thiophene evil hexazinone derivative, quinoline a word used for translation derovatives, benzothioxanthene and analogue thereof, the dicyano vinyl arene derivative.

In order to obtain to have the emitting red light of good purity of color characteristic, in above-mentioned organic fluorescent substance, preferred compound or its metal complex that contains the methylene pyrrole skeleton shown in the following general formula (5) that use.

R ¹¹～R ¹⁷In at least one contain aromatic nucleus or and adjacent substituting group between form condensed ring.Other is selected from hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether group, fragrant thioether group, aryl, heterocyclic radical, halogen, haloalkane, haloalkene, acetylenic halide, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, amino, nitro, silyl, siloxanes, the condensed ring that forms and aliphatics ring between adjacent substituting group.X is carbon or nitrogen, but when being nitrogen, above-mentioned R ¹⁷Do not exist.The metal of metal complex is selected from least a in boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, the platinum.

These substituent explanations are identical with the compound of above-mentioned general formula (1).Also have, in order to obtain high brightness characteristic, the more preferably high compound of fluorescent quantum yield.Therefore, as the metal complex of compound, more preferably use the compound of following general formula (6) expression with above-mentioned methylene pyrrole skeleton.

R ¹⁸～R ²⁴In at least one contain aromatic nucleus or and adjacent substituting group between form and to condense aromatic nucleus.Other and R ²⁵, R ²⁶Be selected from hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl group, alkynyl, hydroxyl, sulfydryl, alkoxyl group, alkylthio, aryl ether group, fragrant thioether group, aryl, heterocyclic radical, halogen, haloalkane, haloalkene, acetylenic halide, cyano group, aldehyde radical, carbonyl, carboxyl, ester group, formamyl, amino, nitro, silyl, siloxanes, the condensed ring that between adjacent substituting group, forms and aliphatics ring.X is carbon or nitrogen, but when being nitrogen, above-mentioned R ²⁴Do not exist.

These substituent explanations are identical with the compound of above-mentioned general formula (1).

Also have,, more preferably use compound as the general formula (1) of methylene pyrrole metal complex compound for the fluorescence intensity that suppresses in the film reduces and the acquisition high brightness luminescent.

As above-mentioned preferred example with compound of methylene pyrrole skeleton, there is no particular limitation, specifiable be above-mentioned general formula (1) metal complex and following shown in object lesson.

When dopant material shifted, the fluorescence spectrum of main material and the overlapping of the absorption spectrum of dopant material (excitation spectrum) were necessary to energy from main material.Here, the fluorescence spectrum of main material is the fluorescence spectrum of measuring under the filminess of main material, and the absorption of doping agent (exciting) spectrum and fluorescence spectrum are respectively absorption (exciting) spectrum and the fluorescence spectrums of measuring under the solution state of dopant material.This is that trace doped dopant material is to exist with the state that is similar to solution in main material owing in luminous element, exist with filminess with respect to main material.In addition, as above-mentioned compound or its metal complex with methylene pyrrole skeleton, the Stokes shift of the dopant material that purity of color is good (excitation spectrum peak and fluorescence spectrum peak poor) is that several-tens nm are wide, in the time of will obtaining the emitting red light of high color purity from the dopant material below the above 720nm of 580nm, the absorption spectrum of dopant material (excitation spectrum) is with regard to yellowing, yellowish-orange, orange, reddish orange, red area (the above 720nm of 540nm is following).If it is little that the fluorescence spectrum of main material is in yellow-green colour, green, blue-greenish colour, blueness, bluish voilet, violet region and the spectra overlapping also shorter than yellow wavelengths, then energy shifts and just can not carry out fast, and can not obtain luminous from dopant material, even obtain also residual luminous from main material of having, and whitening etc. takes place, can not obtain the emitting red light of high color purity.

For the above reasons, luminous with high brightness, high color purity below the above 720nm of 580nm in order to make dopant material, main material more preferably fluorescence peak wavelength is the following material of the above 720nm of 540nm.It is desirable to corresponding material with fluorescence such as yellow, yellowish-orange, orange, reddish orange, redness.Thereby when using general formula (1) as main material, the diketone pyrrolo-of general formula (1) [3,4-c] pyrrole derivative preferably has the material of yellow, yellowish-orange, orange, reddish orange, red fluorescence.

(b) under the situation, contain the methylene pyrrole metal complex compound shown in the general formula (1) as luminescent material.

At present, known methylene pyrrole metal complex compound is as luminescent material, and is particularly luminous as the dopant material exhibit high brilliance, also known to import aromatic nucleus etc. on 1,3,5,7 of methylene pyrrole skeleton in addition, emitting red light can occur.But,, therefore can not obtain to satisfy simultaneously the emitting red light of luminosity and colourity because the concentration delustring takes place present methylene pyrrole compound easily.If on 8 of methylene pyrrole skeleton, import substituting group,, can reduce the concentration delustring by its substituent solid and electronic effect.On the other hand, the substituent rotation on 8 will cause the fluorescent quantum yield of methylene pyrrole metal complex compound to reduce.Therefore, methylene pyrrole metal complex compound of the present invention imports aryl on 8 of methylene pyrrole skeleton, and by suppressing its rotation, the fluorescent quantum yield uprises, and has suppressed the concentration delustring.By making the Ar in the general formula (1) ¹And Ar ⁴, the Ar in the general formula (2) ⁶And Ar ⁹Be aryl simultaneously, can realize the inhibition of this rotation.Methylene pyrrole metal complex compound of the present invention also can be used as main material and uses, but because the half-peak value of fluorescent quantum yield height, luminescent spectrum is little, more preferably uses as dopant material.

Can produce the concentration frosting phenomenon when doping is too much, use with the amount below the 10 weight % with respect to principal goods choosing of fine quality, more preferably below the 2 weight %.As adulterating method, can form by common vapour deposition method with main material, also can with evaporation simultaneously after the main material pre-mixing.In addition, dopant material can be included in the whole main material, also can be included in a part of main material.Dopant material can also can be disperseed by lamination.Even the methylene pyrrole metal complex compound because extremely trace also can be luminous, therefore also can be clipped in main material with the sandwich shape methylene pyrrole metal complex compound of trace and carry out lamination.The dopant material that adds in the luminescent material, there is no need only to be confined to a kind of in the above-mentioned methylene pyrrole metal complex compound, can mix and use multiple methylene pyrrole metal complex compound, also more than one known dopant materials can be mixed use with the methylene pyrrole metal complex compound.Specifically, can make at present Naphthalamide derivatives such as known two (diisopropyl phenyl) perylene tetracarboxylic acid imide, the perinone derivative, with rare earth complexes such as Eu complex compound such as methyl ethyl diketone or benzoyl acetone and phenanthroline etc. as part, 4-(dicyano methylene radical)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans and analogue thereof, the magnesium phthalocyanine, metal phthalocyanine derivatives such as aluminium chlorine phthalocyanine, the rhodamine compound, denitrogenation flavine (the デ ア ザ Off ラ PVC Application) derivative of mixing, coumarin derivatives, coexistences such as quinoline a word used for translation derovatives phenoxazine derivative oxazine compound.

Be not particularly limited as main material, diketone pyrrolo-[3 except above-mentioned substituting group qualification, 4-c] outside pyrrole derivative and other Pyrrolopyrrole derivatives, can use fused-ring derivatives such as anthracene and pyrene, with three (8-quinolinol compound) aluminium is the metal chelating combination oxynoid compound of representative, toluylene radical derivatives such as diphenylethyllene anthracene derivant and diphenylethyllene benzene derivative, the tetraphenylbutadiene derivative, coumarin derivatives oxadiazole derivative, Pyrrolopyridine derivatives, the perinone derivative, cyclopentadiene derivant oxadiazole derivative, thiadiazoles and pyridine derivate, polyphenylene vinylene derivative in the polymer class, the poly(p-phenylene) radical derivative, also has polythiofuran derivative etc.

As the electron transport materials among the present invention, providing the electronics that transports expeditiously from negative electrode between the electrode of electric field to be necessary, so the preferred electron injection efficiency is high and more effectively carry the material that injects electronics.For this reason, preferred electron avidity is big, the electron migration degree is big and excellent in stability, is difficult to produce the material of the impurity that forms trap when preparation and use.Specifically, having with oxine aluminium is oligomeric pyridine derivate, phenanthroline derivative, quinoline, the aromatic series phosphorous oxides etc. such as quinolinol derivative metal complex, tropolone metal complex, flavonol metal complex, perylene derivative, perinone derivative, naphthalene derivatives, coumarin derivatives, oxadiazole derivative, aldazine derivative, toluylene radical derivative, pyrazines derivatives, two pyridines, three pyridines of representative.These electron transport materials both can use separately, also can use with different electron transport materials lamination or mixing.

In order to obtain the more emitting red light of high-level efficiency, high color purity, it is desirable to the height of combination rate again in hole and electronics in above-mentioned luminescent layer, and the combination again that beyond luminescent layer, does not take place.When using diketone pyrrolo-[3,4-c] pyrrole derivative in luminescent material, the ionizing potential of electron transport materials is preferably more than the 5.9eV.Also have, in order to keep long-time stable emitting red light, stable electron transport materials during preferably for long-time energising, therefore the molecular weight of the electron transport materials that uses is preferably more than 400, more preferably more than 500, so that preferred more than 600.This is because molecular weight is lower than at 400 o'clock, easily produces the thermally labile phenomenon.Also have,, can enumerate the second-order transition temperature of materials used, the stable amorphous thin film of the high more easy more formation of second-order transition temperature as the index of the thermostability of filminess.Therefore, the second-order transition temperature of materials used is preferably more than 90 ℃, more preferably more than 110 ℃, so that preferred more than 150 ℃.Above-mentioned electricity is in carrying material preferably to have a plurality of female skeletons by conjugated link(age), aromatic hydrocarbons, aromatic heterocycle or mix the organic compound of the structure of any connection in these the group.Female skeleton can directly use female skeleton of said derivative, but more preferably contains the quinoline ring more than 1 or the organic compound of phosphorous oxides in female skeleton at least.

The hole trapping layer is to prevent from not take place to combine with electronics from negative electrode and the layer that moves providing between the electrode of electric field from the anodic hole again, according to the kind of the material that constitutes each layer, can increase the combination rate again of hole and electronics and can improve luminous efficiency by inserting this layer.Therefore, hole prevention property material is compared than hole transporting material, and preferred highest occupied molecular orbital(HOMO) energy level is low, and material preferred and the formation adjacent layers is difficult to generate the excited state complex compound.Owing to stoping the compound that moves from the anodic hole effectively is preferred, and the material hole prevention that electron transport can be high can be also high, lists so above-mentioned electron transport materials can be used as preferable material.

Above-mentioned hole transporting layer, luminescent layer, electron supplying layer, the hole trapping layer can be also the material more than two kinds can be carried out lamination separately to mix, and also can be dispersed in polymer binder, as be dispersed in polyvinyl chloride, polycarbonate, polystyrene, poly-(N-vinylcarbazole), polymethylmethacrylate, poly-n-butyl methacrylate, polyester, polysulfones, polyphenylene oxide, polyhutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfones, polymeric amide, ethyl cellulose, vinyl acetate between to for plastic, ABS resin, urethane resin equal solvent soluble resin, phenol resins, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, Synolac, Resins, epoxy, use in the cured resins such as silicone resin etc.

The formation method of luminophore is resistive heating evaporation, electron beam evaporation plating, sputter, molecular layer platen press, coating etc., restriction especially, but consider from the characteristic aspect usually and preferred resistive heating evaporation, electron beam evaporation plating.The thickness of layer is subjected to the resistance value influences of luminophore, be selected from usually 1～1000nm between.

So-called electric energy mainly refers to galvanic current, but also can be pulsed current and alternating current.If consider consumption electric power, the life-span of element, current value and magnitude of voltage, preferred alap energy.

Luminous element of the present invention for example can be by matrix-style and segmented mode developing.Above-mentioned matrix-style is meant the pixel that will be used to the show mode with the reticulation configuration, and then represents writings and image with the set of pixel.Shape, the size of pixel are decided by purposes.For example in the image of PC, monitor, TV and the literal indicating meter, using the length of side usually is the following tetragonal pixels of 300 μ m, and the giant display that resembles display panel and so on uses the pixel of the length of side as the mm level.Under the monochromatic situation about showing, often arrange the pixel of same color, in the situation that colour shows, arrange the pixel that shows red, green, blue.In this case, be typically δ type and stripe.And, as the driving method of this matrix-style, can adopt line sequential driving method and active matrix.It is simple in structure that line drives in proper order, but when considering acting characteristic from another point of view, preferred sometimes effectively matrix-style.It is necessary using respectively according to purposes.

Segmented mode is according to showing that preassigned information forms pattern like that, luminous mode in stated limit.For example, the operating state that can enumerate moment in digital dock and the thermometer and temperature demonstration, audio equipment and electromagnetism conditioner etc. shows, the dashboard demonstration of automobile etc.And matrix-style shows and the segmented mode demonstration also can coexist in same dashboard.

Embodiment

Enumerate embodiment and comparative example explanation the present invention below, but the present invention is not subjected to the restriction of these examples.Also have, below among each embodiment the numbering of compound be meant the numbering of above-claimed cpd.The evaluation method of relevant structural analysis is expressed as follows in addition.

¹H-NMR uses superconduction FTNMR EX-270 (NEC (strain) manufacturing), measures in heavy chloroformic solution.

Ultimate analysis uses CHN コ-ダ-MT-3 type (this making of willow institute (strain) manufacturing), ion chromatograph DX320 (Japanese ダ イ オ ネ Network ス (strain) manufacturing) and sequential type ICP Emission Spectrophotometer device SPS4000 (Seiko instrument (strain) manufacturing) to measure.

Mass spectrum uses JMS-DX303 (NEC (strain) manufacturing) to measure.

Absorption spectrum and fluorescence spectrum use U-3200 type spectrophotometer, F-2500 type spectrophotofluorometer (being Hitachi's (strain) makes) respectively, 4 * 10 ^-6Measure in the dichloromethane solution of mol.

Embodiment 1

The synthetic method of compound [1]

At 30ml 1, add 1.3g 2-benzoyl-3 in the 2-ethylene dichloride, 5-two (4-n-hexyl phenyl) pyrroles, 1g 2,4-two (4-n-hexyl phenyl) pyrroles, 0.47ml Phosphorus Oxychloride, reaction is 12 hours under the reflux.After being cooled to room temperature, add 3.6ml diisopropylethylamine, 2.6ml boron trifluoride ethyl ether complex, stirred 6 hours.Add 50ml water, use dichloromethane extraction, concentrate, make with extra care, obtain 1g red-violet colour powder by the column chromatography of using silica gel.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.90(t，12H)，1.29-1.65(m，32H)，2.39(t，4H)，2.64(t，4H)，6.44(t，2H)，6.49(s，2H)，6.60-6.63(m，9H)，6.83(d，2H)，7.25(d，4H)，7.82(d，4H)

Molecular formula C ₆₃H ₇₅N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：83.5％(83.2％)、H:8.4％(8.3％)、N：3.2％(3.1％)、F：3.2％(4.2％)、B：1.2％(1.2％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=908.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [1].Compound [1] shows following optical physics characteristic.

Absorption spectrum: λ max 568nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 613nm (solvent: methylene dichloride).

Subsequently, use compound [1] to make luminous element as follows.The glass substrate (Asahi Glass (strain), 15 Ω/, electron beam evaporation plating product) of piling up the 150nmITO nesa coating is cut into 30 * 40mm, carry out etching.The substrate that obtains is distinguished ultrasonic cleaning 15 minutes in acetone, " セ ミ コ Network リ Application 56 ", clean with ultrapure water then.Then ultrasonic cleaning 15 minutes in Virahol, dipping 15 minutes and dry in hot methanol then.This substrate carried out 1 hour UV-ozonize before making element, be placed in the vacuum deposition apparatus, the vacuum tightness in the device is pumped down to 5 * 10 ^-5Below the Pa.By electrical resistance heating, 4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl of evaporation 50nm at first as hole transporting material.Then use 1 as main material, 4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles, use compound [1] as dopant material, altogether evaporation is thick to 15nm, makes that concentration of dopant is 1 weight %, and it is thick that primary layers of material is pressed into 35nm.Then evaporation 0.5nm lithium, 150nm silver form negative electrode, make the foursquare element of 5 * 5mm.Thickness described here is meant the value that quartzy oscillatory type thickness monitor shows.From the luminescent spectrum of this luminous element obtain spike long for 618nm, luminous efficiency be the emitting red light of 4.2cd/A.

Embodiment 2

The synthetic method of compound [2]

Use 1.2g 2-benzoyl-3,5-phenylbenzene pyrroles, 0.8g 2,4-phenylbenzene pyrroles uses the method identical with compound [1] synthetic.Obtain the 1.4g red powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：6.46(t，2H)，6.52(s，2H)，6.67-6.88(m，11H)，7.43(m，6H)，7.90(d，4H)

Molecular formula C ₃₉H ₂₇N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：82.3％(81.8％)、H：4.8％(4.7％)、N：4.9％(4.9％)、F：6.6％(6.6％)、B：1.9％(2.0％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=572.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [2].Compound [2] shows following optical physics characteristic.

Absorption spectrum: λ max 556nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 600nm (solvent: methylene dichloride).

Subsequently, except using compound [2], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 608nm, luminous efficiency be the high brightness emitting red light of 2.6cd/A.

Embodiment 3

The synthetic method of compound [3]

Use 0.4g 2-(2-methyl benzoyl)-3,5-two (4-n-hexyl phenyl) pyrroles, 0.25g 2,4-two (4-n-hexyl phenyl) pyrroles synthesizes equally with compound [1].Obtain 0.1g red-violet colour powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.88(t，12H)，1.29-1.67(m，32H)，2.39(t，4H)，2.63(t，4H)，3.51(s，3H)，6.00(d，2H)，6.51(s，2H)，6.63-6.73(m，10H)，7.23(d，4H)，7.81(d，4H)

Molecular formula C ₆₄H ₇₇N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：83.3％(83.3％)、H：8.4％(8.4％)、N：3.1％(3.0％)、F：3.2％(4.1％)、B：1.2％(1.2％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=922.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [3].Compound [3] shows following optical physics characteristic.

Absorption spectrum: λ max 568nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 613nm (solvent: methylene dichloride).

Subsequently, except using compound [3], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 618nm, luminous efficiency be the emitting red light of 4.0cd/A.

Embodiment 4

The synthetic method of compound [4]

Use 0.5g 2-(4-phenyl benzoyl)-3,5-two (4-n-hexyl phenyl) pyrroles, 0.25g 2,4-two (4-n-hexyl phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.18g red-violet colour powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.84(t，12H)，1.07-1.65(m，32H)，2.25(t，4H)，2.64(t，4H)，6.53(s，2H)，6.61-6.69(m，11H)，6.88(d，2H)，7.23(d，4H)，7.24-7.37(m，5H)，7.83(d，4H)

Molecular formula C ₆₉H ₇₉N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：84.3％(84.1％)、H：8.1％(8.0％)、N：2.9％(2.8％)、F：3.0％(3.9％)、B：1.2％(1.2％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=984.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [4].Compound [4] shows following optical physics characteristic.

Absorption spectrum: λ max 569nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 615nm (solvent: methylene dichloride).

Subsequently, except using compound [4], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 618nm, luminous efficiency be the emitting red light of 3.8cd/A.

Embodiment 5

The synthetic method of compound [5]

Use 0.45g 2-(4-anisoyl)-3,5-two (4-n-hexyl phenyl) pyrroles, 0.25g 2,4-two (4-n-hexyl phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.15g red-violet colour powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.91(t，12H)，1.28-1.67(m，32H)，2.00(S，3H)，2.38(t，4H)，2.63(t，4H)，6.21(d，1H)，6.43(s，2H)，6.46(d，2H)，6.63(m，8H)，6.80(d，1H)，7.25(d，4H)，7.82(d，4H)

Molecular formula C ₆₄H ₇₇N ₂OF ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：82.1％(81.9％)、H：8.3％(8.2％)、N：3.1％(3.0％)、O：1.8％(1.7％)、F：3.0％(4.0％)、B：1.2％(1.2％)

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=938.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [5].Compound [5] shows following optical physics characteristic.

Absorption spectrum: λ max 566nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 611nm (solvent: methylene dichloride).

Subsequently, except using compound [5], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 615nm, luminous efficiency be the emitting red light of 4.0cd/A.

Embodiment 6

The synthetic method of compound [6]

With 0.4g 2-(4-cyano group benzoyl)-3,5-two (4-n-hexyl phenyl) pyrroles, 0.25g 2,4-two (4-n-hexyl phenyl) pyrroles, use the method identical synthetic with compound [1].Obtain 0.3g sorrel powder.The powder that obtains ¹The H-NMR analytical results is as follows.

Molecular formula C ₆₄H ₇₄N ₃F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：82.6％(82.3％)、H：7.9％(7.9％)、N：4.6％(4.5％)、F：3.3％(4.1％)、B：1.2％(1.2％)

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=933.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [6].Compound [6] shows following optical physics characteristic.

Absorption spectrum: λ max 576nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 626nm (solvent: methylene dichloride).

Embodiment 7

The synthetic method of compound [7]

Use 0.5g 2-(1-naphthoyl)-3,5-two (4-n-hexyl phenyl) pyrroles, 0.25g 2,4-two (4-n-hexyl phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.2g purple powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.93(t，12H)，1.25-1.65(m，32H)，2.21(t，4H)，2.64(t，4H)，6.27(m，8H)，6.40(s，2H)，6.64(t，1H)，7.00(dd，2H)，7.24(d，4H)，7.24-7.34(m，3H)，7.80-7.87(m，5H)

Molecular formula C ₆₇H ₇₇N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：84.3％(83.9％)、H：8.1％(8.0％)、N：2.9％(2.9％)、F：3.1％(4.0％)、B：1.1％(1.2％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=958.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [7].Compound [7] shows following optical physics characteristic.

Absorption spectrum: λ max 571nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 616nm (solvent: methylene dichloride).

Subsequently, except using compound [7], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 619nm, luminous efficiency be the emitting red light of 4.2cd/A.

Embodiment 8

The synthetic method of compound [8]

Use 0.4g 2-benzoyl-3,5-two (4-p-methoxy-phenyl) pyrroles, 0.25g2,4-two (4-p-methoxy-phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.2g bluish voilet powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：3.67(s，3H)，3.86(s，3H)，6.38(d，2H)，6.47(s，2H)，6.54(t，2H)，6.64-6.75(m，5H)，6.85(d，2H)，6.96(d，4H)，7，89(d，4H)

Molecular formula C ₄₃H ₃₅N ₂O ₄F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：75.0％(74.6％)、H：5.2％(5.1％)、N：4.2％(4.0％)、O：9.3％(9.2％)、F：4.4％(5.5％)、B：1.6％(1.6％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=692.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [8].Compound [8] shows following optical physics characteristic.

Absorption spectrum: λ max 584nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 632nm (solvent: methylene dichloride).

Subsequently, except using compound [8], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 641nm, luminous efficiency be the emitting red light of 2.7cd/A.

Embodiment 9

The synthetic method of compound [9]

Use 0.35g 2-benzoyl-3,5-two (4-n-pentyloxy phenyl) pyrroles, 0.25g2,4-two (4-n-pentyloxy phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.1g bluish voilet powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.94(t，12H)，1.38-1.41(m，16H)，1.68-1.83(m，8H)，3.80(t，4H)，4.00(t，4H)，6.36(d，2H)，6.46(s，2H)，6.53(t，2H)，6.62-6.73(m，5H)，6.85(d，2H)，6.94(d，4H)，7.87(d，4H)

Molecular formula C ₅₉H ₆₇N ₂O ₄F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：77.5％(77.3％)、H：7.5％(7.5％)、N：3.2％(3.1％)、O：7.1％(7.0％)、F：3.1％(4.1％)、B：1.2％(1.2％)

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=916.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [9].Compound [9] shows following optical physics characteristic.

Absorption spectrum: λ max 587nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 636nm (solvent: methylene dichloride).

Embodiment 10

The synthetic method of compound [10]

With 0.6g 2-(naphthoyl)-3,5-two (4-aminomethyl phenyl) pyrroles, 0.25g2,4-two (4-aminomethyl phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.55g purple powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：2.00(s，6H)，2.40(s，6H)，6.26(m，8H)，6.39(s，2H)，6.65(t，1H)，7.00(d，1H)，7.12(d，1H)，7.24(d，4H)，7.24-7.33(m，3H)，7.77-7.86(m，5H)

Molecular formula C ₄₇H ₃₇N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：83.5％(83.2％)、H：5.6％(5.5％)、N：4.3％(4.1％)、F：4.8％(5.6％)、B：1.5％(1.6％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=678.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [10].Compound [10] shows following optical physics characteristic.

Absorption spectrum: λ max 575nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 613nm (solvent: methylene dichloride).

Subsequently, except using compound [10], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 620nm, luminous efficiency be the emitting red light of 3.0cd/A.

Embodiment 11

The synthetic method of compound [11]

Use 0.35g 2-benzoyl-3,5-two (4-(2, the 4-3,5-dimethylphenyl) phenyl) pyrroles, 0.25g 2,4-two (4-(2, the 4-3,5-dimethylphenyl) phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.15g purple powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：2.18(s，6H)，2.32(s，6H)，2.36(ss，12H)，6.67(s，2H)，6.81(d，8H)，6.94-7.07(m，11H)，7.11(d，2H)，7.43(d，4H)，8.01(d，4H)

Molecular formula C ₇₁H ₅₉N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：86.4％(86.2％)、H：6.0％(6.0％)、N：2.9％(2.8％)、F：3.0％(3.9％)、B：1.2％(1.1％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=988.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [11].Compound [11] shows following optical physics characteristic.

Absorption spectrum: λ max 576nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 626nm (solvent: methylene dichloride).

Embodiment 12

The synthetic method of compound [12]

Use 0.4g 2-(1-naphthoyl)-3,5-two (4-aminomethyl phenyl) pyrroles, 0.25g 2,4-two (4-p-methoxy-phenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain 0.1g purple powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：1.97(s，3H)，2.40(s，3H)，3.54(s，3H)，3.86(s，3H)，5.99(d，2H)，6.25(s，4H)，6.30-6.39(m，8H)，6.69(t，1H)，6.97(d，3H)，7.14(d，1H)，7.26(d，2H)，7.26-7.37(m，3H)，7.78-7.95(m，5H)

Molecular formula C ₄₇H ₃₇N ₂O ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：79.6％(79.4％)、H：5.1％(5.2％)、N：4.0％(3.9％)、O：4.6％(4.5％)、F：4.6％(5.4％)。B：1.6％(1.6％)

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=710.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [12].Compound [12] shows following optical physics characteristic.

Absorption spectrum: λ max 577nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 624nm (solvent: methylene dichloride).

Subsequently, except using compound [12], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 628nm, luminous efficiency be the emitting red light of 2.9cd/A.

Embodiment 13

The synthetic method of compound [53]

Use 0.4g 2-benzoyl-3,5-two (4-n-butylphenyl) pyrroles, 0.25g2,4-two (4-n-butylphenyl) pyrroles uses the method identical with compound [1] synthetic.Obtain the 0.27g red powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：1.97(s，3H)，2.40(s，3H)，3.54(s，3H)，3.86(s，3H)，5.99(d，2H)，6.25(s，4H)，6.30-6.39(m，8H)，6.69(t，1H)，6.97(d，3H)，7.14(d，1H)，7.26(d，2H)，7.26-7.37(m，3H)，7.78-7.95(m，5H)

Molecular formula C ₅₅H ₅₉N ₂F ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：83.1％(82.9％)、H：7.5％(7.4％)、N：3.6％(3.5％)、F：4.0％(4.8％)、B：1.3％(1.4％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=796.According to The above results, determine that above-mentioned resultant is that red powder is compound [53].Compound [53] shows following optical physics characteristic.

Absorption spectrum: λ max 569nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 611nm (solvent: methylene dichloride).

Subsequently, except using compound [53], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 617nm, luminous efficiency be the emitting red light of 5.0cd/A.

Embodiment 14

The synthetic method of compound [59]

Dissolving 0.5g compound [10] in the 30ml anhydrous tetrahydro furan drips 1.88ml phenyl-magnesium-bromide (1.0mol/L: tetrahydrofuran (THF)), reacted 9 hours at 60 ℃ down at 20 ℃.After being cooled to room temperature, add 50ml water, use dichloromethane extraction, concentrate, make with extra care, obtain 0.32g red-violet colour powder by the column chromatography of using silica gel.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：1.97(s，3H)，2.40(s，3H)，3.54(s，3H)，3.86(s，3H)，5.99(d，2H)，6.25(s，4H)，6.30-6.39(m，8H)，6，69(t，1H)，6.97(d，3H)，7.14(d，1H)，7.26(d，2H)，7.26-7.37(m，3H)，7.78-7.95(m，5H)

Molecular formula C ₅₉H ₄₇N ₂The results of elemental analyses of B is as follows.In the bracket is theoretical value.

C：89.3％(89.2％)、H：6.0％(5.9％)、N：3.5％(3.5％)、B：1.2％(1.4％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=794.According to The above results, determine that above-mentioned resultant is that the red-violet colour powder is compound [59].Compound [59] shows following optical physics characteristic.

Absorption spectrum: λ max 568nm (solvent: methylene dichloride)

Fluorescence spectrum: λ max 613nm (solvent: methylene dichloride).

Subsequently, except using compound [59], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 616nm, luminous efficiency be the emitting red light of 3.8cd/A.

Embodiment 15

Similarly to Example 1, proceed to after the evaporation of hole transporting material, lamination compound [53] is thick to 50nm.Then evaporation 0.5nm lithium, 150nm silver form negative electrode, make 5 * 5mm square element.From the luminescent spectrum of this luminous element obtain spike long for 622nm, luminous efficiency be the emitting red light of 2.5cd/A.

Embodiment 16

Except using compound [63], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 609nm, luminous efficiency be the emitting red light of 1.6cd/A.

Embodiment 17

Except using compound [85], to make luminous element with embodiment 1 identical method as the dopant material.From the luminescent spectrum of this luminous element obtain spike long for 628nm, luminous efficiency be the emitting red light of 1.1cd/A.

Embodiment 18

Similarly to Example 1, evaporation is to hole transporting layer, use is as 1 of main material, 4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles, as 9-diethylamino-5H-benzo (a) phenoxazine-5-ketone (the fluorescence peak wavelength in the dichloromethane solution is 610nm) of dopant material, evaporation is thick to 25nm altogether, and to make concentration of dopant be 0.5 weight %, form luminescent layer after, with 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP) evaporation is thick to 25nm, forms electron supplying layer.Then mix after the 0.5nm lithium, evaporation 150nm silver forms negative electrode, makes the foursquare element of 5 * 5mm.From this luminous element, obtaining based on the glow peak wavelength is that 609nm, spectrum peak width at half height are the emitting red light of the dopant material of 71nm, and luminosity is 3000cd/m under the impressed voltage of 16V ²

Embodiment 19～25, embodiment 28～29, comparative example 1

Except using the compound described in the table 1, make luminous element with method similarly to Example 18 as hole transporting material, main material, dopant material, the negative electrode.Each embodiment the results are shown in the table 1.In addition, the HTM1 that uses among the embodiment 25 is following compound.

Table 1

	Cavity conveying is	Luminescent layer			Electron supplying layer	Negative electrode	Glow peak wavelength (nm)	Spectrum peak width at half height (nm)	Impressed voltage (V)	Luminosity (cd/m 2)
											Main material	The doping agent material	Fluorescence peak wavelength in the dichloromethane solution
		Embodiment 18	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl	1,4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles										9-dimethylamino-5H-benzo (a) fen  piperazine-5-ketone	610nm	BCP	Li 0.5nm Ag 150nm	609	71	16	3000
Embodiment 19	The same				The same	3-ethyl-2-[3-(the inferior thiazolinyl of 3-ethyl-2-benzo)-1-propenyl] benzothiazole father-in-law iodide	596nm	BCP	Li 0.5nm Ag 150nm	602	45	16	1200
		Embodiment 20	The same	The same										4-(dicyano methylene radical)-2-methyl-6-(1,1,7,7-tetramethyl-durene base-9-thiazolinyl)-4H-pyrans	625nm	BCP	Li 0.5nm Ag 150nm	609	88	16	1500
Embodiment 21	The same				The same	Compound [99]	629nm	BCP	Li 0.5nm Ag 150nm	636	33	12	10000
		Embodiment 22	The same	The same										Compound [63]	605nm	BCP	Li 0.5nm Ag 150nm	617	42	16	3000
Comparative example 1	The same				1,4-diketone-2,5-dimethyl-3,6-3,5-dimethylphenyl pyrrolo-[3,4-c] pyrroles	Compound [63]	605nm	BCP	Li 0.5nm Ag 150nm	609	52	16	900
		Embodiment 23	The same	1,4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles										Compound [66]	625nm	BCP	Li 0.5nm Ag 150nm	632	40	19	3200
Embodiment 24	The same				The same	Compound [65]	606nm	BCP	Li 0.5nm Ag 150nm	612	40	17	4200
		Embodiment 25	HTM1	The same										Compound [65]	606nm	BCP	Li 0.5nm Ag 150nm	612	40	14	7000
Embodiment 28	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl				The same	Compound [73]	630nm	BCP	Li 0.5nm Al 150nm	629	38	15	3600
		Embodiment 29	The same	The same										Compound [69]	641nm	BCP	Li 0.5nm Al 150nm	645	32	17	2900

Embodiment 26

Inject except first hole of evaporation 10nm at first and to carry material copper phthalocyanine (CuPc), the evaporation second hole transporting material HTM1 forms outside the cavity conveying layer segment subsequently, makes luminous element with method similarly to Example 24.From this luminous element, obtaining based on the glow peak wavelength is that 612nm, spectrum peak width at half height are the emitting red light of the compound [65] of 40nm, and luminosity is 6400cd/m under the impressed voltage of 14V ²

Embodiment 27

Except using compound [10] (the fluorescence peak wavelength in the dichloromethane solution is 619nm) as dopant material, the main material of evaporation 20nm at first in luminescent layer, evaporation 5nmBCP forms the electron transport part subsequently, use aluminium substitution silver to form outside the negative electrode, make luminous element with method similarly to Example 18.From this luminous element, obtaining based on the glow peak wavelength is that 629nm, spectrum peak width at half height are the emitting red light of the compound [100] of 28nm, and luminosity is 7500cd/m under the impressed voltage of 14V ²

Embodiment 30～47

Except using the compound described in the table 2 and 3, make luminous element with method similarly to Example 27 as hole transporting material, main material, the dopant material.Each embodiment the results are shown in table 2 and 3.

Table 2

Hole transporting layer		Luminescent layer			Electron supplying layer		Negative electrode	Glow peak wavelength (nm)	Spectrum peak width at half height (nm)	Impressed voltage (V)	Luminosity (cd/m 2)
														Main material	Dopant material	Fluorescence peak wavelength in the dichloromethane solution
Embodiment 27	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl	1,4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles	Compound [100]	619nm													Main material 20nm	BCP 5nm	Li 0.5nm Al 150nm	629	28	14	7500
					Embodiment 30	The same	The same	Compound [86]	617nm	Main material 20nm	BCP 5nm	The same	628	43	13	9500
Embodiment 31	The same	1,4-diketone-2,5-two (3-methyl-benzyl)-3,6-two (4-xenyl) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm													Main material 20nm	BCP 5nm	The same	639	28	14	1700
					Embodiment 32	The same	The same	Compound [100]	619nm	Main material 20nm	BCP 5nm	The same	633	28	13	5300
Embodiment 33	The same	1,4-diketone-2,5-two (2-methyl-benzyl)-3,6-two (2-naphthyl) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm													Main material 20nm	BCP 5nm	The same	642	33	14	2700
					Embodiment 34	The same	1,4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (2-(6-methoxyl group naphthyl)) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm	Main material 20nm	BCP 5nm	The same	637	33	14	1000
Embodiment 35	The same	1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-two (2-naphthyl) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm													Main material 20nm	BCP 5nm	The same	637	33	16	3500
					Embodiment 36	The same	1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm	Main material 20nm	BCP 5nm	The same	631	33	15	3100
Embodiment 37	The same	The same	Compound [86]	617nm													Main material 20nm	BCP 5nm	The same	624	43	14	4400

Table 3

	Hole transporting layer	Luminescent layer			Electron supplying layer		Negative electrode	Glow peak wavelength (nm)	Spectrum peak width at half height (nm)	Impressed voltage (V)	Luminosity (cd/m 2)
												Main material	Dopant material	Fluorescence peak wavelength in the dichloromethane solution
		Embodiment 38	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl	1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-two (4-xenyl) pyrrolo-[3,4-c] pyrroles											Compound [99]	629nm	Main material 20nm	BCP 5nm	Li 0.5nm Al 150nm	638	33	15	5200
Embodiment 39	The same				The same	Compound [100]	619nm	Main material 20nm	BCP 5nm	The same	628	28	16	7500
		Embodiment 40	The same	The same											Compound [73]	630nm	Main material 20nm	BCP 5nm	The same	628	38	18	2500
Embodiment 41	The same				The same	Compound [69]	630nm	Main material 20nm	BCP 5nm	The same	645	32	16	1800
		Embodiment 42	The same	1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-(3-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles											Compound [99]	629nm	Main material 20nm	BCP 5nm	The same	631	33	15	2300
Embodiment 43	The same				1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-two (3-p-methoxy-phenyl) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm	Main material 20nm	BCP 5nm	The same	640	33	15	3400
		Embodiment 44	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl	1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-two (4-chloro-phenyl-) pyrrolo-[3,4-c] pyrroles											Compound [99]	629nm	Main material 20nm	BCP 5nm	Li 0.5nm Al 150nm	640	33	15	4200
Embodiment 45	The same				1,4-diketone-2,5-two (3,5-di-t-butyl benzyl)-3,6-two (4-anti--toluylene) pyrrolo-[3,4-c] pyrroles	Compound [99]	629nm	Main material 20nm	BCP 5nm	The same	637	33	17	1900
		Embodiment 46	The same	The same											Compound [73]	630nm	Main material 20nm	BCP 5nm	The same	630	38	22	1200
Embodiment 47	The same				The same	Compound [69]	641nm	Main material 20nm	BCP 5nm	The same	648	32	18	1100

Embodiment 48

Except using 1,4-diketone-2,5-two (2-phenylbenzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles are made luminous element as outside the main material with method similarly to Example 21.From this luminous element, obtaining based on the glow peak wavelength is that 639nm, spectrum peak width at half height are the emitting red light of the compound [99] of 33nm, and luminosity is 2000cd/m under the impressed voltage of 13V ²

Embodiment 49

Except using 1,4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-ethylphenyl) pyrrolo-[3,4-c] pyrroles is as main material, and compound 1 (the fluorescence peak wavelength in the dichloromethane solution is 613nm) is made luminous element as outside the dopant material with method similarly to Example 28.From this luminous element, obtaining based on the glow peak wavelength is that 618nm, spectrum peak width at half height are the emitting red light of the compound [1] of 48nm, and luminosity is 8000cd/m under the impressed voltage of 14V ²

Embodiment 50

Inject except first hole of evaporation 10nm at first and to carry material C uPc, the second thick hole transporting material N of evaporation 50nm subsequently, N '-phenylbenzene-N, N '-two (naphthalene-1-yl)-1,1 '-phenylbenzene-4, (α-NPD) forms hole transporting layer to 4 '-diamines, and the ETM1 shown in below using is as outside the electron transport materials, uses with the same method of embodiment 49 and makes luminous element.The ionizing potential of ETM1 is 5.99eV (using atmospheric condition type ultraviolet electronic analysis device (AC-1: reason is ground gauge (strain)) to measure), and molecular weight is 401.From this luminous element, obtaining based on the glow peak wavelength is that 618nm, spectrum peak width at half height are the emitting red light of the compound [1] of 48nm, and luminosity is 9000cd/m under the impressed voltage of 15V ²

Embodiment 51～53

Except using the compound described in the table 4, use with the same method of embodiment 49 and make luminous element as the electron transport materials.The result of each embodiment is presented in the table 4.The ETM2 of table 4, ETM3, ETM4 are following compounds.

Table 4

	Hole transporting layer	Luminescent layer			Electron supplying layer				Negative electrode	Glow peak wavelength (nm)	Spectrum peak width at half height (nm)	Impressed voltage (V)	Luminosity (cd/m 2)
														Main material	Dopant material	Fluorescence peak wavelength in the dichloromethane solution		Ionizing potential	Molecular weight	Tg (℃)
		Embodiment 49	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl	1,4-diketone-2,5-two (3, the 5-dimethyl benzyl) 3,6-two (4-ethylphenyl) pyrrolo-[3,4-c] pyrroles	Compound [1]	613nm	BCP	5.85eV													360	≤77	Li 0.5nm Al 150nm	618	48	14	8000
Embodiment 51	The same								The same	The same	613nm	ETM2	5.97eV	609	112	The same	618	48	15	8000
		Embodiment 52	The same	The same	The same	613nm	ETM3	6.07eV													670	165	The same	618	48	15	10000
Embodiment 53	The same								The same	The same	613nm	ETM4	6.07eV	672	219	The same	618	48	14	11000
		Embodiment 54	The same	1,4-diketone-2,5-diethyl-3,6-two (1-naphthyl) pyrrolo-[3,4-c] pyrroles	Compound [53]	611nm	ETM4	6.07eV													672	219	The same	615	43	14	12000
Embodiment 55	The same								1,4-diketone-2,5-dimethyl-3,6-two (1-naphthyl) pyrrolo-[3,4-c] pyrroles	Compound [53]	613nm	ETM4	6.07eV	672	219	The same	615	43	15	16000
		Embodiment 56	The same	1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles	Compound [53]	613nm	ETM4	6.07eV													672	219	The same	616	43	13	9000
Embodiment 57	The same								1,4-diketone-2,5-dimethyl-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles	Compound [53]	613nm	ETM4	6.07eV	672	219	The same	616	43	15	15000

Embodiment 54

1,4-diketone-2,5-diethyl-3,6-two (1-naphthyl) pyrrolo-[3,4-c] pyrroles's synthetic method

The 7.3g potassium tert.-butoxide is dissolved in the 36ml tertiary amyl alcohol, adds 10g 1-naphthalene nitrile down at 90 ℃ while stirring.Then, with 2 hours dropping 6.7ml ni-isopropyl succinates.Reflux after 1 day, add 30ml methyl alcohol, 4.4ml acetic acid down, refluxed 30 minutes at 60 ℃.After being cooled to room temperature, filter, use methanol wash.Then, the 2.89g red powder that obtains is dissolved among the 80mlDMF, adds the 2.1g potassium tert.-butoxide, stirred 1 hour.Add the 1.5ml iodic ether, stirred 1 day down at 65 ℃.Add 50ml water, use dichloromethane extraction, concentrate, make with extra care, obtain the 1.5g yellow powder by the column chromatography of using silica gel.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：0.93(tt，6H)，3.35(qq，2H)，3.70(qq，2H)，7.58-7.68(m，6H)，7.76(t，2H)，7.90(m，4H)，8.02(d，2H)

Molecular formula C ₃₀H ₂₄N ₂O ₂Results of elemental analyses as follows.In the bracket is theoretical value.

C：81.2％(81.1％)、H：5.3％(5.4％)、N：6.3％(6.3％)、O：7.2％(7.2％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=444.According to The above results, determine that above-mentioned resultant is that yellow powder is 1,4-diketone-2,5-diethyl-3,6-two (1-naphthyl) pyrrolo-[3,4-c] pyrroles.

Subsequently, except using 1,4-diketone-2,5-diethyl-3,6-two (1-naphthyl) pyrrolo-[3,4-c] pyrroles is as main material, and compound [53] is used with embodiment 53 identical methods and is made luminous elements as outside the dopant material.Obtaining from this luminous element based on the glow peak wavelength is that 615nm, spectrum peak width at half height are the emitting red light of the compound [53] of 43nm, and luminosity is 12000cd/m under the impressed voltage of 14V ²

Embodiment 55

Except using 1,4-diketone-2,5-dimethyl-3,6-two (1-naphthyl) pyrrolo-[3,4-c] pyrroles is as outside the main material, uses with the same method of embodiment 54 and makes luminous element.Obtaining from this luminous element based on the glow peak wavelength is that 615nm, spectrum peak width at half height are the emitting red light of the compound [53] of 43nm, and luminosity is 16000cd/m under the impressed voltage of 15V ²

Embodiment 56

1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles's synthetic method

Except using 4-p-methylphenyl-1-naphthalene nitrile to substitute 1-naphthalene nitrile, 4-methyl-benzyl bromide replaces outside the iodic ether, uses with the same method of embodiment 54 synthetic.Obtain the 1.2g orange powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：2.20(s，6H)，2.49(s，6H)，4.38(t，2H)，4.93(t，2H)，6.69(t，4H)，6.88(t，4H)，7.35(d，4H)，7.42-7.64(m，12H)，8.00(t，4H)

Molecular formula C ₅₆H ₄₄N ₂O ₂Results of elemental analyses as follows.In the bracket is theoretical value.

C：86.6％(86.6％)、H：5.7％(5.7％)、N：3.5％(3.6％)、O：4.1％(4.1％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=776.According to The above results, determine that above-mentioned resultant is that orange powder is 1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles.

Subsequently, except using 1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles are used with embodiment 54 identical methods and are made luminous element as outside the main material.Obtaining from this luminous element based on the glow peak wavelength is that 616nm, spectrum peak width at half height are the emitting red light of the compound [53] of 43nm, and luminosity is 9000cd/m under the impressed voltage of 13V ²

Embodiment 57

1,4-diketone-2,5-dimethyl-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles's synthetic method

Except using 4-p-methylphenyl-1-naphthalene nitrile to replace 1-naphthalene nitrile, methyl iodide replaces outside the iodic ether, uses with the same method of embodiment 54 synthetic.Obtain the 1.4g orange powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：2.49(s，6H)，3.05(s，6H)，7.35(d，4H)，7.44-7.65(m，10H)，7.98(d，2H)，8.02(dd，4H)

Molecular formula C ₄₂H ₃₂N ₂O ₂Results of elemental analyses as follows.In the bracket is theoretical value.

C：84.6％(84.6％)、H：5.4％(5.4％)、N：4.7％(4.7％)、O：5.3％(5.4％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=596.According to The above results, determine that above-mentioned resultant is that orange powder is 1,4-diketone-2,5-dimethyl-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles.

Subsequently, except using 1,4-diketone-2,5-dimethyl-3,6-two (4-p-methylphenyl naphthalene-1-yl) pyrrolo-[3,4-c] pyrroles is as outside the main material, uses with the same method of embodiment 54 and makes luminous element.Obtaining from this luminous element based on the glow peak wavelength is that 616nm, spectrum peak width at half height are the emitting red light of the compound [53] of 43nm, and luminosity is 15000cd/m under the impressed voltage of 15V ²

Embodiment 58

Except using 1,4-diketone-2,5-dimethyl-3-(1-naphthyl)-6-(3,5-two (1-naphthyl) phenyl) pyrrolo-[3,4-c] pyrroles is as main material, and compound [1] is used with embodiment 54 complete same methods and is made luminous element as outside the dopant material.Obtaining from this luminous element based on the glow peak wavelength is that 616nm, spectrum peak width at half height are the emitting red light of the compound [1] of 48nm, and luminosity is 9000cd/m under the impressed voltage of 13V ²

Embodiment 59

1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (1-phenanthryl) pyrrolo-[3,4-c] pyrroles's synthetic method

Except using the luxuriant and rich with fragrance nitrile of 1-to replace 1-naphthalene nitrile, 4-methyl-benzyl bromide replaces outside the iodic ether, uses with the same method of embodiment 54 synthetic.Obtain the 0.9g orange powder.The powder that obtains ¹The H-NMR analytical results is as follows.

¹H-NMR(CDCl ₃(δ＝ppm))：2.18(ss，6H)，4.40(t，2H)，4.90(t，2H)，6.64(t，4H)，6.79(t，4H)，7.62-7.86(m，12H)，7.96(t，2H)，8.79(t，4H)

Molecular formula C ₅₀H ₃₆N ₂O ₂Results of elemental analyses as follows.In the bracket is theoretical value.

C：86.3％(86.2％)、H：5.2％(5.2％)、N：3.9％(4.0％)、O：4.5％(4.6％)。

According to mass spectrum, the main molecules quasi-molecular ions of target compound is m/Z=696.According to The above results, determine that above-mentioned resultant is that orange powder is 1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (1-phenanthryl) pyrrolo-[3,4-c] pyrroles.

Subsequently, except using 1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (1-phenanthryl) pyrrolo-[3,4-c] pyrroles be as outside the main material, uses with the same method of embodiment 54 and make luminous element.Obtaining from this luminous element based on the glow peak wavelength is that 616nm, spectrum peak width at half height are the emitting red light of the compound [53] of 43nm, and luminosity is 13000cd/m under the impressed voltage of 15V ²

Embodiment 60

Except using 1,4-diketone-2,5-dimethyl-3,6-two (1-phenanthryl) pyrrolo-[3,4-c] pyrroles is as outside the main material, uses with the same method of embodiment 54 and makes luminous element.Obtaining from this luminous element based on the glow peak wavelength is that 616nm, spectrum peak width at half height are the emitting red light of the compound [53] of 43nm, and luminosity is 17000cd/m under the impressed voltage of 14V ²

Table 5

	Hole transporting layer	Luminescent layer			Electron supplying layer				Negative electrode	Glow peak wavelength (nm)	Spectrum peak width at half height (nm)	Impressed voltage (V)	Luminosity (cd/m 2)
														Main material	Dopant material	Fluorescence peak wavelength in the dichloromethane solution		Ionizing potential	Molecular weight	Tg (℃)
		Embodiment 58	4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl	1,4-diketone-2,5-dimethyl-3-(1-naphthyl)-6-(3,5-two (1-naphthyl) phenyl) pyrrolo-[3,4-c] pyrroles	Compound [1]	613nm	ETM4	6.07eV													672	219	The same	616	48	13	9000
Embodiment 59	The same								1,4-diketone-2,5-two (4-methyl-benzyl)-3,6-two (1-phenanthryl) pyrrolo-[3,4-c] pyrroles	Compound [53]	613nm	ETM4	6.07eV	672	219	The same	616	43	15	13000
		Embodiment 60	The same	1,4-diketone-2,5-dimethyl-3,6-two (1-phenanthryl) pyrrolo-[3,4-c] pyrroles	Compound [53]	613nm	ETM4	6.07eV													672	219	The same	616	43	14	17000

Embodiment 61

Except using three (5,7-phenylbenzene-8-quinolinol compound) aluminium (III), in order to make luminous element with embodiment 1 identical method as outside the main material.From the luminescent spectrum of this luminous element obtain spike long for 613nm, luminous efficiency be the emitting red light of 3.2cd/A.

Comparative example 2

Except using compound [86], use with embodiment 61 identical methods and make luminous element as the auxiliary material.From the luminescent spectrum of this luminous element obtain spike long for 627nm, luminous efficiency be the emitting red light of 1.0cd/A.

Embodiment 62

The glass substrate (Asahi Glass (strain), 15 Ω/, electron beam evaporation plating product) of piling up 150nm ITO nesa coating is cut into 30 * 40mm, be processed into the striated pattern of 300 μ m rags (remaining wide 270 μ m) * 32 by photolithography.For length direction one side that makes the ITO striped is easy to and outside being electrically connected, extend to 1.27mm rag (the wide 800 μ m of peristome).With the substrate that obtains ultrasonic cleaning 15 minutes in acetone, " セ ミ コ Network リ Application 56 " respectively, wash with ultrapure water then.Then, ultrasonic cleaning is 15 minutes in Virahol, then dipping 15 minutes and dry in hot methanol.This substrate was used UV-ozonize 1 hour before the element of making, be placed in the vacuum deposition apparatus, and the vacuum tightness in the device is pumped down to below 5 * 10-4Pa.By electrical resistance heating, the TPD of evaporation 100nm at first.Then use 1,4-diketone-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-ethylphenyl) pyrrolo-[3,4-c] evaporation 15nm is thick altogether as dopant material as main material, compound [1] for the pyrroles, and make that concentration of dopant is 0.6 weight %, it is thick then above-mentioned ETM2 to be laminated into 50nm.Then, to on the thick Kovar alloy plate of 50nm, be provided with the mask of the peristome (being equivalent to remain wide is 50 μ m, 300 μ m rags) of 16 250 μ m by wet etching, carry out the mask exchange in a vacuum and make mask and ITO striped quadrature, for mask and ITO substrate are adjacent to, fix from the inside with magnetite.Evaporation 50nm magnesium, 150nm aluminium are then made the element of 32 * 16 dot matrixs.During this element of matrix driving, can not have to represent literal under the condition of cross-talk.

Practicality on the industry

The invention provides the high fluorescence methylene pyrrole metal complex compound that can be used in light-emitting component etc. The light-emitting component of efficiency height, high brightness and high color purity can be provided in addition.

Claims (5)

1. luminous element, this element is to have luminophore between anode and negative electrode, and utilizes the luminous element of electric energy, it is characterized in that, this element is luminous below the above 720nm of 580nm at the glow peak wavelength, and has the compound shown in (a);

(a) [3,4-c] pyrrole derivative of the diketone pyrrolo-shown in the general formula (3) and fluorescence peak wavelength are the following organic fluorescent substance of the above 720nm of 580nm,

In the general formula (3), R ⁷And R ⁸Can be the same or different, be selected from carbonatoms and be 1～25 alkyl or following general formula (4), Ar ¹¹And Ar ¹²Can be the same or different, represent unsubstituted phenyl, naphthyl, styryl, or have substituent phenyl, naphthyl, styryl, a carbazyl, wherein said substituting group be selected from alkyl, alkoxyl group, phenyl, tolyl, naphthyl, halogen, and adjacent substituting group between form condense aromatic nucleus and aliphatics ring

In the general formula (4), R ⁹And R ¹⁰Expression hydrogen, Ar ¹³Expression has the substituent phenyl that is selected from alkyl, the phenyl, and n represents 0.

2. the described luminous element of claim 1, wherein, luminophore has luminescent material, hole transporting material and electron transport materials at least, and luminescent material is diketone pyrrolo-[3,4-c] pyrrole derivative and an organic fluorescent substance.

3. the described luminous element of claim 2, wherein, diketone pyrrolo-[3,4-c] pyrrole derivative is a main material, organic fluorescent substance is a dopant material.

4. the described luminous element of claim 1, wherein, organic fluorescent substance is with general formula (6) expression;

In the formula, R ¹⁸～R ²⁴In at least one contain aromatic nucleus or and adjacent substituting group between form and to condense aromatic nucleus, the alkenyl that other is selected from hydrogen, alkyl, replaced by phenyl, phenyl, xenyl, naphthyl, sulfur phenenyl,  azoles base, and adjacent substituting group between form condense aromatic nucleus and aliphatics ring, R ²⁵, R ²⁶The expression fluorine, X represents carbon.

5. the described luminous element of claim 1, wherein, organic fluorescent substance is the light emitting element material with the methylene pyrrole metal complex compound shown in the general formula (1),

In the formula, R ¹, R ²Expression hydrogen, L represents fluorine or phenyl, and M represents boron, and m is 3, Ar ¹～Ar ⁵Expression phenyl, xenyl, naphthyl, these substituting groups can be unsubstituted, also can have substituting group.