TW200835676A - Dithiolene transition metal complexes and compounds analogous to selenium, their use as doping agent, organic semiconductive material containing the complexes, as well as electronic or optoelectronic structural element containing a comple - Google Patents

Abstract

The present invention relates to dithiolene transition metal complexes and their compounds analogous to selenium according to the structures 1 and 2, as well as to their use especially as doping agent for doping an organic semiconductive matrix material, to the organic semiconductive matrix material as well as to electronic and optoelectronic structural elements containing the compounds.

Description

200835676 IX. INSTRUCTIONS: The present invention relates to a disulfide transition metal complex and a selenium-containing compound thereof, which are used as a dopant for doping an organic semiconductor matrix material, used as a charge injection layer, and used as an electrode material. Used as a carrier material, as a matrix material itself or as a storage material for electronic or optoelectronic structural components, as an organic semiconductor matrix material and as an electronic or optoelectronic structural component.

It is known that the electrical properties of the organic semiconductor, particularly the conductivity, are changed by doping, as is the case with inorganic semiconductors such as germanium semiconductors. Depending on the form of dopant used, this achieves a relatively low increase in conductivity, by generating a charge carrier on the host material, resulting in a change in the Fermi level of the semiconductor, where doping results in a charge The increase in conductivity of the conductive layer results in a reduction in _ loss and, as a result, improved charge carrier transport between the contacts and the organic layer. Inorganic doping such as metal (e.g., absolute) or Lewis acid (e.g., FeC13) is disadvantageous in organic matrix materials because of their high diffusion coefficient because the electrical and structural stability of electrical structural components are negatively affected. However, the doping of lysine in the material is known to be prepared by chemical reaction, and the use of such a transfer is not sufficient, for example, the mouth, nT J such as a special ruthenium, and an organic light-emitting diode (OLED). ). Moreover, 'further compounds and/or atoms, for example, atomic hydrogen, are also produced during the release of the dopant, and the (four) containing the corresponding electrical structural elements affects the nature of the ride and the type of acceptor material can also be used as electricity. Producing an anode/receptor/hole tunneling material, such as, for example, an insultable material layer structure. The hole transporting material may be a layer of 6 200835676, , , or a layer of germanium, in particular, The hole transport material may also be doped with a receptor. The anode may be, for example, ITO, and the acceptor layer may be, for example, 〇5-100 nm thick. In one embodiment, the acceptor may be doped with a donor-like molecule.

The present invention has been made to overcome the disadvantages of this state of the art, and in particular to provide compounds which produce improved organic, semiconducting matrix materials, charge injection layers, matrix materials 5, electrode materials, particularly electronic or optoelectronic structural elements. The compound should preferably be of sufficiently high production potential, but will not interfere with the matrix and effectively increase the number of charge carriers for the wire and is relatively easy to handle. Other tasks included in this work include the ability to make the ride reveal, new composite materialization. Material = organic semiconductor material and electronic structural component or optoelectronic structural component.

The first line is solved by a dithione transition metal complex having the following structures 1 and 2 and a code-containing compound.

1 wherein in the structure 1 ·· -Μ is a trivalent transition metal; _QrQ6 is selected independently from the other by S and Se; -RrR6 is independent of the other by a multi-aromatic having at least one acceptor group Group compounds and face compounds, halogenated, non-halogenated carbon-carbon compounds; multi-function, aliphatic or cycloaliphatic carbon gas compounds (where two adjacent groups R1 and R2 or 200835676 3 and can be connected via at least one hetero atom Bridge to another; and CN selected; and the condition is 1 structure: _ M=, Mo, w, Fe, Ru, 〇s V Re; Q^S4

Ri phenyl or benzhydryl or H or CHS or. 2 out or C4 or COOCH3;

Cr, Mg, w, Fe, Ru, Os, V, Re; R!, R3, R5 = phenyl; and quinoxalinyl; M Cr, M 〇, W, Fe; Qi-6 = S; RA = CF3; and M-Mo, W; Se and Ri 6=CF3 are excluded; wherein in structure 2: -Μ is a divalent transition metal; -QrQ4 is independently selected from S and Se; -RrR4 Independent of the other, selected from the group consisting of multiple halogenated aromatic compounds and heterogeneous compounds having at least one acceptor group, secret, non-dentate, aliphatic and cycloaliphatic hydrocarbons and heterocyclic fatty hydrocarbons; multiple halogenated, fat Or a cycloaliphatic hydrocarbon (wherein two adjacent hydrazines and R3 and hydrazine can be bridged to another via at least one heteroatom; and CN; and the condition is 2: M = Fe, 〇), M, Pd, pt; and Ri = R2 = phenyl or benzyl or CH3 or C2H5 or C4H10 or CF3 or c〇〇cro; PCT = &, (: 〇, grab, 1 > (1, ?; and 111 , 13 = phenyl or 11; and R2, R4 = quinoxalin; and M-Ni, Pd, Pt, Cu, Ag, Au; QrQ4 = Se; and RrR4 8 200835676 = CF3 is excluded. In the structure 1, the transition metal is selected from the group consisting of Cr, Mo, W, and Fe. Ru, 0s, Shi, Re, V, Nb and Ta. Or '2 is preferably in the transition-metal structure is selected from Ni, Pd,

Pt, Co, Fe, Ag, Au, and Cu. It is also suggested that RrR6 in structure 1 and RrR4 in structure 2 are selected from perfluorinated or perchlorinated aromatic compounds and heteroaromatic compounds. The 1^_:^ in the structure 1 and the & in the structure 2 are also preferably selected from the group consisting of pentafluorophenyl and tetrafluoro-TI. A specific embodiment is characterized in that the at least one acceptor substrate is selected from the group consisting of CN, N02 ^ NO . CF3 ^ C2F5 > CF2C1 ^ C2F4CI ; C3F7 ; SF5 > COR10 and CO〇R10 ' wherein Ri is selected from halogenated and non-halogenated Aryl and alkyl. Even according to the dithione transition metal complex of the present invention and their selenium-containing compounds, used as a dopant for doping an organic semiconductor host material, as a charge injection layer, as an electrode material, as a transport material, The matrix material itself is either used as a t- or photovoltaic structural component in accordance with the invention. Further, an organic semi-material comprising at least one organic matrix compound and a dopant is according to the present invention, and the doping is a compound containing a disulfide-based compound according to the present invention. Preferably, the doping ratio of the dopant to the matrix molecule or the doping ratio of the dopant to the monomer of the polymer matrix molecule is between 2〇:1 and j•• excitation, _ is preferably Between 10:1 and 1:1, _, between 1:1 and 1:100. Furthermore, an electronic or optoelectronic structural element having an electrically functionally active region is the invention, wherein the electroactive region comprises at least one dithione transition metal complex according to the invention or a selenium-containing compound thereof. Preferably, the electroactive region comprises an organic semiconductor material doped with at least one dithione transition metal complex according to the invention or their ugly compound. Finally, it is proposed to be an organic light-emitting diode, a photovoltaic cell, an organic solar cell b, an organic diode or an electronic or optoelectronic structural element of the type having an airport effect transistor. Surprisingly, it has been found that the use of the disclosed electrically neutral, hexacoordination and dimer of a olefinic transition metal complex and a ruthenium containing compound is better than the previously known receptors (10) _ _ _ stronger And/or more desirable dopants, - the guacamene's 'coordination and dimer transition metal complexes or ruthenium-containing compounds can be reversed (10) as p-doped hetero-organic semiconductor materials. In particular, the conductivity of the charge transport layer is significantly increased when the composite is made according to the present invention and/or the charge carrier of the electronic structural component ridge between the free layers is improved. Without being limited thereto, it is assumed that the CT composite m is formed as a starting point according to the present invention, and the side is transferred by a specific surrounding matrix material by at least one electron, and likewise, the cation of the matrix material is also formed into a silk. (4) Material movement. In this way, the matrix material obtains a higher electrical conductivity than the conductivity of the undoped matrix material, and the conductivity of the undoped matrix material is typically > 1 〇 -8 mhos/cm, particularly often > 1010 Mou / cm. It is to be noted here that the matrix material has a sufficiently high purity which can be obtained by conventional methods, such as gradient sublimation. The conductivity of such a matrix material can generally be increased by doping to a value greater than lG_8 mM, often 200835676 is > l 〇 _ 5 ohm / cm, which is particularly useful for oxidizing potentials greater than _ 〇 5 than Fc / Fc The matrix material is preferably greater than 〇Vaby, especially greater than the publication. 2 volts Fc/Fc' indicator Fc/Fc+ means redox versus ferrocene / -pentane ion, which is a ship-based electrochemistry Cyclic volts, the indicator. According to the present invention, the dimethicone transition metal complex or the code-containing compound may also be used as an injection layer in the electronic structural component, preferably between the electrode and the semiconducting layer. Or as a barrier layer, preferably between the emitter layer and the transport layer in the electronic structural component. The compounds according to the invention have surprisingly high stability with respect to atmospheric reactivity. Preparation of hexacoordination transition metal complexes Electrically neutral, hexacoordinated and dimer transition metal complexes or selenium-containing compounds of disulfene can be synthesized according to known methods, and the synthesis of such compounds is described in For example, in the following citations, they are incorporated by reference in their entirety. Of course, the cited citations are only shown as examples. According to Schrauzer et al., such transition metal complexes can be made from 1,2-diketones or 2-hydroxyketones, phosphorus pentasulfide and suitable transition metal salts. Angew·Chem· (1964) 76 345, Z· Naturforschg· (1%4) 196 1080. The reaction of a transition metal carboxyl group with sulfur and acetylene or a corresponding selenium compound also produces a composite according to the invention, see A. Davison et al., Inorganic Chemistry (1964) 3/6 814; 9/8 (1970). Substituting transition metal carboxyl groups and even other types of 0-mussel transition metal compounds, for example, corresponding cyclooctane disulfide, phosphine', etc., and pure transition metals can also be used, see GN Schrauzer et al, 11 200835676 Ζ· Naturforschg· (1964 ) 19b, 192-8. Preparation of a hexa-coordinate transition metal complex corresponding to acetylene via Wittig reaction or Uhlmann reaction and subsequent elimination of hydrogen and subsequent reaction with sulfur and transition metal _(〇)_ compound or pure transition metal to correspond to transition metal diethylene II Prepared from thiol ester.

However, it is also possible to prepare symmetric, perfluorinated benzoquinones by reaction of an organometallic compound with oxalic acid chloride, which can also be prepared from acetylene, which can then be readily reduced to benzoin, which can then be converted to Transition metal diethylene dithiol ester.

Moreover, acetylene can react with sulfur/selenium to di-heterothiocyclobutene/seellenene cyclobutene, which can then react the opposite portion with the transition metal-(0)-compound or with the transition metal powder to correspond to the transition metal double Ethylene disulfide ester, refer to N. j.

Harris, Α·Ε· Underhill, Journal of the Chemical Society ’ Dalton Trans. (1987) 1683; A· Davision et al., JACS (1964) 86 2799-805. 12 200835676

Ri

Se I Se + M(CO)n

Synthetic methods for the reaction via acetylene and di-gasified disulfide or trithiocarbonate or carbon disulfide and sulfur are also described in the literature / J. Nakayama et al, Tetrahedeon Lett. (2000) 41 8349; B.R.〇, Connor,

F.NJones Journal of Organic Chemistry (1970) 36/6 2002; R. Mayer et al, Angew·Chem. (1964) 76 143; Μ· Ohashi et al.

Chemistry Lett· (1978) 1189. A free radical change has also been described to represent substituted 1,3-dithiol-2-one / γ·Gareau, A· Beauchemin Heterocycles (1998) 48 2003.

Preparation of new transition metal complexes Example A

Roll (12-bis-2_chlorotetrafluoroethylene _ 1,2-dithiolate) 锢 will be 0,24 grams of hexacarbonyl molybdenum and ruthenium, 32 grams of double _ (2_ gas tetrafluoroethyl) _ thiolate The toluene was heated at 10 liters for 24 hours under argon, and after cooling, the blue-black crystals were removed by suction. Yield 75%

Example B Volume (1,2-bis-2-gas tetrafluoroethylethylene·a disulfide vinegar) chromium bismuth, 13 grams of hexacarbonyl chromium and ruthenium, 32 grams of double ♦ chlorotetrafluoroethyl) _ thiolate It was heated under reflux of argon for 4 hours in 10 ml of dry ethylcyclohexane. After cooling, the pale purple black crystals were removed by attraction. The yield was about 65 〇/〇.

Example C will be 354 housek 4_(tetrafluoro-α-pyridyl)_5_(heptafluoro-oxime [bistrifluoromethyl 13 200835676-yl]butan-1-yl)·1,3·dithio-2-one and A solution of 312 Neck hexafluorene in 5% benzene was exposed to argon for 1 hour by means of a xenon lamp. After concentrating to a low level and adding hexane, the black-green crystals precipitated soon, which was removed by attraction. Yield: 17%.

Example D 354 克克 4-(tetrafluorobenzoate-4-yl)_5_(heptafluoro[bistrifluoromethyl]butanyl-1-yl)-1,3-dithioxanone and 287 mg of hexacarbonyl A solution of vanadium in 7 ml of benzene was exposed to argon for 1 hour by means of a xenon lamp. After concentration to low integrity and the addition of tetra, black-blue crystals precipitated, which are removed by attraction. Yield: 21%. Doped with a ruthenium complex, such as Zn(ZnPc), Cu(euPe), Ni'c) or other metals, wherein the ruthenium phthalocyanine ligand may also be substituted for 'p-interchangeable The matrix material, if necessary, may also be substituted or unsubstituted with other metal complexes of cilantroline and Parkin, hydrazine, or even arylated or heteroarylated amine or benzidine derivatives. , especially 螺旋 or even spiral-bonded composites, for example, TPD, a_Npj^, TDATA, spiro_TTB can be used as the matrix material, in particular, a-NpD and spiro_ττβ can be used as the matrix material.

200835676

In addition to polyaromatic hydrogen-hydrogen compounds, even heteroaromatic compounds, such as materials, articles, materials, and tri-filaments, other compounds = used as matrix materials, can optionally use dimers, oligomers or ^ Knife heteroaromatic compound. The heteroaromatic compound is preferably substituted, especially a substituent substituted, for example, a phenyl-substituted or a naphthyl-substituted b-functional compound, in particular, the above-mentioned compound can be used as a base material. Of course, the plant material can also be mixed with each other or with the other hair. Of course, other conjugated silk materials with turning impurities can also be used. Preferably, the dopant is present in a doping concentration of s ι:ι with a monomer of a matrix molecule or a polymer matrix molecule, preferably at a doping concentration of 1:2 or less. : 5 or less or 1:1 〇 or less doping concentration, doping concentration can be 1:1 to 丨: qing (8) turn, turn is 1:5 to 10,000 or 1.1 〇 to 1, 〇 The range of 〇〇 is, for example, in the range of HO to 1: leak or 1:25 to 1:5 ,, and is not limited thereto. The doping of the particular host material using the compounds of the present invention can be carried out by one or a combination of the following methods: a) The source of the host material and the dopant are derived from vacuum mixed evaporation. b) In particular, by sequential deposition of the heat-treated matrix material and p-dopant on the substrate 15 200835676 and subsequent diffusion of dopants. ...^ In particular, the matrix material is doped by heat treatment by subsequent evaporation of the dissolved p. dopant and solvent. d) # Surface doping of the matrix material layer by applying a dopant layer to the surface. e) Preparation of a solution of matrix molecules and dopants and subsequent fabrication of the layers by conventional methods, for example by dissolution or fine-solution. Doping can also be carried out in this age-based manner, so that the _ agent can be self-heated and the _ body compound is reduced. Example 2 'Rebel compounds, diazo compounds or similar compounds can be used as the former compound. It separates CO, nitrogen or others when the dopant is released, and other suitable precursors such as salts, such as, for example, or analogs, may also be used. The heat required for evaporation can be substantially facilitated by irradiation of the compound or precursor to be evaporated or a combination of a complex, such as a charge transfer complex, provided by irradiation, for example, by conversion to The excited state is transferred to the compound and shattered, and the composite may be, for example, the substrate is stabilized, and the substrate is evaporated or tested in an undissociated manner under the given conditions. Of course, other suitable methods can also be used for doping. Therefore, the p-doped layer of the Kasumi square (four) body can be produced in a financial manner. A semi-conducting layer, optionally a half-layer of a heterogeneously formed heterogeneous layer, for example, a pass or a joint, may be made using a transitional gold compound, and 200835676 may also make a conductive channel, a joint or The other conductive structures are only partially performed in the semi-conducting layer where the above-described layer treatment using electromagnetic irradiation is performed, wherein the conduction enthalpy is derived from the amount of the irradiated region, and 剌 is, the unilluminated layer range = the remaining amount can be used as the irradiation Range of insulation. The transition metal complex can be used herein as another compound-derived P-dopant used as a matrix material, and the doping ratio can be 1:1 or less. However, the dopant used may also be present in a high amount relative to a particular other compound or component such that the ratio of dopant to compound may be a ratio of >1:1, for example, > 2:1, 251 II 210 A ratio of 1 or 2 to 20:1 or higher, in the case of producing a doped layer, the specific other component may be similar to a component usable as a matrix material, and is not limited thereto. The dopant used may also optionally exist in the form of a pure substance, for example, in the form of a pure substance layer. The portion comprising the dopant or consisting essentially or completely of the dopant can be contacted in a current-conducting manner, in particular by an organic semiconductor material and/or an inorganic semiconductor material, which portions can be arranged on such a substrate. The so-called electron-deficient transition metal complex compound is preferably used as a p-dopant according to the present invention, for example, in a ratio of $1:1 or S1:2, for example, when using ZnPc 'S_TTB or a-NPD By using an electron-deficient compound which is used as a P-dopant according to the present invention, a semiconducting layer having a conductivity in the range of 1 〇 5 ohms/cm or higher at room temperature, for example, 1 〇 _ 3 can be obtained. Mho/cm or higher, for example 10-1 m/cm. When zinc phthalocyanine is used as a substrate, a conductivity of more than 10·8 mΩ/cm can be obtained, for example, 1 〇 6 m/cm. It has not previously been possible to dope this matrix with an organic acceptor because the reduction potential of the matrix is too small. On the other hand, the conductivity of the undoped zinc phthalocyanine is at most 10 ig m/cm. 17 200835676 Of course, a layer or structure having a dopant may comprise one or more different such electron-deficient transition metal complex compounds. The plurality of electronic structural elements or devices comprising the heavy earth structural elements may be fabricated using a P-doped organic semiconductor layer. When the p-doped organic semiconductor materials are fabricated using the recited compounds, they may be in the form of layers or electrically conductive channels. arrangement. From the point of view of the present invention, even the photovoltaic structural element is included in the viewpoint of "electric structural element". The electrical properties of the active region of the structural element, such as its electrical conductivity, luminescent properties or the like, may advantageously be altered by the novel compounds described. Thus, the conductivity of the doped layer may be improved and/or the charge carrier may be self-contained. The improvement of the contact of the junction into the doped layer. The invention comprises, in particular, organic light-emitting diodes (OLEDs), organic solar cells, field effect transistors, organic diodes, in particular those having a high rectification ratio, for example 103-107, preferably 1〇4-1〇7 , or 1〇5_1〇7, and a field effect transistor made of an electron-deficient transition metal complex compound. The P-doped layer based on the organic matrix material may be present in the electrical structural element, for example, in a layer structure in which the substrate or matrix material of the individual layer is preferably organic: p_i_n: p-doped semiconductor_insulator- N-doped semiconductor, n_i-P: η·doped semiconductor-insulator-p-doped semiconductor, “i” is an undoped layer in its part, “ρ” is a p-doped layer, Here, the contact material is a hole injection, wherein, for example, a layer or a contact of ιτο or may be provided on the P side, or an electron injection, wherein a layer or a contact of IT〇, A1 or Ag may be provided on the n side . 18 200835676 In the above structure, the i layer may be omitted if necessary, and as a result, a layer sequence having a p-n or n_p transistor can be obtained. ^ However, the use of the recited compound is not limited to the specific examples cited above, and in particular, the layer structure may be supplemented or modified by the introduction of additional suitable layers. In particular, QLEDs having such a layer sequence, in particular having a pin structure or having a structure opposite thereto, can be used to ride a compound member. In particular, the metal-insulator-p_doped semiconductor (at least) form or the selective pin form of the organic diode can be fabricated with the aid of the described Ρ·patch, = . These diodes show a rectification ratio of 1G5 and higher, and the it·η electro-crystal structure can be fabricated according to the invention using doping _, which is turned over to the p_doping side and η- The doped side (same as f-p_m), and the described electron-deficient transition metal complex compound are used for P-doped semiconductor materials. Electron-deficient transition metal complex compounds can be used in accordance with the invention for electrical structures. 7 亦可 can also be used for layers, conductive channels, punctate or the like. If the latter is predominant with respect to other components, for example, pure or substantially pure The form is used as an injection layer. Other operations and advantages of the present invention will be apparent from the following examples, which are considered to be illustrative only and not intended to limit the scope of the invention. The example of the solution is very electron-deficient, and the electrically neutral disulfene transition metal complex and the selenium-containing compound are prepared in a very clean manner. The electron-deficient transition metal complex compound placed on the substrate is simultaneously evaporated with the 19 200835676 base 5 material. According to the exemplary embodiment, the matrix material is 駄月辞, 螺-TTB or Xinqing, the p_doping The agent and the matrix material may have a doping ratio of a layer of p_ dopant to a matrix material of 1:1 以 on the layer of the fiber plate. Example 1: Reference (1,2-bis-2-chlorotetrafluoroethylethylene_12_dithiol) molybdenum neutral composite for doping spiro-TTB as a matrix material with dopants· The doping layer with a matrix-to-micron ratio of 1: ig is made by a mixture of a matrix and a dopant and a spiro-TTB, and the conductivity is (4) _5 mΩ/cm. Example 2: ginseng (H bis-2-chlorotetrafluoroethylethylene-i, 2 • dithiol) chromium t-complex _ _ snail · as a matrix material, with a dopant / matrix view The doping ratio is 丨: 1G secret riding system is made of matrix and dopant and spiro-TTB mixed secret (4), and the conductivity is 潇5 mhos/cm. Example 3: Refractory (H tetrafluorogalidyl) 2_(heptafluoro_u_[bistrifluoromethyl]butanyl)-1,2-dithiol) tumbling complex for doping snails - ΤΤΒ as a matrix material, with a dopant: the doping ratio of the matrix material is i · · 1 掺杂 doped layer is made by the mixed evaporation of the matrix and the dopant and the spiro-TTB, the conductivity is 2, 5 mho / cm. Example 4: ginseng (H tetrafluoroanthracene + yl)·2_(heptafluoro-u_[bistrifluoromethyl]butanyl yi,2-dithiol) hunger-neutral complex for doping snails As a matrix material, doped with 20 200835676 agent: the doping layer of matrix material with a doping ratio of 1:10 is made of a matrix and a mixture of dopant and spiro-TTB, and the conductivity is 4,9xlG_5m /cm. Applying a layer of an organic semiconductor material doped with a p-dopant to an ITO layer (indium tin oxide) arranged on the glass material, after the p-doped organic semiconductor layer, by using a suitable metal Vapor deposition _ metal anode to produce organic light-emitting diodes. Of course, the organic light-emitting diode may also have a layer of the same layer as the layer of the substrate - the metal anode - the P - doped organic layer - a transparent conductive protective layer (for example, IT0). Of course, the step-by-step layer can be provided between _. The features disclosed in the foregoing description and claims are individually or in any way. Material (10) which is very different embodiment to achieve the present invention

21 200835676 [Simple description of the diagram] None [Key component symbol description] None

twenty two

Claims (1)

20〇835676 X. Patent application scope: Dithione transition metal complexes with the following structures 1 and 2 and selenium-containing compounds: Wherein in structure 1: • Μ is a trivalent transition metal; • QrQ6 is selected from s and Se independently of each other; - RrR6 is independently derived from a polyhalogenated aromatic compound having at least one acceptor group and a heteroaromatic compound, _, non-halogenated, fat and ring fat money compounds and (iv) fatty hydrocarbons; multiple teeth a fatty, aliphatic or cycloaliphatic carbon ruthenium compound, wherein two adjacent groups & and / or & and R4 or & and oxime may be bridged to each other via preferably at least one heteroatom; and selected from CN; Structure 1 has: M = Cr, Mo, w, Fe, Ru, 0s, v, Rem RrR^phenyl or benzoyl or _CH3 or C2h5 or c4hi〇 or C00CH3; M = Cr, M〇, W , Fe, Ru, OS, v, Re; R, R3, R5 = the base; and R2, R4, Rg = 啥喔琳基, · M = Cr, M〇, W, Fe H ; RrR6 = CF3 ; Μ = Mo, W; Qf Se and Ri 6 = CF3 are excluded; 23 200835676 wherein in structure 2: - Μ is a divalent transition metal; _Qi-Q4 is selected from S and Se independently of each other; -RrR4 is mutually Independently selected from polyhalogenated aromatic compounds and heteroaromatic compounds having at least one acceptor group, halogenated, non-dentated, aliphatic and cyclic aliphatic hydrocarbons and heterocyclic fatty hydrocarbons; multiple _, fat or ring a fatty carbonium compound (wherein two adjacent RAR2 or & R4 can be bridged to each other via at least one heteroatom; and CN is selected; and the condition is structure 2 has: CH3 or C2H5 or C4H10 or CF3 or COOCH3; M = Fe, Co, Ni, Pd, Pt; and Rl, R3 = phenyl or H; and R2, R4 = quinoline; and Μ = Νι, Pd, Pt, Cu, Ag, Au; QA = Se; and RrR4 = # CF3 are excluded. 2. The dithione transition metal complex and the selenium-containing compound as claimed in claim 1 are characterized in that The transition metal in structure 1 is selected from the group consisting of Cr, Mo, W, Fe, Ru, Os, Mn, Re, V, Nb, and Ta. 3. The dithione transition metal complex according to the scope of the patent application and a selenium-containing compound characterized in that the transition metal in the structure 2 is selected from the group consisting of Ni, Pd, Pt, C, Rh, Fe, and Cu. 4. The disulfide according to any one of the patent claims. The olefinic transition metal complex and the selenium-containing compound are characterized in that the RrR4 structure of the structure 2 and at 24 200835676 structure 2 is selected from a perfluorinated or perchlorinated aromatic compound and a heteroaromatic compound. The dithione transition metal complex and the selenium-containing compound of the fourth aspect of the patent are characterized by RrR6 in the structure and structure 2 The R1-R4 is selected from the group consisting of pentafluorophenyl and tetrafluoroacridine. 6. The dithizone metal complex and the nitrate-containing compound according to any one of the preceding claims, characterized in that at least one receptor The base is selected from the group consisting of CN'n〇2'no'cf3'C2f5.cf2ci. c2f4ci; c3f7; SF5, CORM CO〇R10, wherein the Ri(R) is selected from the group consisting of abusive and non-nanal aryl and alkyl groups. The disulfide transition metal derivative and the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ =, as an electrode material, as a transmission material 2 8. The material itself or as a storage material. , the machine fiber and the type of _ an organic half = which is characterized by the fact that the dopant is the scope of the patent application! a disulfide transition metal complex of the same type or an organic semiconductor material of the eighth aspect of the patent containing lr, the pot is characterized by a dopant and a matrix molecule of the matrix, characterized by a mass molecule The doping ratio of the monomer is two or the dopant and the polymer base are preferably between 20:1 and 1:100, _, and the ratio is preferably between 10:1 and 1:1, _ 10. A kind of temple with Lei Gong 4 is between 1:1 and 1:100. An electronic or optoelectronic structural component of the active area of the electric power b, the special 25 200835676 is characterized in that the electric active region comprises at least one of the first two transition metals 11 as claimed in the patent range f 10 or An optoelectronic structural element, characterized in that the electroactive region comprises an organic semiconductor material doped with at least one dithione transition metal complex as claimed in the scope of the patent application, or a selenium-containing compound. To compound. 12. An electronic or optoelectronic structural element as claimed in claim 10 or U is of the type of an organic light emitting diode, a photovoltaic cell, an organic solar cell, an organic diode or an organic field effect transistor. 26