Substituted 1,2,3-trisyltris(cyanomethylidyne)cyclopropanes for vte, electronic devices and semiconductor materials using the same

Abstract

The present invention relates to substituted 1,2,3-triyl tris(cyanomethylidene)cyclopropanes for use in VTE, electronic devices and semiconductor materials using the same. In particular, the present invention relates to a method of preparing an electrically doped semiconductor material comprising a [3]-fused p-dopant or of preparing an electronic device containing a layer comprising a [3]-fused p-dopant, the corresponding [3]-fused compounds as well as semiconductor materials and layers and electronic devices comprising said compounds; said method comprising the steps of (i) loading an evaporation source with a [3]-fused p-dopant, and (ii) evaporating said [3]-fused p-dopant at elevated temperature and reduced pressure, wherein said [3]-fused p-dopant is selected from the group consisting of compounds having a structure according to formula (I), wherein A 1 and A 2 is independently aryl or heteroaryl substituted cyanomethylidene.

Description

[0001] This application is a divisional application of the international application filed on December 16, 2015, with international application number PCT / EP2015 / 080046, which entered the Chinese national phase on June 16, 2017, application number 201580069040.4, and invention title "Substituted 1,2,3-triethylenetris(cyanomethylethylene)cyclopropane for VTE, electronic devices and semiconductor materials using the same". Technical Field

[0002] This invention relates to aryl or heteroaryl substituted 1,2,3-triylidenetris(cyanomethanylylidene)cyclopropane, its use as a p-doper or hole injection material in semiconductor electronic devices, and a stable vacuum thermal evaporation (VTE) method for manufacturing such devices. Background Technology

[0003] Cyanomethyl groups substituted with electron-withdrawing aryl or heteroaryl groups [3]-axylene compounds have been found to be particularly suitable as p-dopersins for common organic light-emitting diode (OLED) hole transport materials (HTMs), see, for example, US 8 057 712B2, which is incorporated herein by reference. For the industrial production of electronic devices and semiconductor materials using these compounds, vacuum thermal evaporation (VTE) methods are typically used. In existing evaporation sources and in the use of these evaporation sources, below 10 - 4 Under pressures of Pa, currently used materials typically vaporize at temperatures between 150 and 300°C. For efficiency, evaporation sources loaded with this material once are preferably kept in operation for as long as possible. The concurrent hole transport matrix compounds used in OLEDs are typically kept exposed to their evaporation temperatures for one or two weeks without significant changes in their impurity distribution. In the mass production of organic electronic devices including electrically doped materials, the insufficient long-term thermal stability of existing dopants often represents a critical limitation on the duration of the production campaign.

[0004] Therefore, one object of the present invention is to provide an improved method for manufacturing electronic devices comprising an axialene p-dopant and an improved semiconductor material, and layers and / or electronic devices that can be prepared by the improved method. Another object of the present invention is to provide an improved axialene p-dopant for use in the improved method. Yet another object of the present invention is to provide an improved method for preparing the improved axialene p-dopant. Summary of the Invention

[0005] The first objective is achieved by a method for preparing electrically doped semiconductor materials containing [3]-axylene p-doped agents, or for preparing electronic devices containing layers containing [3]-axylene p-doped agents, the method comprising the following steps:

[0006] (i) Loading the evaporation source with [3]-axylene p-dopant, and

[0007] (ii) Evaporation of [3]-axylene p-dopant under elevated temperature and reduced pressure,

[0008] The [3]-axylene p-dopant is selected from compounds having a structure according to formula (I).

[0009]

[0010] Where A 1 and A 2 A cyanomethylene group that is independently substituted with an aryl or heteroaryl group.

[0011] The aryl and / or heteroaryl groups in A 1 and A 2 The radical is independently selected from 4-cyano-2,3,5,6-tetrafluorophenyl; 2,3,5,6-tetrafluoropyridin-4-yl; 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl and 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl.

[0012] And at least one aryl or heteroaryl group is 2,3,5,6-tetrafluoropyridin-4-yl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl or 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl, provided that A is true. 1 With A 2 The heteroaryl groups in both cannot be 2,3,5,6-tetrafluoropyridin-4-yl at the same time.

[0013] Next, the vaporized compound (I) is deposited as a pure layer or co-deposited with a suitable matrix material. The pure layer of compound (I) advantageously serves as a hole injection or charge generation layer, preferably adjacent to a layer comprising the matrix material. The matrix material is preferably a hole transport matrix material comprising at least one hole transport matrix compound. Examples of hole transport matrix compounds electrically doped with axial-ene p-dopersants are well known from early Novaled applications, including those cited herein.

[0014] Preferably, the evaporation temperature in step (ii) is in the range of 100-300°C, more preferably in the range of 125-275°C, and even more preferably in the range of 150-250°C.

[0015] The pressure in step (ii) is preferably less than 10. -1 Pa, more preferably less than 10 Pa -2 Pa, or even more preferably less than 10 Pa -3 Pa, optimal value is less than 10 -4 Pa.

[0016] The duration of the evaporation step (ii) is preferably more than 100 hours, more preferably more than 150 hours, and even more preferably more than 200 hours.

[0017] To achieve sufficient doping strength, cyclic voltammetry (CV) was used to perform redox reactions of ferrocene / ferrocene ions (Fc / Fc) in acetonitrile (ACN) targeting the standard. + The redox potential of the measured [3]-axylene p-doped agent is preferably in the range of +0.10V to +0.50V, more preferably in the range of +0.20V to +0.40V, and even more preferably in the range of +0.25V to +0.35V.

[0018] The first objective is also achieved by using [3]-axylene compounds selected from compounds having a structure according to formula (I) as p-dopersants or hole injection materials in electronic devices.

[0019]

[0020] Where A 1 and A 2 A cyanomethylene group that is independently substituted with an aryl or heteroaryl group.

[0021] The aryl and / or heteroaryl groups in A 1 and A 2The radical is independently selected from 4-cyano-2,3,5,6-tetrafluorophenyl; 2,3,5,6-tetrafluoropyridin-4-yl; 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl and 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl.

[0022] And at least one aryl or heteroaryl group is 2,3,5,6-tetrafluoropyridin-4-yl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl or 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl, provided that A is true. 1 With A 2 The heteroaryl groups in both cannot be 2,3,5,6-tetrafluoropyridin-4-yl at the same time.

[0023] The first objective is also achieved by semiconductor materials, semiconductor layers, and / or electronic devices comprising axial ene compounds having formula (I), which may not include experimental OLEDs constructed on glass substrates as described in the following device examples, equipped with the following components: an ITO anode, a 10 nm thick hole injection transport layer (HIL) consisting of a commercially available biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS No. 1242056-42-3) doped with 8 wt% of the test compound, a 130 nm thick hole transport layer made with the same matrix compound as the HIL, a 20 nm thick host compound ABH113, and 3 wt% emitter NUBD370 (all from the same supplier Sun). The light-emitting layer made of FineChemicals (Korea), a 36 nm thick electron transport layer made of (3-(dibenzo[c,h]acrid-7-yl)phenyl)diphenylphosphine oxide and 8-hydroxyquinoline lithium (LiQ, 1:1 w / w), and a 30 nm thick silver cathode, and may not include a layer of such doped material consisting of biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-9-phenyl-9H-carbazol-3-yl)phenyl]-amine doped with 8 wt% of any of the compounds selected from A1, A2, A3, A4, A5, A6, A7, A8 and B1, B2, B3, B4, B5, B6, B7 listed below, and / or a 10 nm thick layer of such doped material.

[0024] Preferably, a semiconductor material or semiconductor layer comprising a compound having formula (I) is contained between the first electrode and the second electrode. Also preferably, the first electrode is an anode and the second electrode is a cathode. In a preferred embodiment, the layer comprising the compound of formula (I) is adjacent to the anode. In another preferred embodiment, the layer comprising the compound of formula (I) serves as a charge-generating layer. Also preferably, the electronic device is an OLED, and in a preferred embodiment, a tandem OLED.

[0025] The second objective is achieved through [3]-axylene compounds having a structure according to formula (I).

[0026]

[0027] in

[0028] A 1 and A 2 A cyanomethylene group that is independently substituted with an aryl or heteroaryl group.

[0029] The aryl and / or heteroaryl groups in A 1 and A 2The radical is independently selected from 4-cyano-2,3,5,6-tetrafluorophenyl; 2,3,5,6-tetrafluoropyridin-4-yl; 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl and 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl.

[0030] And at least one aryl or heteroaryl group is 2,3,5,6-tetrafluoropyridin-4-yl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl or 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl, provided that A is true. 1 With A 2 The heteroaryl groups in both cannot be 2,3,5,6-tetrafluoropyridin-4-yl at the same time.

[0031] The compound (I) of the present invention is designed such that, in embodiments of the method of the present invention (whereby compound (I) is co-evaporated with a hole transport matrix material and then co-deposited), for vaporization temperatures in the range of 100-300°C and relative to Fc + / Fc reference redox pair is any hole transport matrix compound in acetonitrile with a redox potential in the range of 0.00-0.50V. A thermally stable compound (I) with sufficient p-doping strength and a vaporization temperature less than 50°C different from that of the selected hole transport matrix compound can be selected.

[0032] The third objective is achieved by synthesizing [3]-axylene compounds having the structure according to formula (I).

[0033]

[0034] in

[0035] A 1 and A 2 A cyanomethylene group that is independently substituted with an aryl or heteroaryl group.

[0036] The aryl and / or heteroaryl groups in A1 and A 2 The radical is independently selected from 4-cyano-2,3,5,6-tetrafluorophenyl; 2,3,5,6-tetrafluoropyridin-4-yl; 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl and 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl.

[0037] And at least one aryl or heteroaryl group is 2,3,5,6-tetrafluoropyridin-4-yl; 2,4-bis(trifluoromethyl)-3,5,6-trifluorophenyl; 2,5-bis(trifluoromethyl)-3,4,6-trifluorophenyl; 2,4,6-tris(trifluoromethyl)-1,3-diazin-5-yl; 3,4-dicyano-2,5,6-trifluorophenyl; 2-cyano-3,5,6-trifluoropyridin-4-yl; 2-trifluoromethyl-3,5,6-trifluoropyridin-4-yl; 2,5,6-trifluoro-1,3-diazin-4-yl or 3-trifluoromethyl-4-cyano-2,5,6-trifluorophenyl, provided that A is true. 1 With A 2 The heteroaryl group in both cannot be 2,3,5,6-tetrafluoropyridin-4-yl at the same time.

[0038] In this embodiment, the compound of formula (I) is formed in the final synthetic step, which is carried out in a solvent containing at least one saturated halocarboxylic acid. It should be understood that the saturated carboxylic acid contains only a single (σ) carbon-carbon bond. The saturated halocarboxylic acid can be aliphatic or alicyclic. More preferably, it is a saturated halocarboxylic acid that is liquid at 20°C, and even more preferably, it is a saturated halocarboxylic acid that is liquid at 0°C. In one embodiment, the saturated halocarboxylic acid is a saturated perhalocarboxylic acid. In a preferred embodiment, the saturated perhalocarboxylic acid is trifluoroacetic acid.

[0039] Preferably, the concentration of saturated halocarboxylic acid is in the range of 5-95 wt%, more preferably in the range of 10-90 wt%, even more preferably in the range of 15-85 wt%, and most preferably in the range of 20-80 wt%.

[0040] The solvent may also contain saturated carboxylic acids and / or inorganic acids. Saturated carboxylic acids may be acetic acid, and inorganic acids may be nitric acid.

[0041] Preferably, an oxidizing agent is present in the final synthetic step in which compound (I) is formed. Also preferably, nitric acid is used as the oxidizing agent. Also preferably, the nitric acid contains water. Also preferably, the final synthetic step in which compound (I) is formed is substantially free of free halogens, as described in WO2015 / 007729. Also preferably, the reaction temperature in the final synthetic step is in the range of 0-100°C, more preferably in the range of 10-90°C, even more preferably in the range of 15-85°C, and most preferably in the range of 20-80°C. Particularly high yields and / or purity are achieved when using this method. Attached Figure Description

[0042] Figure 1 The temperature T with 0.5% weight loss at atmospheric pressure is shown in the TGA analysis. 99.5 The rate onset temperature T measured in a high vacuum test chamber tc (Specified as T in the figure) sub The correlation between them; expressed as a linear relationship y = 0.7326*T. 99.5％ The correlation coefficient of -50.084 was used to estimate the T of the compound. tc Values, of which experimental values ​​have not yet been obtained. Detailed Implementation

[0043] The [3]-axylene p-doped known from US 8 057 712 B2 has proven to be a highly successful p-doping concept, especially for OLED displays. This conclusion can be obtained from other documents such as WO2010 / 075836, WO2010 / 132236, WO2011 / 134458, WO2014 / 009310, US2012 / 223296, WO2013 / 135237, WO2014 / 037512, and WO2014 / 060526.

[0044] Depending on the device design and the specific compound selected as the matrix for hole transport, electron blocking, and / or light emission layers (where p-dopers can be used in or adjacent to these layers), the energy level of the lowest unoccupied molecular orbital (LUMO) of the dopant and its optimal evaporation temperature can vary over a fairly wide range, as required for optimal compatibility with the properties of the selected hole transport matrix and the materials selected for adjacent layers.

[0045] This variability is the main impetus for further development of new compounds to provide a wide range of [3]-axylene p-doped agents, thereby enabling the provision of dopants that are well-matched to the highest occupied molecular orbital (HOMO) energy level of the selected matrix and the evaporation temperature of the matrix for various specific conditions in industrial evaporation sources.

[0046] A common criterion for selecting a suitable structure is that the provided p-dopant must have high long-term thermal stability, thereby enabling the evaporation source loaded with the compound to have a reasonably long production life.

[0047] In the candidate compounds, this requirement was checked using a specially designed “ampoule test.” Samples of each specific compound, dispensed into quartz ampoules and sealed under vacuum, were kept in a thermostat at various temperatures for a period ranging from 100 to 350 hours. Changes in the distribution of impurities in the samples were examined using spectroscopic and chromatographic methods specifically designed for [3]-axylene p-dopersants. Specific structural motives that could achieve stable purity after a treatment time of at least 100 hours at the compound’s evaporation temperature were ultimately identified.

[0048] The new structural theme lies in novel substitution modes for aryl or heteroaryl substituents in formula (I). Other studies have shown that a large number of thermally stable p-dops with varying strengths and volatility can be obtained by combining newly identified advantageous structural features together in an axial ene molecule or by combining these features with carefully selected substitution modes known in the prior art.

[0049] Regarding equation (I), all A 1 They are all the same, but A 1 and A 2 They may be the same as or different from each other.

[0050] It should be understood that, for the sake of brevity, structural part A... 1 and A 2 All compounds of formula (I) having the same substitution pattern are designated as "symmetric" in this application. Similarly, structural part A... 1 and A 2 All axialene compounds with different substitution modes are designated as "asymmetric". This designation does not cover possible geometric isomers formed by various combinations of E- and Z-substitution on the exocyclic double bonds. It is assumed that although the exemplary structures depicted for the axialene compounds of the present invention and comparisons are dominant, the materials synthesized by the method may contain all possible geometric isomers.

[0051] Similarly, for the sake of brevity, all possible tautomers and geometric isomers of ester intermediates, betaine intermediates, and axylene precursors (the reduced form of the desired axylene compound) are simplified with the exemplary structures depicted, but these structures actually represent all possible isomers and tautomers for each individual case.

[0052] It was found that for structural part A 1 and A 2Any formula (I) test structure containing two different aryl and / or heteroaryl substituents is represented by cyclic voltammetry in acetonitrile targeting Fc / Fc. + The dopant strength of the redox potential of a reference redox pair measured under standard conditions can be within 10% accuracy of the redox potential derived from a symmetric parent alkene compound containing an aryl / heteroaryl substitution mode combined in the resulting asymmetric structure.

[0053] It was found that each heteroaryl-substituted cyanomethylene structural unit in the [3]-axylene molecule functions as an independent part contributing to the total redox potential in a constant increment, which is not affected by the substitution mode of the heteroaryl substituents at the two remaining turns connected to the [3]-axylene core. This fact makes it easy to predict the redox potential of the asymmetric structure based on the redox potential measured for the symmetric “mother” structure containing the corresponding substitution mode.

[0054] In other words, the redox potential of any asymmetric structure belonging to equation (I) can be estimated as a linear combination of the increments from the structural parts of the corresponding symmetric structure.

[0055] The objective is demonstrated by comparing the properties of the compounds of the present invention with those of comparative compounds known from or that can be obtained from combinations thereof in the prior art documents cited above.

[0056] The technical effects of this invention can be summarized in three points: the improved axialene p-dopants according to this invention retain the good properties of known compounds in electronic devices (such as OLED displays) and semiconductor materials, and allow for stable VTE methods to manufacture organic electronic devices containing axialene p-dopants, suitable for industrial scale.

[0057] Specifically, this invention allows for the independent adjustment of the volatility and doping intensity of the dopant within a sufficiently wide range, based on the dopant availability and volatility of the selected matrix. Furthermore, compared to existing technologies, the method of this invention for manufacturing the p-dopants can be carried out on an industrial scale with more stable quality and higher yield.

[0058] Furthermore, in any case where the new compound of formula (I) is used instead of the existing p-dopants with lower redox potentials, the stronger p-dopant can be used at a lower concentration. This provides additional freedom for designers of electronic devices, for example, in reducing the optical absorption of doped layers, which can be provided using the materials of this invention compared to existing p-dopants.

[0059] Exemplary structures of the comparative compounds are

[0060]

[0061]

[0062] Exemplary symmetrical structure of the compound of the present invention

[0063]

[0064]

[0065] Asymmetric structure

[0066]

[0067]

[0068] Table 1

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] Explanation of the table:

[0075] Melting point (mp) temperature was measured by DSC at a heating rate of 10 K / min, and the reported values ​​correspond to the peak temperature of the endothermic melting observed on the DSC curve. dec This represents the peak temperature of the decomposition peak on the TGA / DSC curve. The expected vaporization temperature in an industrial VTE source used for mass production of OLED displays is estimated using two experimentally measured parameters. The first, T... tc , is the evaporation temperature of the compound in a high-vacuum test chamber equipped with a temperature sensor that measures the temperature at the bottom of a vaporization crucible filled with a standard amount of the test compound. The table below reports the temperatures corresponding to the vaporization initiation temperatures measured by a detector placed above the crucible. The second parameter, T... 99.5％ The TGA curves, corresponding to the temperature at which the test compound experiences a 0.5% weight loss at atmospheric pressure and a heating rate of 10 K / min, show the onset of evaporation of the compound at atmospheric pressure. 0 The value representing the electrochemical redox potential is derived from the Fc / Fc ratio of the standard reference in an acetonitrile solution of the test compound. +Cyclic voltammetry curves were measured. All tested compounds showed reversible redox properties under these conditions.

[0076] It was found that in mass-produced gasification sources, from specific materials T tc and T 99.5％ The arithmetic mean of the calculated values ​​fits well with the observed vaporization temperature for this material. For materials where T can be obtained... tc With T 99.5％ For the compounds of both, the estimated vaporization temperature T in the industrial evaporation sources reported in the table is... est This corresponds to the arithmetic mean.

[0077] For only T can be obtained 99.5％ Compounds, T est Calculated in the same way, only the T used in the calculation tc It is used from Figure 1 The T shown 99.5％ With T tc The linear relationship between them is y = 0.7326*T. 99.5％ -50.084, from the observed T 99.5％ The value of y is calculated.

[0078] Table 1 shows the properties of the new compounds that satisfy the objectives of this invention, thus providing a wide range of available redox potentials and vaporization temperatures. For the test compounds, reasonable long-term thermal stability was demonstrated at the expected vaporization temperatures of industrial VTE sources.

[0079] Of course, this does not preclude the possibility that the compounds of this invention could also be advantageous in methods developed as alternatives to VTE, particularly in solution treatment. The new compounds have been shown to offer not only a wide range of volatility but also a wide range of solubility in various solvents.

[0080] Example

[0081] Synthesis Examples

[0082] The synthesis of the symmetrical compounds is based on the procedures described in patent US 8 057 712 and application EP13176542.

[0083] The synthesis of the asymmetric substituted derivatives is based on the procedure described in US 3 963 769 and J. Am. Chem. Soc. 1976, Vol. 98, pp. 610-611.

[0084] betaine precursor

[0085] Betaine C2-B

[0086] Tetrachlorocyclopropene (8.30 g, 46.7 mmol) was added to a 500 mL Schlenk flask, followed by the addition of 2-(4-cyano-2,3,5,6-tetrafluorophenyl)acetonitrile (C2-A, 20.0 g, 93.4 mmol) and anhydrous dichloromethane (DCM, 160 mL). The mixture was stirred and cooled to -30 °C, and triethylamine (30.7 g, 304 mmol) was added dropwise over 30 min. The mixture was warmed to room temperature over 1 h. Water (24 mL) was added dropwise and the mixture was filtered. The solid was washed with DCM (3 × 50 mL), MeOH (2 × 50 mL), and water (4 × 50 mL) and dried under vacuum to give 28 g of crude product. Recrystallization from acetonitrile gave the product as a yellow solid (19 g, 34 mmol).

[0087] TGA-DSC (screening): 0.5% mass loss = 215℃, Tdec. (initial) = 217℃.

[0088] ESI / APCI-MS: m / z=532 (M-C2H5).

[0089] IR[cm -1 ]: 2987(w), 2243(m), 2196(m), 1851(m), 1642(s), 1479(s), 1422(s), 1368(s), 1313(s), 1200(m), 1139(m), 975(s), 894(m), 812(m).

[0090] 19 F NMR (471MHz, CD3CN) δ = -136.53, -141.77.

[0091] 1 H NMR (500MHz, CD3CN) δ = 3.90 (q, 2H), 1.42 (t, 3H).

[0092] Betaine C4-B

[0093] Tetrachlorocyclopropene (4.15 g, 23.3 mmol) was added to a 250 mL Schlenk flask, along with 2-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)acetonitrile (C4-A, 12.0 g, 46.7 mmol) and anhydrous DCM (80 mL). The mixture was stirred and cooled to -30 °C, and triethylamine (15.4 g, 152 mmol) was added dropwise over 30 min. The mixture was warmed to room temperature over 1 h. Water (12 mL) was added dropwise and the mixture was filtered. The solid was washed with water (2 × 140 mL) and dried under vacuum to give 6 g of crude product. The filtrate was concentrated to 30 mL, from which a precipitate formed. The precipitate was filtered to give a second batch of crude product (6 g). Each batch was stirred for 1 h at room temperature in the presence of diethyl ether (25 mL), filtered, and the solid was dried under vacuum. The product was obtained as a colorless solid (5.49 g and 5.81 g, which equal 11.3 g, 17.5 mmol).

[0094] ESI-MS: pos. 436,648(M) + ,686;neg.618(M-Et-H) -

[0095] 19 F NMR (471MHz, CD3CN) δ = -57.05, -142.79, -144.39.

[0096] 1 H NMR (500MHz, CD3CN) δ = 3.89 (q, 2H), 1.43 (t, 3H).

[0097] IR[cm -1 ]:2996(w),2185(m),1862(w),1652(m),1654(s),1461(s),1419(s),1397(m),13 35(s),1316(m),1254(s),1170(m),1150(m),1124(s),1043(m),977(s),812(m).

[0098] The betaine-like intermediates C3-B, A1-B, A2-B, A3-B, A4-B, A5-B, A6-B, A7-B and A8-B, which are substituted with symmetric axial alkenes C3, A1, A2, A3, A4, A5, A6-B, A7-B and A8-B, can be prepared similarly to C2-B and C4-B.

[0099] Compare compound C5

[0100] Axylene precursor (reduced form) C5-P

[0101] Under argon atmosphere, betaine C2-B (5.61 g, 10.0 mmol), anhydrous potassium phosphate (4.46 g, 21.0 mmol), and 4-dimethylaminopyridine (1.22 g, 10.0 mmol) were added to a 500 mL Schlenk flask. The flask was cooled on ice and anhydrous DMF (185 mL) was added. The mixture was stirred on ice for 10 min, and a solution of 2-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)acetonitrile C4-A (2.70 g, 10.5 mmol) in DMF (15 mL) was added over 10 min. After stirring on ice for 4 h, the cooling bath was removed and the mixture was warmed to room temperature. After a total reaction time of 27 h, the dark red mixture was added to brine (150 mL) and EtOAc (400 mL). The phases were separated and the organic layer was washed with semi-concentrated brine (2 × 150 mL), 2M HCl aqueous solution (3 × 150 mL) (the solution turned dark green), and saturated NaHCO3 aqueous solution (3 × 100 mL) (the solution turned black / red). The organic phase was dried over MgSO4 and concentrated. Column chromatography (silica gel) was performed using DCM / MeOH to obtain a dark red solution, which was then concentrated to give the product (4.88 g) as a black solid.

[0102] This intermediate is not further purified and is used directly in the final step.

[0103] Axyne C5

[0104] The precursor C5-P (4.82 g) was dissolved in glacial acetic acid (67 mL), and an aqueous nitric acid solution (65% w / w, 67 mL) was added dropwise at room temperature. The solution changed from black / green to red / orange. After stirring for 16 h, an orange precipitate formed, and the mixture was cooled on ice. Water (70 mL) was added dropwise, and the mixture was stirred for 15 min. The orange solid was filtered and washed with cold water (10 × 40 mL) until the filtrate was neutral. It was dried in air and under vacuum with an oil pump to give 3.25 g of solid, which was dissolved in hot 1-chlorobutane (100 °C, 400 mL). The solution was cooled to room temperature and filtered through a glass frit. The filtrate was concentrated to about 50 mL to give a suspension containing the orange solid. After filtration and drying in air and under vacuum with an oil pump, the product (2.62 g) was obtained as an orange powder and further purified by sublimation under high vacuum.

[0105] ESI-MS: m / z = 715 (neg.)

[0106] UV-Vis (acetonitrile (ACN)): λ max =457nm.

[0107] IR[cm -1]: 2249(w),1662(w),1563(m),1486(s),1415(m),1343(m),1328(m),1257(m),1194(m),1155(m),1069(m),978(s),909(m),813(m),717(m).

[0108] TGA-DSC (Volatile): 0.5% mass loss at 281℃, T dec. (Initial) = 325℃.

[0109] 19 F NMR (471MHz, CH3CN): δ = -57.43, -77.04, -132.42, -134.43, -135.08, -139.98.

[0110] Compare compound C6

[0111] Axylene precursor (reduced form) C6-P

[0112] Cs₂CO₃ (3.42 g, 10.5 mmol) and DMF (90 mL) were added to a 250 mL Schlenk flask. The mixture was stirred on ice for 10 min and betaine C₄-B (3.24 g, 5.0 mmol) was added. After 10 min, a solution of 2-(4-cyano-2,3,5,6-tetrafluorophenyl)acetonitrile C₂-A (1.09 g, 5.1 mmol) in DMF (10 mL) was added. The mixture was stirred on ice and the cooling bath was removed after 19 h. After a total reaction time of 1 day and 19 hours, the dark red mixture was added to brine (80 mL) and EtOAc (200 mL). The phases were separated and the organic layer was washed with semi-concentrated brine (2 × 80 mL), dried with MgSO₄ and concentrated to give a product (6.29 g) containing some residual DMF as a dark red oil.

[0113] This intermediate is not further purified and is used directly in the final step.

[0114] C6-axis alkene

[0115] The precursor C6-P (6.29 g) was dissolved in 83 mL of glacial acetic acid, and an aqueous nitric acid solution (65% w / w) was added dropwise at room temperature. The solution changed from dark green to reddish-orange. After stirring for 16 h, an orange precipitate formed, and the mixture was cooled on ice. 100 mL of water was added dropwise, and the mixture was stirred for 15 min. The orange solid was filtered and washed with cold water (8 × 30 mL) until the filtrate was neutral. After drying in air and under vacuum with an oil pump, the product (3.07 g) was obtained as an orange powder, which was further purified by sublimation under high vacuum.

[0116] ESI-MS: m / z = 758 (neg.)

[0117] UV-Vis(ACN): λ max =454nm.

[0118] IR[cm -1 ]: 2248(w),1662(w),1565(m),1483(s),1416(m),1339(s),1252(m),1198(m),1148(s),1060(m),984(s),907(m),812(m),785(w),715(m).

[0119] TGA-DSC (Volatile): 0.5% mass loss at 252℃, T dec. (Initial) = 320℃.

[0120] 19 F NMR (471MHz, CD3CN) δ = -57.46, -132.46, -134.50, -135.15, -140.04.

[0121] Compound B5 of this invention

[0122] Step 1: 1-Cyano-1-(2-Cyano-3,5,6-trifluoropyridin-4-yl)-2-ethoxy-2-oxoethyl-1-ylpotassium (ester intermediate A3-eE)

[0123]

[0124] In a 250 mL flask, 7.2 g (142 mmol) of 2-cyano-3,4,5,6-tetrafluoropyridine, 60 mL of acetonitrile, and 6.78 g (170.4 mmol) of potassium carbonate were added to a solution of 4.6 g (142 mmol) of ethyl cyanoacetate dissolved in 10 mL of ACN. After stirring at room temperature for 3 days, the precipitate was filtered and washed with 2 × 20 mL of ACN. The organic solvent was evaporated. The mixture was then heated under vacuum (10 °C). -3 The remaining orange solid was dried in millibars and used in the next step without any further purification.

[0125] Yield: 10.4g (83%)

[0126] ESI-MS: M(neg.) = 268.

[0127] HPLC-MS m / z = 268 (neg.).

[0128] Step 2: 4-(cyanomethyl)-3,5,6-trifluoromethylpyridinium

[0129] (Nitrile intermediate A3-A)

[0130]

[0131] In a 250 mL round-bottom flask, 10.39 g (33.8 mmol) of ester intermediate A3-eE was dissolved in 86 mL of aqueous acetic acid (50% w / w). 1.3 mL of concentrated sulfuric acid was added, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the mixture was poured into a 1 L beaker containing 200 mL of ice water. 200 mL of ethyl acetate was added, and the mixture was stirred at room temperature for 30 min. The organic layer was separated, and the aqueous layer was extracted with 2 × 200 mL of ethyl acetate. The combined organic layers were washed with 200 mL of water, 200 mL of saturated sodium bicarbonate solution, and 200 mL of water. After drying with sodium sulfate, the solvent was removed from the solution under vacuum to obtain a yellow oil. Distillation under vacuum yielded a pale yellow oil (T). 浴 : 190℃; bp: at 4×10 -3 (At 110℃).

[0132] Yield: 4.5g (68%).

[0133] TLC(SiO2,DCM): R f =0.65

[0134] GC-MS: t R =9.02min., m / z=197,95%; t R =8.86min., m / z=197,5%.

[0135] 1 H-NMR (600MHz, CD3CN): δ = 4.03 (s, 2H).

[0136] 19 F-NMR (282MHz, CD3CN): δ=-81.11 (t, J=25.4, 1F), -114.21 (dd, J=8.1, 26.5, 1F), -122.46 (dd, J=8.0, 24.3, 1F).

[0137] Step 3: (Z)-4-(cyano(2-(cyano(2,3,5,6-tetrafluoro-4-(trifluoromethyl)-phenyl)methyl)-3-(cyano(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)-methylene)cycloprop-1-en-1-yl)methyl)-3,5,6-trifluoromethylpyridinium

[0138] (Axylene precursor B5-P)

[0139]

[0140] In a 250 mL Schlenk flask, under argon atmosphere, 3.3 g of Cs₂CO₃ was suspended in 90 mL of DMF. The suspension was cooled to 0 °C and 3.1 g (4.8 mmol) of betaine intermediate C4-B was added, resulting in an orange suspension. After adding 1.0 g of a solution of 4-(cyanomethyl)-3,5,6-trifluoromethylpyridinium nitrile (A3-A, 5.0 mmol) in 10 mL of anhydrous DMF at 0 °C, the cooling bath was removed and the mixture was stirred overnight. The brown suspension was then stirred at room temperature for 24 hours, and the mixture was poured into 100 mL of saturated NaCl solution. Extraction was performed with 100 mL of ethyl acetate, followed by washing twice with 50 mL of NaCl aqueous solution. The mixture was dried over Na₂SO₄ to remove the solvent, yielding a red oily substance, which was then dried under vacuum.

[0141] Crude material yield: 6.89 g (191%)

[0142] HPLC-MS: m / z=371((m / z) / 2),742(m / zH,C 29 H1F 17 N5 2- ),t R =7.8

[0143] min., m / z = 741(m / zH, C 29 F 17 N5 -. ),t R =13.9min.

[0144] Step 4: (2Z,2'E)-2,2'-((E)-3-(cyano(2-cyano-3,5,6-trifluoropyridin-4-yl)methylene)cyclopropyl-1,2-diethylene)bis(2-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)-phenyl)acetonitrile)

[0145] (Axylene compound B5)

[0146]

[0147] 3.3 g (1.0 mmol) of the axonylene precursor B5-P was dissolved in 44 mL of glacial acetic acid and treated dropwise with 44 mL of nitric acid aqueous solution (65% w / w) at room temperature. The resulting red solution was stirred overnight and then poured into 80 mL of cold water. After stirring at room temperature for 1 h, the resulting orange precipitate was filtered off, washed with water until the pH was neutral, and dried under vacuum.

[0148] Yield: 1.26g (39%)

[0149] The crude product is recrystallized from the mixture of cyclohexane and chlorohexane.

[0150] Compound B6 of this invention

[0151] Step 1: Potassium salt of 2-cyano-2-(2,3,5-trifluoro-4,6-bis(trifluoromethyl)phenyl)ethyl acetate (ester intermediate A2-eE)

[0152]

[0153] In a 250 mL flask, 10 g of perfluoro-m-xylene, 65 mL of DMF, and 5.8 g of anhydrous potassium carbonate were mixed. After stirring for 5 min, 3.75 mL of ethyl cyanoacetate was added dropwise to the continuously stirred yellow suspension. After 48 h at room temperature, the reaction was considered complete according to TLC analysis. The precipitate formed during the reaction was removed by filtration and washed with acetonitrile. The filtrate was rotary evaporated to dryness, and the resulting oily substance was dissolved in 40 mL of toluene and evaporated again to dryness to remove residual DMF.

[0154] Crude product yield: 18.8g (129%)

[0155] ESI-MS: m / z = 378 (m / z K, C) 13 H5F9NO2 - (neg.)

[0156] IR(ATR): 3443,2161,1662,1599,1469,1352,1262,1215,1125,1062,936,879,732cm -1 .

[0157] Step 2: 2-(2,3,5-trifluoro-4,6-bis(trifluoromethyl)phenyl)acetonitrile

[0158] (Nitrile intermediate A2-A)

[0159]

[0160] In a 250 mL flask, 18.0 g of crude 2-cyano-2-(2,3,5-trifluoro-4,6-bis(trifluoromethyl)phenyl)ethyl acetate potassium salt (A2-eE, from a previous step) and 4.6 mL of concentrated sulfuric acid were dissolved in an aqueous acetic acid solution (50% v / v). The mixture was heated under reflux for 48 hours. After cooling to room temperature, the mixture was poured into a 500 mL beaker containing 100 mL of ice water and stirred for 5 min. The mixture was extracted with 3 × 50 mL of ethyl acetate. The combined organic layers were washed with 2 × 50 mL of saturated sodium bicarbonate aqueous solution and 100 mL of water. After drying the organic layers with sodium sulfate, the solvent was removed under vacuum to give a brown oily substance. Distillation under vacuum gave a colorless liquid (bp: at 10 -2 (At 75-80℃, under millibars; main fraction).

[0161] Yield: 8.45g (64%).

[0162] GC-MS: m / z = 307.

[0163] IR(ATR): 1650,1608,1495,1469,1354,1243,1142,1081,1033,963,894,733,655cm -1 .

[0164] Step 3: 4-(cyano(2-(cyano(2,3,5-trifluoro-4,6-bis(trifluoromethyl)phenyl)-methyl)-3-(cyano(4-cyano-2,3,5,6-tetrafluorophenyl)methyl)cycloprop-2-en-1-ylidene)-methyl)-2,3,5,6-tetrafluorobenzonitrile

[0165] (Axylene precursor B6-P)

[0166]

[0167] In a 100 mL Schlenk flask, under argon atmosphere, 2.12 g of cesium carbonate was suspended in 45 mL of anhydrous dimethylformamide and cooled to 0 °C. A solution of 1.0 g of 2-(2,3,5-trifluoro-4,6-bis(trifluoromethyl)phenyl)acetonitrile in 5 mL of anhydrous dimethylformamide was slowly added to the suspension. The mixture was stirred for 5 min, and 1.74 g of betaine intermediate C2-B as a solid was added. Stirring continued for 24 h, and the reaction was allowed to reach ambient temperature. The reaction mixture was poured into a 250 mL separatory funnel containing 100 mL of water and 80 mL of ethyl acetate. The organic layer was separated, washed twice with 80 mL of semi-saturated NaCl aqueous solution, twice with 80 mL of 2 M HCl aqueous solution, and twice with 80 mL of saturated sodium bicarbonate aqueous solution.

[0168] Finally, the organic layer was dried with magnesium sulfate and the solvent was carefully removed by vacuum evaporation to obtain a deep purple solid.

[0169] Crude product yield: 2.8g (115%).

[0170] ESI-MS: m / z=766,382 (neg.).

[0171] IR(ATR): 2233,2165,1639,1475,1370,1339,1257,1214,1134,969,815,732cm -1 .

[0172] Step 4: (4,4'-((1Z,1'E)-((E)-3-(cyano(3,5,6-trifluoro-2,4-bis(trifluoromethyl)phenyl)methylene)cyclopropane-1,2-diethylene)bis(cyanomethylethylene))bis(2,3,5,6-tetrafluorobenzonitrile)

[0173] (Axylene compound B6)

[0174]

[0175] In a 100 mL flask equipped with a dropping funnel, 1.44 g (1.88 mmol) of axylene precursor B6-P was dissolved in 19 mL of glacial acetic acid. 19 mL of concentrated nitric acid (65%, w / w) was added dropwise with vigorous stirring. During the addition of nitric acid, the color of the solution changed from yellow-green to deep red. Stirring continued overnight. The solution was then cooled to 0 °C and 40 mL of water was added dropwise to induce a bright orange product precipitation. The crude solid product was collected on sintered glass frit and washed with 3 × 15 mL of water. The moist raw material was dried in a vacuum drying oven at 40 °C for 3 h, followed by drying under high vacuum (10 °C) at ambient temperature. -2 The material was dried in a solution of 1-chlorobutane and cyclohexane in a 3:2 (v / v) mixture. The dried material was then recrystallized from the mixture.

[0176] Yield: 333 mg (23%)

[0177] Compound B7 of this invention

[0178] Step 1: 2-(tert-butoxy)-1-cyano-2-oxo-1-(2,5,6-trifluoropyrimidin-4-yl)eth-1-potassium (ester intermediate A7-tbE)

[0179]

[0180] In a 250 mL flask, 10 g (65.8 mmol) of perfluoropyrimidine and 18.2 g (132 mmol) of anhydrous potassium carbonate were dissolved / suspended in 130 mL of acetonitrile. A solution of 11.14 g (78.9 mmol) of tert-butyl 2-cyanoacetate in 10 mL of acetonitrile was added with stirring, and the reaction mixture was observed to turn yellow. The reaction mixture was stirred at ambient temperature for 3 days and then filtered to remove solids. The solvent was removed from the filtrate, and the resulting yellow solid was ground with 120 mL of DCM.

[0181] Yield: 20.1g (98%)

[0182] 1 H-NMR (CD3CN, 300MHz): 1.47 (s, 9H).

[0183] 19 F-NMR (CD3CN, 282.3MHz): -53.2(d,1F), -93.4(d,1F), -163.7(br s,1F).

[0184] IR(ATR,cm -1 ): 2185,1738,1646,1606,1539,1461,1442,1377,1281,1198,1155,1115,1027,899,840,775.

[0185] Step 2: 2-(2,5,6-trifluoropyrimidin-4-yl)acetonitrile

[0186] (Nitrile intermediate A7-A)

[0187]

[0188] 5.5 g (17.7 mmol) of A7-tbE and 60 mL of dioxane were loaded into a screw-capped pressure tube. 17.7 mL of a 4 M anhydrous HCl solution in dioxane was added to this mixture, and the tube was sealed. The reaction mixture was heated to 100 °C for 4 h, then poured into 100 mL of water. The mixture was extracted with 3 × 50 mL of EtOAc and the collected organic layer was washed with 50 mL of water and 50 mL of brine. After drying with Na₂SO₄ to remove the solvent, the mixture was distilled using a bulb-to-bulb method (140 °C, 3 × 10⁻⁶ mL). -3 (Use millibars) to purify the crude product.

[0189] Yield: 2.02g (66%)

[0190] 19F-NMR (CDCl3, 282.3MHz): -45.2(d,1F), -72.3(d,1F), -156.2(m,1F).

[0191] GC-MS: m / z = 173 (M + ,100),153(20),108(20)

[0192] IR(ATR,cm -1 ): 2269,1609,1462,1402,1243,1105,1050,1017,928,769,725.

[0193] Step 3: (Z)-2-(2-(cyano(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)-methyl)-3-(cyano(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)methylene)cycloprop-1-en-1-yl)-2-(2,5,6-trifluoropyrimidin-4-yl)acetonitrile

[0194] (Axylene precursor B7-P)

[0195]

[0196] In a 250 mL Schlenk flask, under argon atmosphere, 3.6 g of Cs₂CO₃ was suspended in 90 mL of DMF. The suspension was cooled to 0 °C and betaine intermediate C4-B (3.6 g, 5.6 mmol) was added, resulting in an orange suspension. At 0 °C, a solution of 1.0 g of 2-(2,5,6-trifluoropyrimidin-4-yl)acetonitrile (A7-A, 5.7 mmol) in 10 mL of anhydrous DMF was added to the stirred mixture. The cooling bath was removed and the mixture was stirred overnight. The brown suspension was then stirred at room temperature for 24 hours. The reaction mixture was then poured into 100 mL of saturated NaCl aqueous solution. Extraction was performed with 100 mL of ethyl acetate, followed by washing twice with 50 mL of NaCl solution. The mixture was dried over Na₂SO₄ to remove the solvent, yielding a red oily substance, which was then dried under vacuum.

[0197] Crude product yield: 6.06 g (151%).

[0198] HPLC-MS: m / z=358((m / z) / 2), 718(MH).

[0199] Step 4: (2Z,2'E)-2,2'-((E)-3-(cyano(2,5,6-trifluoropyrimidin-4-yl)methylene)-cyclopropane-1,2-diethylene)bis(2-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)-acetonitrile)

[0200] (Axylene compound B7)

[0201]

[0202] 3.0 g (4.2 mmol) of A7-P was dissolved in 42 mL of glacial acetic acid and treated dropwise with 42 mL of nitric acid aqueous solution (65% w / w) at room temperature. The resulting red solution was stirred overnight and then poured into 80 mL of cold water. After stirring at room temperature for 1 h, the resulting orange precipitate was filtered off, washed with water until the pH was neutral, and dried under vacuum.

[0203] Crude product yield: 0.9g (30%)

[0204] The crude product is recrystallized from the mixture of cyclohexane and chlorohexane.

[0205] Device Examples

[0206] An experimental OLED constructed on a glass substrate is equipped with the following components: an ITO anode, a 10 nm thick hole injection transport layer (HIL) consisting of a commercially available biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-9-phenyl-9H-carbazol-3-yl)phenyl]amine (CAS No. 1242056-42-3) doped with 8 wt% of the test compound, a 130 nm thick hole transport layer made with the same matrix compound as the HIL, a 20 nm thick host compound ABH113, and a 3 wt% emitter NUBD370 (all from the same supplier, Sun Fine). The light-emitting layer made of (chemicals, Korea), the 36 nm thick electron transport layer made of (3-(dibenzo[c,h]acrid-7-yl)phenyl)diphenylphosphine oxide and 8-hydroxyquinoline lithium (LiQ, 1:1 w / w), and the 30 nm thick silver cathode showed similar performance in terms of voltage, efficiency, shelf life, and color coordinates to the comparative compound and the compound of the present invention.

[0207] The features of the invention disclosed individually in the foregoing description and claims may also be used in any combination to implement the invention in various embodiments.

[0208] Abbreviations and symbols used throughout the application

[0209] ACN Acetonitrile

[0210] bp boiling point

[0211] br wide peak

[0212] CAS (Chemical Abstracts Service)

[0213] conc. thick

[0214] CV cyclic voltammetry

[0215] DCM dichloromethane

[0216] DMF N,N-dimethylformamide

[0217] DSC Differential Scanning Calorimetry

[0218] E 0 Electrochemical redox potential

[0219] EIL Electron Injection Layer

[0220] ESI Electrospray Ionization

[0221] ETL (Electron Transport Layer)

[0222] ETM Electron Transport Matrix

[0223] EtOAc (ethyl acetate)

[0224] Fc + / Fc Ferrocene ions / Ferrocene reference system

[0225] GC gas chromatography

[0226] HIL Hole Injection Layer

[0227] HOMO highest occupied molecular orbital

[0228] HTL Hole Transport Layer

[0229] HTM Hole Transport Matrix

[0230] IR (Infrared, Light, Spectrum)

[0231] Indium Tin Oxide (ITO)

[0232] LiQ 8-hydroxyquinoline lithium

[0233] LUMO (lowest unoccupied molecular orbital)

[0234] mol% (mol percentage)

[0235] MeOH (methanol)

[0236] mp melting point

[0237] MS mass spectrometry

[0238] m / z mass / charge ratio

[0239] neg. Anion

[0240] OLED Organic Light Emitting Diode

[0241] R f Retention factor

[0242] TGA pyrolysis gravimetric analysis

[0243] THF Tetrahydrofuran

[0244] TLC (Thin Layer Chromatography)

[0245] t r Retention time

[0246] UV-vis (ultraviolet-visible light, spectrum)

[0247] vol% (vol percentage)

[0248] v / v (volume to volume ratio, percentage by volume)

[0249] VTE vacuum thermal evaporation

[0250] wt% (weight percentage)

[0251] w / w weight ratio (percentage by mass).

Claims

1. A method for preparing an electrically doped semiconductor material containing a [3]-axylene p-doper, the method comprising the following steps: (i) Loading the evaporation source with [3]-axylene p-dopant, and (ii) Evaporation of the [3]-axylene p-dopant under elevated temperature and reduced pressure, The [3]-axylene p-doper is , or .

2. The method according to claim 1, wherein the temperature in step (ii) is in the range of 100-300°C.

3. The method of claim 1, wherein the duration of step (ii) is at least 100 hours.

4. The method according to claim 1, wherein in step (ii), a hole transport material comprising at least one hole transport matrix compound is co-evaporated with the [3]-axylene p-dopant, and in a subsequent step (iii), the [3]-axylene p-dopant is co-deposited with the hole transport matrix compound to form a semiconductor material.

5. The method of claim 1, wherein step (ii) is performed at a time less than 10 -1 The test was conducted under a pressure of Pa.

6. The method according to any one of claims 1 to 5, wherein the [3]-axylene p-dopant has a reversible redox potential, which is measured in acetonitrile for a ferrocene / ferrocene ion reference system by cyclic voltammetry, the redox potential being in the range of +0.10 to +0.50 V.

7. A method for preparing an electronic device comprising a layer including a [3]-axylene p-doped agent, the method comprising the following steps: (i) Loading the evaporation source with [3]-axylene p-dopant, and (ii) Evaporation of the [3]-axylene p-dopant under elevated temperature and reduced pressure, The [3]-axylene p-doper is , or .

8. The method according to claim 7, wherein the temperature in step (ii) is in the range of 100-300°C.

9. The method of claim 7, wherein the duration of step (ii) is at least 100 hours.

10. The method of claim 7, wherein in step (ii), a hole transport material comprising at least one hole transport matrix compound is co-evaporated with the [3]-axylene p-dopant, and in a subsequent step (iii), the [3]-axylene p-dopant is co-deposited with the hole transport matrix compound to form a semiconductor material.

11. The method of claim 7, wherein step (ii) is performed at a time less than 10 -1 The test was conducted under a pressure of Pa.

12. The method according to any one of claims 7 to 11, wherein the [3]-axylene p-dopant has a reversible redox potential, which is measured in acetonitrile for a ferrocene / ferrocene ion reference system by cyclic voltammetry, the redox potential being in the range of +0.10 to +0.50 V.

13. A [3]-axylene compound having the structure according to formula (I) （I）， The [3]-axylene compound is , or .

14. The compound of claim 13, having a reversible redox potential, said redox potential being measured by cyclic voltammetry in acetonitrile for a ferrocene / ferrocene ion reference system, said redox potential being in the range of +0.10 to +0.50 V.

15. A semiconductor material comprising the compound according to claim 13 or 14 and a matrix material, wherein the matrix material comprises at least one hole transport matrix compound.

16. A semiconductor layer comprising a compound according to claim 13 or 14 or a semiconductor material according to claim 15.

17. Use of the compound according to claim 13 or 14, wherein the compound is used as a p-doper in semiconductor materials, semiconductor layers and / or electronic devices.

18. An electronic device comprising, between a first electrode and a second electrode, a semiconductor material according to claim 15 and / or a semiconductor layer according to claim 16.

19. The electronic device according to claim 18, wherein it is an organic light-emitting diode.

20. The electronic device according to claim 18 or 19, wherein the compound having formula (I) is contained within a hole injection layer and / or a hole transport layer and / or a charge generation layer.

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