Compound and application thereof
1. A compound of the formula (1):
in the formula (1), X is CH or N;
the L is selected from one of single bond, substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene;
ar is selected from one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; ar is preferably selected from one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the R, R1And R2Each independently selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; n is an integer of 0 to 2;
when the substituent group exists in the groups, the substituent group is selected from one or a combination of at least two of halogen, cyano, carbonyl, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkenyl of C2-C10, alkoxy or thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl or condensed ring aryl of C6-C30, monocyclic heteroaryl or condensed ring heteroaryl of C3-C30.
2. The compound of claim 1, having the structure of formula (2):
in the formula (2), X, L, Ar and R1And R2Are all as defined in formula (1);
the R is3And R4Each independently selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl.
3. The compound of claim 2, having a structure represented by formula (2-1) or (2-2):
in the formulae (2-1) and (2-2), said X, L, R1、R2、R3And R4Are all as defined in formula (2);
in the formula (2-1), the Y1、Y2、Y3、Y4And Y5Each independently selected from CR5Or N, and Y1-Y5At least one of them is N, R5One selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups5Can be fused into a ring;
in the formula (2-2), the Z1、Z2、Z3、Z4And Z5Each independently selected from CR6Or N, and Z1-Z5At least one of them is N, R6One selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups6Can be fused into a ring;
when the substituent group exists in the groups, the substituent group is selected from one or a combination of at least two of halogen, cyano, carbonyl, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkenyl of C2-C10, alkoxy or thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl or condensed ring aryl of C6-C30, monocyclic heteroaryl or condensed ring heteroaryl of C3-C30.
4. The compound of any one of claims 1-3, wherein L is selected from one of a single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene.
5. The compound of any one of claims 1-3, wherein L is selected from a single bond or one of the following substituted or unsubstituted groups: phenylene, naphthylene, pyridylene, biphenylene.
6. The compound of claim 1, having the structure shown below:
7. use of a compound according to any one of claims 1 to 6 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner or electronic paper;
preferably, the compound is used as an electron transport material in an organic electroluminescent device.
8. An organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layers contain the compound according to any one of claims 1 to 6;
preferably, the light-emitting functional layer comprises a hole transport region, a light-emitting layer and an electron transport region, the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is arranged between the hole transport region and the electron transport region; wherein the electron transport region comprises an electron transport layer containing the compound of any one of claims 1 to 6.
Background
Organic Light Emission Diodes (OLED) devices are a kind of devices with sandwich-like structure, which includes positive and negative electrode films and Organic functional material layers sandwiched between the electrode films. And applying voltage to the electrodes of the OLED device, injecting positive charges from the positive electrode and injecting negative charges from the negative electrode, and transferring the positive charges and the negative charges in the organic layer under the action of an electric field to meet for composite luminescence. Because the OLED device has the advantages of high brightness, fast response, wide viewing angle, simple process, flexibility and the like, the OLED device is concerned in the field of novel display technology and novel illumination technology. At present, the technology is widely applied to display panels of products such as novel lighting lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with fast development and high technical requirements.
With the continuous advance of OLEDs in both lighting and display areas, much attention has been paid to the research on their core materials. This is because an efficient, long-lived OLED device is generally the result of an optimized configuration of the device structure and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures. Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like.
In order to prepare an OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device need to be innovated, and photoelectric functional materials in the OLED device need to be continuously researched and innovated, so that functional materials with higher performance can be prepared. Based on this, the OLED material industry has been working on developing new organic electroluminescent materials to achieve low starting voltage, high luminous efficiency and better lifetime of the device.
In order to further satisfy the continuously increasing demand for the photoelectric properties of OLED devices and the energy saving demand of mobile electronic devices, new and efficient OLED materials need to be continuously developed, wherein the development of new electron transport materials with high electron injection capability and high mobility is of great significance.
Disclosure of Invention
An object of the present invention is to provide a compound capable of improving light emitting efficiency and reducing driving voltage when applied to an OLED device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a compound having a structure represented by formula (1);
in the formula (1), X is CH or N;
the L is selected from one of single bond, substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene; preferably, L is selected from one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
ar is selected from one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; preferably, Ar is selected from one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the R, R1And R2Each independently selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; n is an integer of 0 to 2;
when the substituent group exists in the groups, the substituent group is selected from one or a combination of at least two of halogen, cyano, carbonyl, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkenyl of C2-C10, alkoxy or thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl or condensed ring aryl of C6-C30, monocyclic heteroaryl or condensed ring heteroaryl of C3-C30.
Further preferably, the compound represented by formula (1) of the present invention has a structure represented by the following formula (2):
in the formula (2), X, L, Ar and R1And R2Are all as defined in formula (1);
the R is3And R4Each independently selected from one of H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl.
Further preferably, the compound represented by the formula (2) of the present invention has a structure represented by the following formula (2-1) or (2-2):
in the formulae (2-1) and (2-2), said X, L, R1、R2、R3And R4Are all as defined in formula (2);
in the formula (2-1), the Y1、Y2、Y3、Y4And Y5Each independently selected from CR5Or N, and Y1-Y5At least one of them is N, R5One selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups5Can be fused into a ring;
in the formula (2-2), the Z1、Z2、Z3、Z4And Z5Each independently selected from CR6Or N, and Z1-Z5At least one of them is N, R6One selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, two adjacent R groups6Can be fused into a ring;
when the substituent group exists in the groups, the substituent group is selected from one or a combination of at least two of halogen, cyano, carbonyl, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkenyl of C2-C10, alkoxy or thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic heteroaryl or fused heteroaryl of C3-C30.
Still further preferably, in the formulae (1), (2-1) and (2-2):
l is selected from a single bond or one of the following substituted or unsubstituted groups: phenylene, naphthylene, pyridylene, biphenylene;
still more preferably, R is as defined above1、R2、R3、R4、R5And R6Each independently selected from hydrogen or the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, grottoyl, perylenyl, anthrylenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenylPhenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, quinoxalinyl, benzoimidazolyl, pyrrolyliyl, benzoisothiazolyl, benzoimidazolyl, and benzoimidazolyl, Oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrolylyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahnthracenyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4, 5-diazenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocaineyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, phenanthreneyl, phenanthrolinyl, 1,2, 4-thiadiazolyl, 1, 2-thiadiazolyl, 1, 3-diazenyl, 1, 3-thiadiazolyl, and the like, 1,2, 5-thiadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, or a combination of two of the foregoing groups.
Further, the compounds described by the general formula of the present invention may preferably be compounds of the following specific structures, which are merely representative:
as another aspect of the present invention, there is also provided a use of the compound as described above in an organic electroluminescent device. In particular, the use as an electron transport layer material in organic electroluminescent devices is preferred.
As still another aspect of the present invention, there is also provided an organic electroluminescent device comprising a first electrode, a second electrode, and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layer contains the compound of the general formula of the present invention represented by any one of the above formula (1), formula (2-1) or formula (2-2), or contains a compound represented by each of the above specific structural formulae.
Specifically, one embodiment of the present invention provides an organic electroluminescent device including a substrate, and a first electrode, a plurality of light-emitting functional layers, and a second electrode sequentially formed on the substrate; the light-emitting functional layer comprises a hole transport region, a light-emitting layer and an electron transport region, wherein the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is arranged between the hole transport region and the electron transport region; wherein, the electron transport region comprises an electron transport layer, and the electron transport layer contains the compound with the general formula of the invention shown in any one of the formula (1), the formula (2-1) or the formula (2-2), or contains the compound shown in each specific structural formula.
More specifically, the organic electroluminescent device of the present invention will be described in detail.
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used2) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-34; or any combination thereof.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI-1 to HI-3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI-1 to HI-3 described below.
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent host material may be selected from, but not limited to, the combination of one or more of BFH-1 through BFH-17 listed below.
In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent dopant may be selected from, but is not limited to, combinations of one or more of BFD-1 through BFD-12 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, one or more of GPH-1 to GPH-80.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer can be selected from, but is not limited to, one or more of GPD-1 to GPD-47 listed below.
Wherein D is deuterium.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more of YPD-1 to YPD-11 listed below.
The organic electroluminescent device of the present invention includes an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
The electron transport region may also be formed using the compound of the present invention for a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL), although the material of the electron transport region may also be combined with one or more of ET-1 to ET-57 listed below.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following:
Liq、LiF、NaCl、CsF、Li2O、Cs2CO3、BaO、Na、Li、Ca。
the specific reason why the above-mentioned compound of the present invention has excellent performance is not clear, and it is presumed that the following reasons may be:
the general formula compound of the invention takes pyridazinopyrrole or pyridazinoimidazole as a mother nucleus, Ar is designed to be an electron-deficient group which is connected with the mother nucleus through a bridging single bond, and compared with the compound which is commonly used in the prior art and adopts a single oxazole, thiazole, imidazole, triazole or triazine structure, the structure of the compound of the invention has relatively stronger electron-deficient property, thereby being beneficial to the injection of electrons. Meanwhile, the compound contains electron-deficient groups with large conjugated structures, so that molecules have good plane conjugation, and the mobility of electrons is improved. The structural characteristics of the two aspects can make the molecule show good electron injection and migration performance. Therefore, when the compound is used as an electron transport layer material in an organic electroluminescent device, the electron injection and migration efficiency in the device can be effectively improved, so that the excellent effects of high luminous efficiency and low starting voltage of the device are ensured.
In addition, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.
Detailed Description
The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples. The method and materials for obtaining the compound are not limited to the synthetic methods and materials used in the invention, and other methods or routes can be selected by those skilled in the art to obtain the novel compound provided by the invention. The compounds of the present invention, for which no synthetic method is mentioned, are commercially available starting products or are prepared by the starting products according to known methods.
The synthetic route of the compound shown by the general formula of the invention is as follows:
in the first step, raw material compounds and aryl substituted aldehyde are subjected to an aldehyde-amine condensation reaction in ethanol to obtain an intermediate M2; in the second step, intermediate M2 is reacted with an alkyne or arylalkyne in [ Cp RhCl ]2]2After catalytic coupling, the target compound is further synthesized after copper acetate oxidation ring closure. Wherein, X, R1-R4L and Ar have the same meanings as in the general formula (2).
Basic chemical materials such as ethanol, triethylamine, sodium sulfate, methanol, tetrahydrofuran, dichloromethane, 1, 4-dioxane, potassium carbonate, potassium acetate, copper acetate, and 3, 5-dibromopyrazine-2-amino group used in the following synthesis examples were obtained from Shang Tai Tanku technology Co., Ltd and Xiong chemical Co., Ltd. The mass spectrometer used for the following compounds was a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).
Synthesis example 1:
synthesis of Compound C1
(1) Preparation of Compound 1-1
The compound 1-aminopyrrole (82.0g, 1.0mol) was added to a (2L) flask containing 1L of absolute ethanol, p-chlorobenzaldehyde was added slowly in portions with stirring at room temperature, the reaction was controlled at room temperature with attention to ice bath, and TLC after 2 hours showed completion of the reaction. And adding water and dichloromethane into the reaction solution for separating liquid, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, and performing column chromatography separation and purification to obtain the compound 1-1(183g, yield 90%).
(2) Preparation of Compounds 1-2
Compound 1-1(163g, 0.8mol), tolane (142g, 0.8mol) and 1L dioxane were charged into a 2L flask, after replacement of nitrogen gas, dichloro (pentamethylcyclopentadienyl) rhodium (4.9g,8.0mmol) and copper acetate (290g, 1.6mol) were added, respectively, replaced with nitrogen gas 4 times, and the reaction was refluxed with stirring at 120 ℃ for 16 hours, and the end of the reaction was monitored by TLC. And cooling the reaction to room temperature, slowly pouring the cooled reaction product into 2L of cold water, precipitating a large amount of solid, leaching the filtered solid with water and ethanol for three times respectively, drying the solid, and performing column chromatography separation and purification to obtain the compound 1-2(205g, yield 67%).
(3) Preparation of Compounds 1-3
Compound 1-2(205g, 0.54mol), pinacol diboron ester (206g, 0.81mol), and potassium acetate (106g, 1.08mol) were charged into a 2L flask containing 1L of 1, 4-dioxane, and after replacing nitrogen with palladium acetate (2.43g, 10.8mmol), 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (8.9g, 21.6mmol) were added under stirring at room temperature. After the addition was completed, nitrogen was replaced four times, the reaction was refluxed with stirring for 12 hours, and the end of the reaction was monitored by TLC. The 1, 4-dioxane was removed by rotary evaporation, and the mixture was separated with water and dichloromethane, and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 1-3(236g, yield 93%).
(4) Preparation of Compound C1
Compound 1-3(10g, 21mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.6g, 21mmol), potassium carbonate (5.8g, 42mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (146mg, 0.2mmol) was added to a flask containing 100mL of tetrahydrofuran and 25mL of water, the nitrogen was replaced and the reaction was refluxed under nitrogen with heating for 4 hours, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to give compound C1(8.6g, yield 71%). Calculated molecular weight: 577.23, found C/Z: 577.2.
synthesis example 2:
synthesis of Compound C35
(1) Preparation of Compound 2-1
The compound 2-bromo-1-aminopyrrole (80.0g, 0.5mol) was added to a (2L) flask containing 1L of absolute ethanol, p-chlorobenzaldehyde (77g, 0.55mol) was added slowly in portions with stirring at room temperature, the reaction was carried out at room temperature with attention paid to ice bath control, and TLC after 2 hours showed completion of the reaction. And adding water and dichloromethane into the reaction solution for separation, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, and performing column chromatography separation and purification to obtain the compound 2-1(113g, yield 80%).
(2) Preparation of Compound 2-2
Compound 2-1(20g, 71mmol), tolane (12.6g, 71mmol) and 300mL dioxane were charged into a 1L flask, and after nitrogen gas was replaced, [ Cp ] RhCl was added2]2(Mr. 618) (0.43g,0.7mmol) and copper acetate (25.7g, 142mmol), the reaction was refluxed for 16 hours at 120 ℃ with replacement of nitrogen 4 times, and the end of the reaction was monitored by TLC. And cooling the reaction to room temperature, slowly pouring the cooled reaction product into 500mL of cold water, precipitating a large amount of solid, leaching the filtered solid with water and ethanol for three times respectively, drying the solid, and performing column chromatography separation and purification to obtain the compound 2-2(19g, yield 58.4%).
(3) Preparation of Compounds 2-3
Compound 2-aminoquinazoline (5.9g, 41mmol), compound 2-2(18.8g,41mmol), potassium carbonate (11.1g, 82mmol) was charged into a 500mL flask containing 200mL of t-butanol, and after replacing nitrogen with stirring at room temperature, palladium acetate (90mg, 0.41mmol), 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (0.34g, 21.6mmol) was added. After the addition was completed, nitrogen was replaced four times, the reaction was refluxed with stirring for 10 hours, and the end of the reaction was monitored by TLC. Tert-butanol was removed by rotary evaporation and purified by column chromatography to give compound 2-3(16.7g, yield 80%).
(4) Preparation of Compounds 2-4
Compound 2-3(16.7g, 32.8mmol), pinacol diboron (12.5g, 49.2mmol), and potassium acetate (6.4g, 65.6mol) were charged into a 1L flask containing 300mL of 1, 4-dioxane, and after replacing nitrogen with nitrogen at room temperature under stirring, palladium acetate (0.15g, 0.66mmol), 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (0.54g, 1.32mmol) were added. After the addition was completed, nitrogen was replaced four times, the reaction was refluxed with stirring for 12 hours, and the end of the reaction was monitored by TLC. The 1, 4-dioxane was removed by rotary evaporation, the mixture was separated with water and dichloromethane, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 2-4(14.6g, yield 73%).
(5) Preparation of Compound C35
Compound 2-4(14.6g, 24.3mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (6.5g, 24.3mmol), potassium carbonate (6.7g, 48.6mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (175mg, 0.24mmol) was added to a flask containing 160mL tetrahydrofuran and 40mL water, the nitrogen was replaced and the reaction was heated to reflux under nitrogen for 4 hours and TLC indicated completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to give compound C35(11.8g, yield 77%). Calculated molecular weight: 629.23, found C/Z: 629.2.
synthesis example 3:
synthesis of Compound C108
(1) Preparation of Compound 3-1
Adding 50g (256mmol, 1.0eq) of 2, 4-dichloroquinazoline into a 1L single-neck bottle, adding 400mL of dichloromethane, cooling to 0 ℃ in an ice bath, adding 64g (632mmol, 3.0eq) of triethylamine, stirring until a reaction solution is clear, dropwise adding 18.6g (316mmol, 1.5eq) of hydrazine hydrate in the ice bath, gradually precipitating solids in the reaction process, stirring for 3 hours, monitoring the reaction by TLC, allowing the raw materials to disappear, adding 4.0L of water, and continuing stirring for 1 hour. Filtration and drying were carried out to obtain Compound 3-1(33g, yield: 81%).
(2) Preparation of Compound 3-2
3-133 g (170mmol, 1.0eq), 19.8g (187mmol, 1.1eq) of benzaldehyde and 500mL of ethanol were added to a 1.0L single-neck flask, stirred until the solution was clear, then stirred for 30 minutes, and TLC monitored for disappearance of starting material. 60g (187mmol, 1.1eq) iodobenzene diacetic acid were added portionwise (temperature controlled below 20 ℃ C. for the addition). After the addition was completed, stirring was carried out overnight, a solid was gradually precipitated, TLC monitored reaction was completed, filtration was carried out, the filter cake was rinsed with ethanol until the filtrate was colorless clear liquid, rinsed with PE for 2 to 3 times, and dried to obtain compound 3-2(39g, yield: 82%).
(3) Preparation of Compound C108
Compound 1-3(10g, 21mmol), compound 3-2(5.9g, 21mmol), potassium carbonate (5.8g, 42mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (146mg, 0.2mmol) was added to a flask containing 100mL of tetrahydrofuran and 25mL of water, the nitrogen was replaced and the reaction was heated under reflux under nitrogen for 4 hours and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to obtain compound C108(9.2g, yield 74%). Calculated molecular weight: 590.22, found C/Z: 590.2.
synthesis example 4:
synthesis of Compound C115
(1) Preparation of Compound 4-1
3, 5-Dibromopyrazine-2-amino (25g, 100mmol), phenylboronic acid (14.6g, 120mmol), potassium carbonate (27.6g, 200mmol), Pd (dppf) Cl were added to a single-neck flask2(0.73g, 1.0mmol), the solvent tetrahydrofuran 400mL, water 100mL was added, nitrogen was replaced three times and the reaction refluxed at 85 ℃ overnight under nitrogen. TLC (monitoring the reaction completion of the 3, 5-dibromopyrazine-2-amino group, stopping the reaction, cooling to room temperature, spin-drying THF, adding an appropriate amount of water, extracting with DCM, drying, and purifying by column chromatography to obtain compound 4-1(21g, yield 84%).
(2) Preparation of Compound 4-2
After compound 4-1(21g, 84mmol) was dissolved in 250mL dioxane, it was added to a 500mL three-necked flask, and ethoxycarbonyl isothiocyanate (13.2g, 100mmol) was gradually added dropwise while keeping the temperature at not higher than 15 ℃ and stirred at room temperature overnight. TLC detection reaction is complete, dioxane is concentrated, ethanol is stirred and washed, and after filtration, column chromatography separation and purification are carried out to obtain the compound 4-2(24.4g, yield 77%).
(3) Preparation of Compound 4-3
A500 mL three-necked flask was charged with hydroxylamine hydrochloride (19.2g, 288mmol), 150mL of ethanol and 150mL of methanol were further added, and then triethylamine (19.2g, 288mmol) was added in portions, and the mixture was stirred at room temperature for one hour. Then adding compound 4-2(24g, 64mmol), heating to reflux, reacting for about 4h, detecting by TLC, and cooling to room temperature. Filtering, rinsing with water, rinsing with ethanol, drying, and purifying by column chromatography to obtain compound 4-3(15.2g, 93%).
(4) Preparation of Compound 4-4
Reacting CuBr2(23.4g, 106mmol) and acetonitrile (MeCN)200mL were added to a 500mL single-neck flask, followed by the slow dropwise addition of tert-butyl nitrite (11g, 106mmol) and heating at 50 ℃ with stirring for one hour, followed by the addition of compound 4-3(15.2g, 53mmol) in portions and continued stirring at 50 ℃. Reacting for 3h, detecting by TLC, enabling the compound 4-3 to completely react, cooling the reaction liquid, pouring the cooled reaction liquid into 1L of water, separating out a large amount of yellow-green solid, filtering, leaching with ethanol, drying, extracting and separating with DCM, drying with organic phase anhydrous sodium sulfate, and purifying by column chromatography to obtain the compound 4-4(15g, yield 81%).
(5) Preparation of Compound C115
Compound 1-3(10g, 21mmol), compound 4-4(7.4g, 21mmol), potassium carbonate (5.8g, 42mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (146mg, 0.2mmol) was added to a flask containing 100mL of tetrahydrofuran and 25mL of water, the nitrogen was replaced and the reaction was heated under reflux under nitrogen for 4 hours and TLC showed completion. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to obtain compound C115(11.3g, yield 87%). Calculated molecular weight: 616.24, found C/Z: 616.2.
synthesis example 5:
synthesis of Compound C122
(1) Preparation of Compound 5-1
The compound 4-bromo-1-aminopyrrole (16.0g, 0.1mol) was added to a (500mL) flask containing 200mL of absolute ethanol, p-chlorobenzaldehyde (15.4g, 0.11mol) was added slowly in portions with stirring at room temperature, the reaction was controlled with ice bath during the course, and TLC showed completion after 2 hours. The reaction solution was separated by spin-drying with water and dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 5-1(23g, yield 81%).
(2) Preparation of Compound 5-2
Compound 5-1(20g, 71mmol), tolane (12.6g, 71mmol) and 300mL dioxane were charged into a 1L flask, and after displacing nitrogen gas, [ Cp. RhCl ] was added separately2]2(Mr. 618) (0.43g,0.7mmol) and copper acetate (25.7g, 142mmol), the reaction was refluxed for 16 hours at 120 ℃ with replacement of nitrogen 4 times, and the end of the reaction was monitored by TLC. And cooling the reaction to room temperature, slowly pouring the cooled reaction product into 500mL of cold water, precipitating a large amount of solid, leaching the filtered solid with water and ethanol for three times respectively, drying the solid, and performing column chromatography separation and purification to obtain the compound 5-2(20g, yield 61.5%).
(3) Preparation of Compound 5-3
Compound 5-2(20g, 43.6mmol), phenylboronic acid (5.9g, 48mmol) and potassium carbonate (12g, 87.2mmol), Pd (PPh)3)4(1.0g, 0.87mol) was charged into a 1L flask containing 200mL of toluene, 40mL of ethanol and 40mL of water, the nitrogen was replaced and the reaction was refluxed under nitrogen for 4 hours, and TLC showed completion of the reaction. Cooling to room temperature, separating, extracting water phase with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, and purifying by column chromatography to obtain compound 5-3(17.4g, yield 87%).
(4) Preparation of Compounds 5-4
Compound 5-3(17.4g, 38mmol), pinacol diboron ester (14.5g, 57mmol) and potassium acetate (7.4g, 76mol) were charged into a 1L flask containing 300mL of 1, 4-dioxane, and after nitrogen exchange at room temperature with stirring, palladium acetate (0.17g, 0.76mmol) and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (0.62g, 1.52mmol) were added. After the addition was completed, nitrogen was replaced four times, the reaction was refluxed with stirring for 12 hours, and the end of the reaction was monitored by TLC. The 1, 4-dioxane was removed by rotary evaporation, the mixture was separated with water and dichloromethane, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 5-4(16.5g, yield 79%).
(5) Preparation of Compound C122
Compound 5-4(16.5g, 30mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (8.1g, 30mmol), potassium carbonate (8.3g, 60mmol), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (0.22g, 0.3mmol) was added to a (1L) flask containing 200mL tetrahydrofuran and 50mL water, the nitrogen was replaced and the reaction was heated to reflux under nitrogen for 4 hours, and TLC indicated completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to give compound C122(14.3g, yield 73%). Calculated molecular weight: 654.25, found C/Z: 654.2.
synthesis example 6
Synthesis of comparative example compound D1:
(1) preparation of Compound 1B
Compound 1A (65.6g, 100mmol), phenylboronic acid (12.2g, 100mmol) and potassium carbonate (27.6g, 200mmol), Pd (PPh)3)4(1.0g, 0.87mol) was charged into a 2L flask containing 500L of toluene, 100mL of ethanol and 100mL of water, the nitrogen was replaced and the reaction was refluxed under nitrogen for 4 hours, and TLC showed completion of the reaction. Cooling to room temperature, separating, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying over anhydrous sodium sulfate, and purifying by column chromatography to obtain compound 1B (58.2g, 89% yield).
(2) Preparation of Compound 1C
Compound 1B (58g, 88.7mmol), pinacol diboron ester (33.8g, 133mmol), and potassium acetate (17.4g, 177.4mol) were charged into a 1L flask containing 600mL of 1, 4-dioxane, and after replacing nitrogen with stirring at room temperature, palladium acetate (0.4g, 1.78mmol), 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (1.46g, 3.56mmol) were added. After the addition was completed, nitrogen was replaced four times, the reaction was refluxed with stirring for 12 hours, and the end of the reaction was monitored by TLC. The 1, 4-dioxane was removed by rotary evaporation, the mixture was separated with water and dichloromethane, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound 1C (51g, yield 82%).
(3) Preparation of Compound D1
Compound 1C (50g, 71mmol), 5-chloro-imidazo [1,5-A]Pyridine (10.8g, 71mmol), potassium carbonate (8.3g, 60mmol), Pd2(dba)3(0.22g, 0.3mmol) was charged into a (1L) flask containing 600mL of tetrahydrofuran and 60mL of water, the nitrogen was replaced and the reaction was heated under reflux under nitrogen for 8 hours, and TLC showed completion of the reaction. The precipitated solid was filtered, rinsed with water and ethanol, respectively, dried and purified by column chromatography to obtain comparative example 1(38g, yield 77%). Calculated molecular weight: 654.25, found C/Z: 654.2.
device example 1
The embodiment provides a preparation method of an organic electroluminescent device, which comprises the following specific steps:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing until the pressure is less than 10-5Pa, performing vacuum evaporation on the anode layer film by using a multi-source co-evaporation method to obtain HI-3 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-4 on the hole injection layer in vacuum to serve as a first hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 40 nm;
evaporating HT-14 on the first hole transport layer in vacuum to serve as a second hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 10 nm;
a luminescent layer of the device is vacuum evaporated on the second hole transport layer, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material BFH-4 is adjusted to be 0.1nm/s, the evaporation rate of the dye BFD-6 is set in a proportion of 5%, and the total film thickness of evaporation is 20nm by using a multi-source co-evaporation method;
vacuum evaporating ET-17 on the luminescent layer to be used as a hole blocking layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 5 nm;
evaporating an electron transport layer on the hole blocking layer by using a multi-source co-evaporation method, adjusting the evaporation rate of the compound C1 to be 0.1nm/s, setting the proportion of the evaporation rate to the evaporation rate of ET-57 to be 100%, and setting the total film thickness of evaporation to be 23 nm;
LiF with the thickness of 1nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 80nm is used as a cathode of the device.
Device examples 2-9 differ from device example 1 only in that compound C1 was replaced by another compound, as specified in table 1.
Comparative device example 1
The difference from device example 1 is that compound C1 was replaced by comparative compound D1.
And (3) performance testing:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 9 and comparative example 1 were measured at the same brightness using a PR 750 type photoradiometer of Photo Research, a ST-86LA type brightness meter (photoelectric instrument factory of university of beijing) and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency;
the results of the performance tests are shown in table 1.
Table 1:
as can be seen from table 1, under the condition that the material schemes and the preparation processes of other functional layers in the organic electroluminescent device structure are completely the same, the current efficiency of each organic electroluminescent device prepared in the device embodiments 1 to 9 of the present invention is relatively high and the driving voltage is relatively low, wherein the current efficiency is 6.34 to 7.31cd/a, and the driving voltage is 4.17 to 4.78V.
The compound D1 used in comparative example 1 has a structure in which 4, 5-diazafluorene is used as a mother nucleus and 3-and 6-positions are respectively linked to imidazo [1,5-a ] pyridine and biphenyl groups, rather than the structure in which the electron-deficient group Ar is linked to a single bond of the mother nucleus of pyridazinopyrrole or pyridazinoimidazole as specified in the compound of the present invention, and the device has a driving voltage of 4.60V and a current efficiency of 5.83cd/a, and has a higher voltage, especially a lower current efficiency, as compared with the devices of examples.
Therefore, the structure that Ar is connected with the single bond of the pyridazinopyrrole or the pyridazinoimidazole in the compound of the invention can enable the compound to have higher electron injection and migration performance, so that a device has higher current efficiency and lower driving voltage, and the structure that the non-single bond is connected with the pyridazinopyrrole or the pyridazinoimidazole can not realize the technical effect of the invention.
Comparing example 1 with example 2, it can be seen that R is a triazine group when Ar is a pyridazine pyrrole parent nucleus1When the phenyl group is substituted, the comprehensive performance of the device is slightly reduced, because the specific structure and the large conjugated structure of the phenyl group reduce the electron injection and mobility, so that the voltage is increased, and the current efficiency is reduced
Comparing example 1 with examples 3,4 and 5, it can be seen that R is R when Ar is a triazine group and pyridazinopyrrole is a parent nucleus1When the compound is an electron-withdrawing group such as quinazoline, 9, 9-spirobifluorene, cyano and the like, the comprehensive performance of the device is obviously improved, because the electron-withdrawing capability of the quinazoline, the 9, 9-spirobifluorene and the cyano is stronger than that of a single benzene ring and the electron-deficiency property and the plane conjugation property of the whole molecule are better under the condition of equivalent plane conjugation, so that the electron injection and migration properties can be further improved.
It is understood from comparative example 1 and example 6 that when pyridazinoimidazole is used as a parent nucleus and the remaining structure is not changed, the improvement of the current efficiency and the reduction of the driving voltage of the device are almost the same. This indicates that the parent nucleus of pyridazinopyrrole or pyridazinoimidazole has little influence on the whole structure, and electron injection and mobility require an overall coordinated coordination of the Ar group and the R group to be adjusted to the optimum electron injection and mobility.
Comparing example 1 with examples 7 and 8, it can be seen that by changing the structure of the Ar electron-deficient group, it is found that compared with 4, 6-diphenyltriazine structures, quinazolinotriazole and pyrazinotriazole, electron injection and migration performance can be further improved, because compared with two new electron-deficient structures, the electron-deficient conjugation property after the 4, 6-diphenyltriazine structures are connected with the pyridazinopyrrole or pyridazinoimidazole parent nucleus single bond is stronger, and the device performance is shown to be that the current efficiency is improved by 15-20% on the premise that the voltage is not increased much.
The experimental data show that the novel organic material is an organic luminescent functional material with good performance as an electron transport material of an organic electroluminescent device, and has wide application prospect.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
