WO2022121920A1 - Boron-nitrogen compound, organic electroluminescent composition and organic electroluminescent device containing same - Google Patents

Abstract

Disclosed are a boron-nitrogen compound represented by formula (I) or (II), a composition containing the compound and an application thereof in the field of organic electroluminescence. Also disclosed is a method for preparing a boron-nitrogen compound represented by formula (I) or (II). An organic electroluminescent device made using the compound or the composition provided by the present disclosure can achieve efficient green and red electroluminescence having narrow spectral emission.

Description

A boron-nitrogen compound, organic electroluminescent composition and organic electroluminescent device comprising the same technical field

The embodiments of the present disclosure relate to the technical field of organic electroluminescence, such as a boron-nitrogen compound and a method for synthesizing the same, an organic electroluminescence composition, and an organic electroluminescence device comprising the aforementioned compound or composition.

Background technique

Organic electroluminescence technology has shown great application prospects in the fields of full-color display and solid-state white light illumination, and has received extensive research and attention in the scientific research and industrial circles. Organic small-molecule optoelectronic materials have been widely used as high-performance electroluminescent materials due to their clear structure, easy modification, and simple purification and processing. At present, traditional fluorescent dye molecules often have high photoluminescence quantum yields, but electroluminescence devices based on these fluorescent materials are limited by the internal quantum efficiency of 25%, and the external quantum efficiency of electroluminescence devices is generally lower than 5%, there is still a big gap with the efficiency of phosphorescent devices. At present, fluorescent electroluminescence devices that can break through the limit of 25% internal quantum efficiency mainly use the delayed fluorescence mechanism, which can effectively utilize the triplet excited state energy in the device. Delayed fluorescence mechanisms mainly include two types: (1) TTA (Triplet-Triplet Annihilation, triplet-triplet annihilation) mechanism; (2) TADF (Thermally Activated Delayed Fluorescence, thermally activated delayed fluorescence) mechanism. The TTA mechanism is a mechanism that utilizes the fusion of two triplet excitons to generate singlet excitons and improves the generation rate of singlet excitons, but the maximum internal quantum efficiency of the device is only 40% to 62.5%. The TADF mechanism utilizes small organic molecules with a small singlet-triplet energy level difference (ΔE _ST ), and its triplet excitons can be transformed into a reverse intersystem crossing (RISC) process under ambient thermal energy. The mechanism of singlet excitons. Theoretically, the internal quantum efficiency of the device can reach 100%. However, its device has a large efficiency roll-off at high brightness, which limits its application in full-color display and white lighting. TADF molecules are mainly doped as guest materials in wide-bandgap host materials to achieve high-efficiency thermally activated delayed fluorescence (see J.Am.Chem.Soc.2012,134,14706;Nature,2012,492,234;Mater.Horiz., 2014, 1, 264).

Different from traditional fluorescent molecular localized state (LE) emission, TADF emission mainly originates from the transition of intramolecular charge transfer (ICT: intramolecular charge transfer) state. Since most TADF light-emitting molecular structures adopt the form of conjugation or non-conjugation between electron donor (D:donor) groups and electron acceptor (A;acceptor) groups, the so-called D-A structure (Structure 1) , its electron donor group and electron acceptor group are separated in space, and this type of molecule is defined as: separated D-A structure. This D-A structure is conducive to the spatial separation of the highest occupied molecular orbital (HOMO: the highest occupied molecular orbital) and the lowest unoccupied molecular orbital (LUMO: the lowest unoccupied molecular orbital), and thus easy to obtain TADF luminescence. Moreover, based on the D-A structure, it is easy to realize the regulation of the peak position (wavelength) of the emission spectrum, that is, the emission color. However, the D-A structure shown in structure 1 can easily lead to configuration and conformation changes when the molecule is in the ground state and excited state, and generate abundant molecular vibrational modes. The emission spectra of most of these luminescent molecules are more than 100 nm wide at half maximum. Although a wider spectrum is beneficial for lighting applications, it cannot meet the requirements of high color purity in the display field. The main purpose of OLED light emission is display, so the narrow spectral design of TADF material (ie, smaller half-peak width) is very necessary.

Structure 1. D-A molecular structure

Reports in recent years (see Angew.Chem.2018,130,11486; J.Am.Chem.Soc., 2018,140,1195; Adv.Mater.2016,28,2777; CN109155368A; WO2016/152544A1; WO2017/188111A1; WO2018/150832A1; WO2018/186374A1; WO2018/216990A1) some light-emitting compounds based on tri-coordinated B (boron), the structural features of which are that the light-emitting compounds contain at least one B atom coordinated with three benzene rings to form a very rigid light-emitting compound. The chromophore core structure, and the three benzene rings that coordinate with B are covalently connected to N. Such molecules are called B-N complexes (structure 2), that is, the compounds are formed by the coordination of aromatic amine organic molecules with B. luminescent compounds.

Structure 2. Molecular model structure based on tricoordinate B-N complexes.

The frontier molecular orbitals of such tricoordinate B complexes have a characteristic, that is, the highest occupied orbital (HOMO: the highest occupied molecular orbital) and the lowest unoccupied orbital (LUMO: the lowest unoccupied molecular orbital) are alternately occupied (the so-called so-called The resonance structure of ) is distributed in the coordination system, with B in the LUMO orbital and N in the HOMO orbital. This type of B-N complexes have excited state charge transfer and TADF luminescence properties due to their unique HOMO and LUMO alternating electronic structure (resonance structure) (this type of molecule is defined as: resonance type D-A molecule), and it is very important. Its emission spectral band is very narrow, and the half-peak width of the emission spectrum can reach about 20 nm. Based on these compounds, high-performance blue or sky blue (the peak of the luminescence spectrum is between 450-490nm) organic electroluminescence devices can be prepared, and the electroluminescence spectrum is very narrow (the half-peak width is about 25nm). However, there has been no report on the preparation of materials with narrow emission spectrum for green light (the emission peak is between 520-535 nm) and red light (the emission peak is between 625-640 nm) based on this resonant B-N coordination structure. . The main reason is that although the molecules with the emission peaks in the green or even red region can be obtained by expanding the degree of conjugation of aromatic amines, the expansion of the conjugation system will destroy the electronic structure of the alternating layout of HOMO and LUMO, thus resulting in a change in the emission spectrum. Broad, narrow-spectrum emitting materials cannot be obtained.

Therefore, there is still a need for novel green and red organic electroluminescent materials with narrow spectral emission properties.

SUMMARY OF THE INVENTION

The following is an overview of the topics detailed in this article. This summary is not intended to limit the scope of protection of the claims.

In order to overcome the defect that the emission spectrum of the existing green light and red light organic electroluminescent materials is too broad, the present disclosure provides an organic compound, a composition and the same that emit light in the green light to red light region and have narrow-spectrum TADF emission characteristics. Organic Electroluminescent Devices.

The present disclosure provides a boron-nitrogen compound having the structure shown in formula I or II,

Each occurrence of R ¹ is independently H, D (deuterium), fluorine, CN, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl substituted by one or more ^Ra , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more ^Ra , Diphenylamino, or diphenylamino substituted with one or more ^Ra ;

E is a single key or

Each occurrence of R ¹¹ and R ²² is independently H, D (deuterium), C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;

R is:

H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ substituted by one or more R ^d aryl, 5- to 18-membered heteroaryl, or 5- to 18-membered ^heteroaryl substituted with one or more R;

Each occurrence of R ⁴ , R ⁵ and R ⁶ is independently H, D (deuterium), fluorine, CN, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkane aryl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl substituted by one or more R ^d , 5- to 18-membered heteroaryl, or 5- to 18 substituted by one or more R ^d -membered heteroaryl;

Each occurrence of R ^a is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₄ aryl substituted by one or more R ^b , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^b , diphenylamine group, or diphenylamino group substituted by one or more R ^b ;

Each occurrence of R ^b is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl base, C ₆ -C ₁₄ aryl substituted by one or more R ^c , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^c , diphenylamine group, or diphenylamino group substituted by one or more R ^c ;

Each occurrence of R ^c is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₄ aryl substituted by one or more R ^d , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^d , diphenylamine group, or diphenylamino group substituted by one or more R ^d ;

Each occurrence of R ^d is independently D (deuterium), fluorine, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, or C ₆ -C ₁₄ aryl substituted by one or more R ^e ;

Each occurrence of R ^e is independently D (deuterium), fluorine, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, or C ₆ -C ₁₄ aryl ;

The above-mentioned alkyl groups, alkoxy groups, cycloalkyl groups, aryl groups, and heteroaryl groups are optionally substituted by one or more substituents selected from the group consisting of halogen, -CN, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, C ₁ -C ₁₂ haloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, or 5- to 18-membered heteroaryl.

In yet another aspect, the present disclosure provides a method for preparing the above-mentioned boron-nitrogen compound, which comprises the steps shown in the following reaction formulas (1) and (2):

In the reaction formula (1), the carbazole skeleton-containing boron nitrogen core compound is used as the reactant, which is dissolved in an organic solvent, heated to reflux in the presence of a catalyst, and the para-hydrogen atom of the boron atom of the b benzene ring is activated. and replaced by boron ester;

In the reaction formula (2), the electron-withdrawing group is introduced into the boron-nitrogen skeleton by using the Suzuki reaction, and the introduced electron-withdrawing group is located in the para position of the B atom of the b benzene ring in the boron-nitrogen skeleton;

In the reaction formula (2), ArX is any one of the following three molecules:

X is Br or Cl;

R ¹ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ²² , and R are as defined above.

In another aspect, the present disclosure provides an organic electroluminescent composition comprising the above-mentioned boron-nitrogen compound. Further, the present disclosure also provides an organic electroluminescence composition comprising the above-mentioned boron nitride compound and a host material.

In yet another aspect, the present disclosure provides an organic electroluminescent device comprising the above-mentioned boron nitride compound or organic electroluminescent composition.

Other aspects will become apparent upon reading and understanding of the drawings and detailed description.

Description of drawings

The accompanying drawings of the embodiments will be briefly introduced below. Obviously, the accompanying drawings in the following description only relate to some embodiments of the present disclosure, rather than limit the present disclosure.

Figure 1 is a schematic diagram of the device structure used in Effect Example 2, wherein 1 is an ITO anode, 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light-emitting layer, 5 is an electron transport layer, and 6 is an electron injection layer layer, 7 is the metal cathode.

Figure 2 is the photoluminescence spectrum of the compound BN-66 doped film, wherein the composition of the doped film is H1-1 (97wt%):BN-66 (3wt%).

3 is the electroluminescence spectrum of the compound BN-66 doped film in Effect Example 2, wherein the composition of the doped film is H1-1 (97wt%):BN-66 (3wt%).

FIG. 4 is the temperature-resolved spectrum of the compound BN-66 doped film, wherein the composition of the doped film is H1-1 (97 wt %):BN-66 (3 wt %).

FIG. 5 is a graph showing the change of external quantum efficiency with luminance of the compound BN-66 doped device, wherein the doping weight percentage of the light-emitting layer is composed of H1-1 (97wt%):BN-66 (3wt%).

Detailed ways

The technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present disclosure. Obviously, the described embodiments are some, but not all, embodiments of the present disclosure. Based on the described embodiments of the present disclosure, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present disclosure.

It should be understood that, without conflict, any and all embodiments of the present disclosure may be combined with features from any other embodiment or embodiments to yield additional embodiments. The present disclosure includes such combinations resulting in additional embodiments.

All publications and patents mentioned in this disclosure are hereby incorporated by reference into this disclosure in their entirety. To the extent that the usage or terminology used in any publications and patents incorporated by reference conflicts with the usage or terminology used in this disclosure, the usage and terminology of this disclosure shall control.

Section headings used herein are for the purpose of organizing the article only and should not be construed as limiting the subject matter described.

Unless otherwise defined, all technical and scientific terms used herein have the ordinary meaning in the art to which the claimed subject matter belongs. If more than one definition exists for a term, the definitions herein prevail.

Unless otherwise stated, when disclosing or claiming a range of any type (eg, wavelength, half width, and number of substituents), it is intended to disclose or claim individually each possible value that the range could reasonably encompass, including those encompassed in any subrange within it. For example, numerical ranges such as 0 to 6, 1-4, 1 to 3, etc. defined in the substituents herein indicate integers within the range, wherein 0-6 is understood to include 0, 1, 2, 3, 4, 5, 6, also including 1-4 and 1-3.

As used in this disclosure, "comprising," "containing," or "comprising" and similar words mean that the elements appearing before the word encompass the recited elements appearing after the word and their equivalents, but do not exclude unrecited elements. The terms "containing" or "including (including)" as used herein can be open, semi-closed and closed. In other words, the term also includes "consisting essentially of," or "consisting of."

The terms "moiety", "structural moiety", "chemical moiety", "group", "chemical group" as used herein refer to a specific fragment or functional group in a molecule. A chemical moiety is usually thought of as a chemical entity embedded or attached to a molecule.

It should be understood that singular forms (eg, "a") used in this disclosure may include plural referents unless stated otherwise.

Unless otherwise indicated, the present disclosure employs standard nomenclature and standard laboratory procedures and techniques of analytical chemistry, synthetic organic chemistry, and optics. In some cases, standard techniques are used for chemical synthesis, chemical analysis, and performance testing of light-emitting devices. Unless otherwise specified, the present disclosure adopts traditional methods of mass spectrometry and elemental analysis, and each step and condition may refer to the conventional operation steps and conditions in the art.

The compounds of the present disclosure may contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute the compounds. For example, compounds can be labeled with isotopes, such as deuterium (D). All transformations of the isotopic composition of the compounds of the present disclosure, whether radioactive or not, are included within the scope of the present disclosure.

The reagents and starting materials used in the present disclosure are commercially available or can be prepared by conventional chemical synthesis methods.

The term "optional" is used herein to describe an event, meaning that the event may or may not occur. For example, optionally fused to a ring means that it is fused to a ring or not to a ring. For example, the term "optionally substituted" as used herein refers to being unsubstituted or having at least one non-hydrogen substituent that does not destroy the luminescent properties possessed by the unsubstituted analog.

In the present disclosure, unless otherwise specified, the number of "substitutions" can be one or more; when there are more than one, it can be 2, 3 or 4. In addition, when the number of the "substitution" is plural, the "substitution" may be the same or different.

In the present disclosure, the position of "substitution" can be arbitrary unless otherwise specified.

In the present disclosure, unless otherwise specified, the hydrogen or H is the hydrogen element in natural abundance, that is, a mixture of the isotopes protium, deuterium and tritium, wherein the abundance of protium is 99.98%.

In the present disclosure, the deuterium is D or ² H, also called deuterium, and the abundance of deuterium at the deuterium substitution site is greater than 95%.

Definitions of standard chemical terms can be found in references including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4TH ED." Vols. A (2000) and B (2001), Plenum Press, New York.

In this specification, groups and their substituents can be selected by those skilled in the art to provide stable moieties and compounds. When substituents are described by conventional chemical formulae written from left to right, the substituents also include the chemically equivalent substituents obtained when the structural formula is written from right to left. For example _-CH2O- is equivalent to _-OCH2- .

The term "halogen" or "halo" as used herein refers to fluorine, chlorine, bromine or iodine. In one embodiment, the halogen or halo is preferably fluoro or fluoro.

In the present disclosure, the term "alkyl" as a group or part of other groups (eg, as used in halogen-substituted alkyl groups and the like) is meant to include branched and straight chain chains having the specified number of carbon atoms. Saturated aliphatic hydrocarbon group. For example, C ₁ -C ₂₀ alkyl includes straight-chain or branched-chain alkyl groups having 1 to 20 carbon atoms. As defined in " _C1 - _C6 alkyl" is meant to include groups having 1, 2, 3, 4, 5, or 6 carbon atoms in a straight or branched chain structure. For example, in the present disclosure, the C ₁ -C ₆ alkyl groups are each independently methyl, ethyl, propyl, butyl, pentyl or hexyl; wherein, the propyl group is a C ₃ alkyl group (including the same isomers such as n-propyl or isopropyl); butyl is _C4 alkyl (including isomers such as n-butyl, sec-butyl, isobutyl or tert-butyl); pentyl is _C5 alkyl (including isomers such as n-pentyl, 1-methyl-butyl, 1-ethyl-propyl, 2-methyl-1-butyl, 3-methyl-1- butyl, isopentyl, tert-amyl or neopentyl); hexyl is _C6 alkyl (including isomers such as n-hexyl or isohexyl).

"Substituted alkyl" refers to an alkyl group substituted at any available point of attachment with one or more substituents, preferably 1 to 4 substituents. The term "haloalkyl" refers to an alkyl group having one or more halogen substituents, eg, halomethyl including, but not limited to, eg -CH2Br, _-CH2I , _-CH2Cl , _-CH2F , _- Groups such as CHF ₂ and -CF ₃ .

The term "alkoxy," as used herein, refers to an alkyl group, as defined above, attached via an oxygen bond (-O-), respectively. The term "substituted alkoxy" refers to a substituted alkyl group, as defined above, attached via an oxygen bond.

In this disclosure, the term "Cn-m aryl" as part of a group or other group refers to a monocyclic or polycyclic aromatic group having n to m ring carbon atoms (the ring atoms are only carbon atoms) having at least one carbocyclic ring with a conjugated pi electron system. Examples of the above-mentioned aryl unit include phenyl, biphenyl, naphthyl, indenyl, azulenyl, fluorenyl, phenanthryl, or anthracenyl. In one embodiment, the aryl group is preferably a _C6-14 aryl group such as phenyl, biphenyl and naphthyl, more preferably phenyl.

In the present disclosure, the term "n-m membered heteroaryl" as part of a group or other group means that ring atoms contain one or more ( eg 1, 2, 3 and 4) selected from nitrogen, oxygen and sulfur The heteroatom of the aromatic group has n to m ring atoms, and the heteroaryl group is a monocyclic, bicyclic, tricyclic or tetracyclic ring system, wherein at least one ring is an aromatic ring. Heteroaryl groups within the scope of this definition include, but are not limited to: acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, furyl, thienyl , benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, tetrahydroquinoline , imidazolyl, triazolyl, tetrazolyl, thiazolyl, isothiazolyl, furazanyl, thiadiazolyl, oxadiazolyl, triazinyl, purinyl, pteridyl, naphthyridinyl, quinazole Linoyl, phthalazinyl, imidazopyridyl, imidazothiazolyl, imidazoxazolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, isoindolyl, indazolyl, pyrrolo Pyridyl, thienopyridyl, furopyridyl, benzothiadiazolyl, benzoxadiazolyl, pyrrolopyrimidinyl, thienofuranyl. In one embodiment, as preferred examples of "5-18-membered heteroaryl", furyl, thienyl, pyrrolyl, imidazolyl, thiazolyl, pyrazolyl, oxazolyl, isoxazolyl can be listed , isothiazolyl, pyridyl, pyrimidinyl and carbazolyl, more preferably carbazolyl.

The term "fused" as used herein means that two or more carbocyclic or heterocyclic rings share a ring edge to form a polycyclic ring.

The term C _n -C _m cycloalkyl as used herein refers to a monocyclic or polycyclic alkyl group having n to m carbon atoms, such as C ₃ -C ₁₀ cycloalkyl and C ₃ -C ₆ cycloalkyl. Examples include adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and bicycloheptyl. In one embodiment, the C3 _{- C10} cycloalkyl is preferably adamantyl or cyclohexyl.

The present disclosure provides a method for designing and synthesizing organic light-emitting molecules with a luminescent peak between 495-630 nm and a narrow emission spectrum. 1) and HOMO and LUMO alternate layout electronic structure (resonance structure, as shown in structure 2) is different. The specific molecular design adopted in the present disclosure is as follows:

Structure 3. Representative model molecular structure.

Structure 3 presents a representative molecular design model structure provided by the present disclosure. The definition of the Ar group is as described above. It is a pyrimidine derivative with electron withdrawing ability. The general method and principle of molecular design provided are: in HOMO and An additional pyrimidine derivative electron acceptor group is introduced into the functional skeleton of the LUMO alternate layout electronic structure (resonance structure), a C (carbon) atom of the introduced pyrimidine derivative and a C atom on the resonance structure group They are linked by a single bond, and the additional pyrimidine derivatives are covalently linked by para-substitution with respect to the B atom in the resonance structure (as shown in structure 3). Since the additional pyrimidine derivative C atom is connected to the C of the LUMO orbital arrangement on the resonance structure group, the LUMO orbital of the molecule provided by the present disclosure is formed by the LUMO orbital of the resonance structure part merged with the LUMO orbital of the additional pyrimidine derivative acceptor formed, and the HOMO orbital of the molecule provided by the present disclosure is the same as the HOMO orbital of the resonance structure part in the molecule. Therefore, the organic light-emitting molecule provided by the present disclosure is sterically separated from the molecular structure to the frontier orbital electronic structure and the existing electron donor group and electron acceptor group. D-A type structure and HOMO and LUMO alternate layout electronic structure (resonance structure) are different.

The advantage of the organic light-emitting molecule design method provided by the present disclosure is that it combines the advantages of the isolated D-A structure and the resonance D-A molecule, and overcomes the disadvantages of these two types of molecules. Since the additional pyrimidine derivative acceptor and B atom take a para-substituted form, and because the pyrimidine derivative acceptor has a strong electron-withdrawing ability, it will significantly improve the intramolecular charge transfer characteristics of the target molecule, and the strong intramolecular charge transfer characteristics It is beneficial to the realization of long-wavelength emission. Using the molecular design method provided by the present disclosure, an organic light-emitting material with a narrow emission spectrum with an emission peak wavelength from 495 nm to 630 nm can be obtained, for example, the half-peak width of the emission spectrum is less than or equal to 65 nm.

Using the technical method provided by the present disclosure can effectively design and synthesize organic molecules that emit light in the green to red region and have narrow-spectrum TADF luminescence characteristics. Such organic molecules and their compositions with some materials can be used as luminescent materials to prepare organic electroluminescence. The light-emitting layer of the device, the organic electroluminescent device prepared here has the advantages of narrow emission spectrum, high efficiency, and high color purity of the device.

The present disclosure provides a boron-nitrogen compound having the structure shown in formula I or II,

Each occurrence of R ¹ is independently H, D (deuterium), fluorine, CN, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl substituted by one or more ^Ra , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more ^Ra , Diphenylamino, or diphenylamino substituted with one or more ^Ra ;

E is a single key or

Each occurrence of R ¹¹ and R ²² is independently H, D (deuterium), C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;

R is:

H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ substituted by one or more R ^d aryl, 5- to 18-membered heteroaryl, or 5- to 18-membered ^heteroaryl substituted with one or more R;

Each occurrence of R ⁴ , R ⁵ and R ⁶ is independently H, D (deuterium), fluorine, CN, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkane aryl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl substituted by one or more R ^d , 5- to 18-membered heteroaryl, or 5- to 18 substituted by one or more R ^d -membered heteroaryl;

Each occurrence of R ^a is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₄ aryl substituted by one or more R ^b , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^b , diphenylamine group, or diphenylamino group substituted by one or more R ^b ;

Each occurrence of R ^b is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl base, C ₆ -C ₁₄ aryl substituted by one or more R ^c , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^c , diphenylamine group, or diphenylamino group substituted by one or more R ^c ;

Each occurrence of R ^c is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₄ aryl substituted by one or more R ^d , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^d , diphenylamine group, or diphenylamino group substituted by one or more R ^d ;

Each occurrence of R ^d is independently D (deuterium), fluorine, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, or C ₆ -C ₁₄ aryl substituted by one or more R ^e ;

Each occurrence of R ^e is independently D (deuterium), fluorine, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, or C ₆ -C ₁₄ aryl ;

The above-mentioned alkyl, alkoxy, cycloalkyl, aryl, and heteroaryl are optionally substituted by one or more substituents selected from the group consisting of halogen, -CN, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, C ₁ -C ₁₂ haloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, or 5- to 18-membered heteroaryl.

In a certain embodiment of the present disclosure, each occurrence of R ¹ is independently H, F, CF ₃ , C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, cyclohexyl, adamantyl, phenyl, naphthyl, phenyl substituted by one or more ^Ra , carbazolyl, carbazolyl substituted by one or more ^Ra , diphenylamino, or diphenyl substituted by one or more ^Ra Anilino, the R ^a is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ fluoroalkyl and C ₁ -C ₆ alkoxy.

^In a certain embodiment of the present disclosure, each occurrence of R4, ^R5 and R6 is independently H, F, _CF3 , _C1 ^- _C20 alkyl, _C1 - _C20 alkoxy, cyclo Hexyl, adamantyl, phenyl, naphthyl, phenyl substituted by one or more R ^d , carbazolyl and carbazolyl substituted by one or more R ^{d selected} from C ₁ to C ₁₂ alkyl, C ₁ -C ₁₂ fluoroalkyl, C ₁ -C ₁₂ alkoxy, phenyl and phenyl substituted with one or more ^Re selected from ^C ₁ -C ₆ Alkyl, C ₁ -C ₆ fluoroalkyl and C ₁ -C ₆ alkoxy.

In a certain embodiment of the present disclosure, each occurrence of R ¹¹ and R ²² is independently H, methyl, methoxy or CF ₃ .

In a certain embodiment of the present disclosure, the frontier molecular orbitals of the boron-nitrogen compounds of Formulas I and II have the following characteristics:

HOMO and LUMO are distributed alternately on the ring atoms of ring c11, ring c12, ring c13, ring c14, ring b1 of formula I and one B and two N which are connected to three of the rings at the same time. HOMO is distributed on the two Ns, and LUMO is distributed on the B atom, ring m1 and ring ph1;

HOMO and LUMO are distributed alternately on the ring atoms of ring c21, ring c22, ring c23, ring c24, ring b2 of formula II and one B and two N which are connected to three of the rings at the same time. The HOMO is distributed on the two Ns, and the LUMO is distributed on the B atom, ring m2 and ring ph2.

In a certain embodiment of the present disclosure, the emission peaks of the emission spectra of the compounds of formula I and II are at 490-630 nm and the half-peak width of the emission spectra is less than or equal to 60 nm.

In a certain embodiment of the present disclosure, the emission peaks of the emission spectra of the compounds of formula I and II are 500-600 nm and the half-peak width of the emission spectrum is less than or equal to 60 nm.

In a certain embodiment of the present disclosure, E is a single bond or ^a benzene ring; each occurrence of R is independently H, methyl, tert-butyl, phenyl, 4-tolyl, 3-tolyl, 3 ,5-xylyl, 4-tert-butylphenyl, 3-tert-butylphenyl, 3,5-di-tert-butylphenyl, diphenylamino, bis(p-tolyl)amino, or bis( p-tert-butylphenyl)amino; R ¹¹ and R ²² are H; R is H or

R ⁴ and R ⁶ are the same and are tert-butyl, phenyl, 4-tolyl, 3-tolyl, 3,5-xylyl, 4-tert-butylphenyl, 3-tert-butylphenyl, 3 ,5-di-tert-butylphenyl, 4-C ₁ -C ₁₀ alkoxyphenyl, 3-C ₁ -C ₁₀ alkoxyphenyl, or 3,5-diC ₁ -C ₁₀ alkoxy Phenyl ^; R5 is H.

In a certain embodiment of the present disclosure, the molecular structure composition of the compounds represented by formulas I and II satisfies the following definitions:

wherein E in formula I is a single bond or

where in formula II

for

wherein in formulas I and II

Any of the following groups:

wherein in formulas I and II

Any of the following groups:

In a certain embodiment of the present disclosure, the compound represented by formula I and II is any one of the following compounds:

The present disclosure also provides a method for preparing the above-mentioned boron-nitrogen compound, which comprises the steps shown in the following reaction formulas (1) and (2):

In the reaction formula (1), the carbazole skeleton-containing boron nitrogen core compound is used as the reactant, which is dissolved in an organic solvent, heated to reflux in the presence of a catalyst, and the para-hydrogen atom of the boron atom of the b benzene ring is activated. and replaced by boron ester;

In the reaction formula (2), the electron-withdrawing group is introduced into the boron-nitrogen skeleton by using the Suzuki reaction, and the introduced electron-withdrawing group is located in the para position of the B atom of the b benzene ring in the boron-nitrogen skeleton;

In the reaction formula (2), ArX is any one of the following three molecules:

X is Br or Cl;

R ¹ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ²² , and R are as defined above.

The compound of formula I described in the present disclosure can be prepared according to conventional chemical synthesis methods in the art, and its steps and conditions can refer to the steps and conditions of similar reactions in the art. The present disclosure provides a preparation method of compounds represented by formulas (I and II, which may include the following schemes:

in

The present disclosure also provides an organic electroluminescent device comprising an anode, an emission layer, an optional hole injection layer, an optional hole transport layer, an optional electron transport layer, an optional electron injection layer, and a cathode , wherein at least one layer of the light-emitting layer, the electron injection layer, the electron transport layer, the hole transport layer, and the hole injection layer contains the above-mentioned boron nitride compound. The organic electroluminescent devices of the present disclosure may also include an optional hole blocking layer, an optional electron blocking layer, an optional capping layer, and the like. In one embodiment, the organic electroluminescent device has the structure shown in Figure 1, wherein 1 is an ITO anode, 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light-emitting layer, and 5 is an electron The transport layer, 6 is the electron injection layer, and 7 is the metal cathode.

In a certain embodiment of the present disclosure, the boron nitride compound represented by formula I or II is used to prepare a light-emitting layer in an organic electroluminescent device.

In a certain embodiment of the present disclosure, the boron nitride compound represented by formula I or II is used to prepare a light-emitting layer in an organic electroluminescent device, and the molecular structures of the compounds represented by I and II are defined as follows:

wherein E in formula I is a single bond or

where in formula II

for

wherein in formulas I and II

is any one of formulas B-1 to B-100;

wherein in formulas I and II

is any one of formulae M-1 to M-88.

In a certain embodiment of the present disclosure, the boron nitride compounds represented by formulae BN-1 to BN-584 are used to prepare light-emitting layers in organic electroluminescent devices.

In a certain embodiment of the present disclosure, the organic electroluminescent device further includes a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer sequentially formed on the substrate; the organic light-emitting functional layer includes The light-emitting layer containing the above-mentioned boron nitride compound may further comprise any one or a combination of any one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer .

The present disclosure provides an organic electroluminescent composition comprising a boron nitride compound (as a dopant material) as represented by formula I or II and a host material; the host material is capable of transporting electrons and/or holes And its triplet excited state energy is higher than or close to the triplet excited state energy of the doped material.

In a certain embodiment of the present disclosure, the host material in the organic electroluminescent composition may be a carbazole derivative and/or a carboline represented by formulae (H-1) to (H-6) derivative. The organic electroluminescent composition preferably contains 0.3-30.0wt% (weight percentage) any compound represented by formula I or II as a doping material, and the remaining 99.7-70.0wt% components are formula (H -1) A host material composed of 1-2 kinds of compounds in (H-6). In one embodiment, the host material contains two compounds of formulae (H-1) to (H-6) in a weight ratio of 1:5 to 5:1.

wherein X ₁ , Y ₁ and Z ₁ are CH or N, and at most one of X ₁ , Y ₁ and Z ₁ is N.

wherein R ^1H and R ^2H are independently any of the following:

wherein X ₂ , Y ₂ and Z ₂ are CH or N, and at most one of X ₂ , Y ₂ and Z ₂ is N.

wherein R ^aH and R ^bH are independently H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkyl substituted C ₆ -C ₂₀ Aryl or C ₁ -C ₂₀ alkoxy substituted C ₆ -C ₂₀ aryl.

In an embodiment of the present disclosure, the host material in the organic electroluminescent composition is 1-2 kinds of compounds H1-1 to H1-427; in the organic electroluminescent composition, It contains 0.3-30.0wt% (weight percentage) of any compound represented by formula I or II, and the remaining 99.7-70.0wt% components are 1-2 compounds among compounds H1-1 to H1-427. In a preferred embodiment of the present disclosure, the organic electroluminescent composition contains two compounds of formula H1-1 to H1-427 as host materials, and the weight ratio of the two compounds is 1:5 to 5: 1.

In a certain embodiment of the present disclosure, the dopant material in the organic electroluminescent composition is any compound represented by formula I or II (the content is 0.3wt%-30.0wt%); the host material ( content of 99.7wt%-70.0wt%) is represented by any one of the 1,3,5-triazine derivatives represented by formulae Trz1-A, Trz2-A and Trz3-A and formulae H-1 to H-6 The composition of any of the compounds shown. In a preferred embodiment, the 1,3,5-triazine derivatives represented by Trz1-A, Trz2-A or Trz3-A in the host material are combined with H-1, H-2, H-3, H- 4. The weight ratio between the compounds represented by H-5 or H-6 is 1:5 to 5:1.

One or two of R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are independently R ^Tz , and the rest are the same or different independently hydrogen, deuterium, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₆ -C ₁₈ aryl, C ₁ -C ₈ alkyl substituted C ₆ -C ₁₈ aryl or C ₁ -C ₈ alkoxy substituted C ₆ -C ₁₈ Aryl; R ^Tz is any one of the groups Tz-n (n=1-61) shown in the following formula:

In a certain embodiment of the present disclosure, the dopant material in the organic electroluminescent composition is any compound represented by formula I or II (the content is 0.3wt%-30.0wt%); the host material ( The content is 99.7wt%-70.0wt%) by any one of 1,3,5-triazine derivatives represented by formulae TRZ-1 to TRZ-56 and carbazole or carbazole represented by formulae H1-1 to H1-427 Any of the morpholine derivatives. In a preferred embodiment, the weight ratio between the 1,3,5-triazine derivative and the carbazole or carboline derivative in the host material is 1:5 to 5:1.

The present disclosure provides an application of the organic electroluminescent composition as described above as an organic electroluminescent material.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is used to prepare a light-emitting layer in an organic electroluminescent device.

The present disclosure also provides an organic electroluminescent device comprising an anode, an emission layer, an optional hole injection layer, an optional hole transport layer, an optional electron transport layer, an optional electron injection layer, and a cathode , wherein at least one layer of the light-emitting layer, the electron injection layer, the electron transport layer, the hole transport layer, and the hole injection layer comprises the organic electroluminescence composition as described above. In a preferred embodiment, the light-emitting layer of the organic electroluminescent device comprises an organic electroluminescent composition as described above.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is a light-emitting layer, and the light-emitting principle of the light-emitting layer is based on the energy transfer from the host material to any compound represented by formula I or II or the loading of the light-emitting material itself. Stream capture.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is a light-emitting layer; the host material in the organic electroluminescent composition can be as formula (H-1) to (H-6) The carbazole derivatives and/or carboline derivatives shown. In a preferred embodiment, the organic electroluminescent composition contains 0.3-30.0 wt % of any compound represented by formula I or II, and the remaining 99.7-70.0 wt % components are formula (H-1) The main body composed of 1-2 compounds in (H-6). For example, when the host contains two compounds of formulae (H-1) to (H-6), the weight ratio of the two compounds is 1:5 to 5:1.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is a light-emitting layer; the host material in the composition is 1-2 kinds of compounds H1-1 to H1-427. In a preferred embodiment, the organic electroluminescent composition contains 0.3-30.0wt% of any compound represented by formula I or II, and the remaining 99.7-70.0wt% components are compounds H1-1 to 1-2 compounds in H1-427. For example, when two compounds of formulae H1-1 to H1-427 are contained in the composition, the weight ratio of the two compounds is 1:5 to 5:1.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is a light-emitting layer; the dopant material in the organic electroluminescent composition is any compound represented by formula I or II ( The content is 0.3wt-30.0wt%); the host material (content is 99.7wt-70.0wt%) is composed of any of the 1,3,5-triazine derivatives shown in formula Trz1-A, Trz2-A and Trz3-A One and any one of the compounds represented by formulae H-1 to H-6. For example, in the host material, 1,3,5-triazine derivatives represented by Trz1-A, Trz2-A or Trz3-A are combined with H-1, H-2, H-3, H-4, H The weight ratio between the compounds represented by -5 or H-6 is 1:5 to 5:1.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is a light-emitting layer; the dopant material in the organic electroluminescent composition is any compound represented by formula I or II ( The content is 0.3wt-30.0wt%); the host material (content is 99.7wt-70.0wt%) is composed of any one of the 1,3,5-triazine derivatives shown in the formula TRZ-1 to TRZ-56 and the formula It is composed of any one of the carbazole or carboline derivatives represented by H1-1 to H1-427. For example, in the host material, the weight ratio between the 1,3,5-triazine derivative and the carbazole or carboline derivative is 1:5 to 5:1.

In a certain embodiment of the present disclosure, the organic electroluminescent composition is a light-emitting layer; the doping material in the organic electroluminescent composition is any of the formulas BN-1 to BN-584. A compound (content is 0.3wt-30.0wt%); the host material (content is 99.7wt-70.0wt%) is composed of any of the 1,3,5-triazine derivatives shown in formula TRZ-1 to TRZ-56 It is composed of any one of the carbazole or carboline derivatives represented by the formulae H1-1 to H1-427. For example, in the host material, the weight ratio between the 1,3,5-triazine derivative and the carbazole or carboline derivative is 1:5 to 5:1.

In a certain embodiment of the present disclosure, the organic electroluminescent device further includes a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer sequentially formed on the substrate; the organic light-emitting functional layer includes The light-emitting layer containing the organic electroluminescent composition as described above may further comprise any one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer, or various combinations.

The present disclosure provides an application of the organic electroluminescence device in an organic electroluminescence display or an organic electroluminescence illumination light source.

The present disclosure provides a molecular structure design method for designing and synthesizing organic light-emitting materials, which has the advantages of combining the advantages of the isolated D-A structure and the resonance D-A molecule, and overcoming the disadvantages of these two types of molecules. Based on the molecular design method, the existing green and red organic electroluminescent materials can effectively overcome the defects of excessively broad emission spectrum, and provide an organic molecule that emits light in the green-red region and even near-infrared and has narrow-spectrum emission characteristics. Design synthesis and preparation technology methods; and further provide an organic compound and composition that emits light in the green to red light region and has narrow-spectrum emission characteristics as shown in formulas I and II, and its use in the field of organic electroluminescence Applications. The organic molecules provided by the present disclosure and their compositions with some materials can be used as light-emitting materials to prepare the light-emitting layer of the organic electroluminescent device, and the organic electroluminescent device prepared here has a narrow emission spectrum (relative to the separated D-A structure emitting light) The electroluminescence spectrum of the material), high efficiency and high efficiency.

The present disclosure provides a synthesis method for coupling a tricoordinate B complex of 1,3-dicarbazole (or its derivative) benzene with a pyrimidine derivative. The advantage of the synthesis method is that it can combine electron withdrawing properties The pyrimidine derivative group is coupled with the C atom occupied by the LUMO orbital in the tricoordinate B resonance framework, so based on this synthesis method, pyrimidine derivatives with a conjugated structure and strong electron withdrawing properties can be effectively synthesized groups are introduced into the tricoordinate B resonance framework.

According to conventional synthetic ideas, researchers in the field usually follow the following reaction route (3) to synthesize molecules containing a tri-coordinated B resonance skeleton and a pyrimidine derivative group. In the following reaction test, Ar is a pyrimidine derivative. Our The experimental research results show that the tricoordinate B structure cannot be formed according to the following reaction route, that is, the boron atom cannot achieve coordination with 1,3-dicarbazole (or its derivative) benzene under this condition. obtain the target product. The main reason is that when the pyrimidine derivative with strong electron withdrawing group exists, its para carbon atom is in an electron-deficient state, that is, the electron cloud density is low, so that the carbon atom cannot form a covalent bond with the boron atom.

The definitions of R ¹ and Ar are as previously described.

The technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some, but not all, embodiments of the present disclosure. Based on the described embodiments of the present disclosure, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present disclosure.

The present disclosure is further described below by means of embodiments, but the present disclosure is not limited to the scope of the described embodiments. The experimental methods that do not specify specific conditions in the following examples are selected according to conventional methods and conditions, or according to the product description.

Molecular mass spectrometry data (Mass Spectra: MS) with relative molecular weight below 1000 was measured by Thermo Fisher's ITQ1100 ion trap gas chromatography-mass spectrometer, and molecular mass spectrometry data with relative molecular weight above 1000 was obtained by Bruker's Autoflex Speed matrix Auxiliary group laser desorption time-of-flight mass spectrometry measured. The machine used for elemental analysis of the final product was Flash EA1112 from Elemental analysis company.

The UV-Vis absorption spectrum of the sample film was measured by a LAMBDA 35 UV-Vis spectrophotometer of PerkinElmer Company. The fluorescence spectrum was measured by the RF-5301PC fluorescence photometer of Shimadzu Company in Japan, and the excitation wavelength selected during the test was the maximum absorption wavelength.

Specifically, the raw material-1 used includes the following molecules:

Specifically, the raw material-2 used includes the following molecules:

Specifically, the raw material-3 used includes the following molecules:

The basic process route of the compound synthesis involved in the present disclosure is as follows, and the reaction is divided into four steps. The first two steps are the synthesis of BNCz parent nucleus; the core of the final product synthesis is the successful preparation of the precursor BN-Bpin. We used the originally synthesized boron-nitrogen core containing carbazole skeleton as the substrate, dissolved it in tetrahydrofuran, and added 1% equivalent of the main catalyst methoxy (cyclooctadiene) iridium dimer, 2% equivalent Under the condition of cocatalyst 4,4'-di-tert-butyl-2,2'-bipyridine, the reaction system is heated to reflux, and the boron atom replaces the para-hydrogen atom of the benzene ring to activate and is replaced by a boron ester. Next, a simple Suzuki reaction can flexibly obtain a variety of electron-withdrawing substituted compounds. The specific synthetic process steps are:

in

Synthesis Example

In the first step, 60 ml of anhydrous DMF (N,N-dimethylformamide) solution containing 35.2 mmol of carbazole derivatives was slowly added dropwise to 50 ml of anhydrous solution containing 5.4 g of potassium tert-butoxide (48.0 mmol). To the DMF solution, after stirring at room temperature for 2 hours, 20 ml of an anhydrous DMF solution containing 3.1 g of 2-bromo-1,3-difluorobenzene (16.0 mmol) was added dropwise thereto. The reaction system was stirred at 140°C for 24 hours, then cooled to room temperature and poured into ice water. The white solid was filtered off with suction, dried in vacuo and further purified by column chromatography using a mixed eluent of dichloromethane/petroleum ether to give the intermediate BrNCz as a white solid.

In the second step, under the protection of nitrogen atmosphere, 19.4 mL of n-hexane solution of tert-butyllithium (25.2 mmol) was slowly added to 100 mL of tert-butylbenzene solution (-30°C) containing 12.6 mmol of intermediate BrNCz. The temperature was slowly raised to 60°C, and after stirring for 2 hours, n-hexane was removed in vacuo, then cooled to -30°C, 2.4 mL of boron tribromide (6.3 mmol) was added, and the reaction mixture was stirred at room temperature for 1 hour. Next, 15.6 mL of N,N-diisopropylethylamine (91.1 mmol) was added at 0°C, and the reaction mixture was heated to 130°C and stirred for 5 hours before cooling to room temperature. 5 ml of methanol was added to the reaction mixture to quench residual _BBr3 . The reaction was concentrated in vacuo and purified by column chromatography eluting with a mixture of dichloromethane/petroleum ether to give the BNCz parent nucleus.

In the third step, at room temperature, the carbazole skeleton-containing boron nitrogen raw material (6.5 mmol) and 1.7 g of pinacol diboronate (6.5 mmol) were added to tetrahydrofuran (60 mL), and the mixture was bubbled with nitrogen for 10 minutes, and 34.9 mg of 4,4'-di-tert-butyl-2,2'-bipyridine (0.13 mmol) and 43.1 mg of methoxy(cyclooctadiene)iridium dimer (0.065 mmol) were added under high flow of nitrogen . After stirring for 10 minutes, the mixture was heated to reflux and stirred for 24 hours. After the reaction system was cooled to room temperature, it was directly concentrated under reduced pressure and purified by column chromatography to obtain the precursor BN-Bpin.

In the fourth step, Ar-X (Ar is defined as above, X is bromine) (0.6 mmol), BN-Bpin (0.5 mmol), 0.14 g potassium carbonate (1 mmol) and water (2 mL) were added to tetrahydrofuran (16 mL). ), the mixture was sparged with nitrogen for 10 minutes and 28.9 mg of tetrakis(triphenylphosphine)palladium (0.025 mmol) was added under high flow of nitrogen. The mixture was heated to reflux and stirred for 12 hours. After the reaction system was cooled to room temperature, the reaction mixture was extracted with dichloromethane and water, the organic phase was heated under vacuum to dry, and then purified by column chromatography to obtain the target product BN-n (n=1-584).

Taking compound BN-66 as an example to illustrate the specific details of the synthesis example experiment: In the first step, 60 ml of anhydrous DMF (N, N-dimethylcarbazole) containing 9.8 g of 3,6-di-tert-butylcarbazole (35.2 mmol) Formamide) solution was slowly added dropwise to 50 ml of anhydrous DMF solution containing 5.4 g of potassium tert-butoxide (48.0 mmol), and after stirring at room temperature for 2 hours, 20 ml of 2-bromo-1 containing 3.1 g of 2-bromo-1 was added dropwise thereto. 3-Difluorobenzene (16.0 mmol) in dry DMF. The reaction system was stirred at 140°C for 24 hours, then cooled to room temperature and poured into ice water. The white solid was filtered off with suction, dried in vacuo and further purified by column chromatography using a mixed eluent of dichloromethane/petroleum ether to give 10.5 g of intermediate BrNCz as a white solid (92% yield).

In the second step, under the protection of nitrogen atmosphere, 19.4 mL of n-hexane solution of tert-butyllithium (25.2 mmol) was slowly added to 100 mL of tert-butylbenzene solution containing 9.0 g (12.6 mmol) of intermediate BrNCz (-30°C). ). The temperature was slowly raised to 60°C, and after stirring for 2 hours, n-hexane was removed in vacuo, then cooled to -30°C, 2.4 mL of boron tribromide (6.3 mmol) was added, and the reaction mixture was stirred at room temperature for 1 hour. Next, 15.6 mL of N,N-diisopropylethylamine (91.1 mmol) was added at 0°C, and the reaction mixture was heated to 130°C and stirred for 5 hours before cooling to room temperature. 5 ml of methanol was added to the reaction mixture to quench residual _BBr3 . The reaction system was concentrated in vacuo, and purified by column chromatography with a mixture eluent of dichloromethane/petroleum ether to obtain 2.9 g of BNCz parent nucleus as a yellow solid (yield 35%) (the experiment can be repeated many times to enrich the raw materials. ).

In the third step, 4.2 g of BNCz (6.5 mmol) and 1.7 g of pinacol diboronate (6.5 mmol) were added to tetrahydrofuran (60 mL) at room temperature, the mixture was bubbled with nitrogen for 10 minutes, and the mixture was heated under high flow nitrogen. 34.9 mg of 4,4'-di-tert-butyl-2,2'-bipyridine (0.13 mmol) and 43.1 mg of methoxy(cyclooctadiene)iridium dimer (0.065 mmol) were added. After stirring for 10 minutes, the mixture was heated to reflux and stirred for 24 hours. After the reaction system was cooled to room temperature, it was directly concentrated under reduced pressure and purified by column chromatography to obtain the precursor 4.5g BN-Bpin (yield 90%).

In the fourth step, 187 mg of 2-bromo-4,6-diphenylpyrimidine (0.6 mmol), 383 mg of BN-Bpin (0.5 mmol), 0.14 g of potassium carbonate (1 mmol) and water (2 mL) were added to tetrahydrofuran (16 mL) The mixture was sparged with nitrogen for 10 minutes and 28.9 mg of tetrakis(triphenylphosphine)palladium (0.025 mmol) was added under high flow of nitrogen. The mixture was heated to reflux and stirred for 12 hours. After the reaction system was cooled to room temperature, the reaction mixture was extracted with dichloromethane and water, the organic phase was heated and spin-dried under vacuum, and then purified by column chromatography to obtain 284 mg of the target product BN-66 as a yellow solid (yield 58%). ).

Table 1. Elemental analysis of compounds BN-1 to BN-584 (percentage of C, H and N in the compounds), molecular weight measured by mass spectrometry, and synthetic reaction yield data (four-step reaction total yield).

compound	raw material-1	raw material-2	Raw material-3	molecular weight	Elemental Analysis (%) (C, H, N)	Yield(%)
BN-1	S1	S2-1	S3-1	494.36	C, 82.61; H, 3.87; N, 11.33	17
BN-2	S1	S2-1	S3-2	646.56	C, 85.45; H, 4.21; N, 8.67	18
BN-3	S1	S2-1	S3-3	758.78	C, 85.48; H, 5.71; N, 7.38	20
BN-4	S1	S2-1	S3-4	814.88	C, 85.49; H, 6.31; N, 6.88	twenty one

BN-5	S1	S2-1	S3-5	702.67	C, 85.47; H, 5.02; N, 7.97	20
BN-6	S1	S2-1	S3-6	702.67	C, 85.47; H, 5.02; N, 7.97	17
BN-7	S1	S2-1	S3-7	870.99	C, 85.50; H, 6.83; N, 6.43	16
BN-8	S1	S2-1	S3-8	846.88	C, 82.26; H, 6.07; N, 6.62;	twenty three
BN-9	S1	S2-1	S3-9	730.72	C, 85.47; H, 5.38; N, 7.67	15
BN-10	S1	S2-1	S3-10	1151.53	C, 85.53; H, 8.67; N, 4.87	twenty two
BN-11	S1	S2-1	S3-11	1247.53	C, 78.95; H, 8.00; N, 4.49;	twenty one
BN-12	S1	S2-1	S3-12	798.76	C, 87.22; H, 4.42; N, 7.01	20
BN-13	S1	S2-1	S3-13	910.97	C, 87.02; H, 5.64; N, 6.15	19
BN-14	S1	S2-1	S3-14	910.97	C, 87.02; H, 5.64; N, 6.15	17
BN-15	S1	S2-1	S3-15	950.95	C, 88.41; H, 4.56; N, 5.89	15
NN-16	S1	S2-1	S3-16	950.95	C, 88.41; H, 4.56; N, 5.89	twenty three
BN-17	S1	S2-1	S3-17	722.66	C, 86.43; H, 4.32; N, 7.75	twenty one
BN-18	S1	S2-1	S3-18	834.87	C, 86.32; H, 5.67; N, 6.71	25
BN-19	S1	S2-1	S3-19	834.87	C, 86.32; H, 5.67; N, 6.71	twenty one
BN-20	S1	S2-1	S3-20	890.98	C, 86.28; H, 6.22; N, 6.29	20
BN-21	S1	S2-1	S3-21	778.77	C, 86.37; H, 5.05; N, 7.19	15
BN-22	S1	S2-1	S3-22	778.77	C, 86.37; H, 5.05; N, 7.19	twenty two
BN-23	S1	S2-1	S3-23	947.09	C, 86.24; H, 6.71; N, 5.92	twenty one
BN-24	S1	S2-1	S3-24	922.98	C, 83.29; H, 6.01; N, 6.07;	20
BN-25	S1	S2-1	S3-25	806.82	C, 86.34; H, 5.37; N, 6.94	20
BN-26	S1	S2-1	S3-26	1227.63	C, 86.10; H, 8.46; N, 4.56	twenty one
BN-27	S1	S2-1	S3-27	1323.62	C, 79.85; H, 7.84; N, 4.23;	20
BN-28	S1	S2-1	S3-28	874.85	C, 87.87; H, 4.49; N, 6.40	17
BN-29	S1	S2-1	S3-29	987.07	C, 87.61; H, 5.62; N, 5.68	16
BN-30	S1	S2-1	S3-30	989.07	C, 86.22; H, 5.61; N, 7.08	twenty three
BN-31	S1	S2-1	S3-31	1027.05	C, 88.88; H, 4.61; N, 5.46	15
BN-32	S1	S2-1	S3-32	1027.05	C, 88.88; H, 4.61; N, 5.46	20
BN-33	S1	S2-2	S3-1	550.47	C, 82.91; H, 4.94; N, 10.18	twenty one
BN-34	S1	S2-2	S3-2	702.67	C, 85.47; H, 5.02; N, 7.97	20
BN-35	S1	S2-2	S3-3	814.88	C, 85.49; H, 6.31; N, 6.88	20
BN-36	S1	S2-2	S3-4	870.99	C, 85.50; H, 6.83; N, 6.43	twenty one
BN-37	S1	S2-2	S3-5	758.78	C, 85.48; H, 5.71; N, 7.38	20

BN-38	S1	S2-2	S3-6	758.78	C, 85.48; H, 5.71; N, 7.38	twenty one
BN-39	S1	S2-2	S3-7	927.10	C, 85.51; H, 7.28; N, 6.04	20
BN-40	S1	S2-2	S3-8	902.99	C, 82.47; H, 6.59; N, 6.20;	17
BN-41	S1	S2-2	S3-9	786.83	C, 85.48; H, 6.02; N, 7.12	16
BN-42	S1	S2-2	S3-10	1207.64	C, 85.53; H, 8.93; N, 4.64	20
BN-43	S1	S2-2	S3-11	1303.63	C, 79.24; H, 8.27; N, 4.30;	19
BN-44	S1	S2-2	S3-12	854.86	C, 87.11; H, 5.07; N, 6.55	17
BN-45	S1	S2-2	S3-13	967.08	C, 86.94; H, 6.15; N, 5.79	15
BN-46	S1	S2-2	S3-14	967.08	C, 86.94; H, 6.15; N, 5.79	twenty three
BN-47	S1	S2-2	S3-15	1007.06	C, 88.26; H, 5.10; N, 5.56	twenty one
BN-48	S1	S2-2	S3-16	1007.06	C, 88.26; H, 5.10; N, 5.56	15
BN-49	S1	S2-2	S3-17	778.77	C, 86.37; H, 5.05; N, 7.19	twenty three
BN-50	S1	S2-2	S3-18	890.98	C, 86.28; H, 6.22; N, 6.29	twenty one
BN-51	S1	S2-2	S3-19	890.98	C, 86.28; H, 6.22; N, 6.29	25
BN-52	S1	S2-2	S3-20	947.09	C, 86.24; H, 6.71; N, 5.92	twenty one
BN-53	S1	S2-2	S3-21	834.87	C, 86.32; H, 5.67; N, 6.71	15
BN-54	S1	S2-2	S3-22	834.87	C, 86.32; H, 5.67; N, 6.71	20
BN-55	S1	S2-2	S3-23	1003.20	C, 86.20; H, 7.13; N, 5.58	twenty one
BN-56	S1	S2-2	S3-24	979.09	C, 83.42; H, 6.49; N, 5.72;	20
BN-57	S1	S2-2	S3-25	862.93	C, 86.30; H, 5.96; N, 6.49	20
BN-58	S1	S2-2	S3-26	1283.74	C, 86.08; H, 8.72; N, 4.36	twenty one
BN-59	S1	S2-2	S3-27	1379.73	C, 80.09; H, 8.11; N, 4.06;	20
BN-60	S1	S2-2	S3-28	930.96	C, 87.73; H, 5.09; N, 6.02	20
BN-61	S1	S2-2	S3-29	1043.18	C, 87.51; H, 6.09; N, 5.37	17
BN-62	S1	S2-2	S3-30	1043.18	C, 87.51; H, 6.09; N, 5.37	16
BN-63	S1	S2-2	S3-31	1083.16	C, 88.71; H, 5.12; N, 5.17	twenty three
BN-64	S1	S2-2	S3-32	1083.16	C, 88.71; H, 5.12; N, 5.17	15
BN-65	S1	S2-3	S3-1	718.80	C, 83.55; H, 7.15; N, 7.79	twenty two
BN-66	S1	S2-3	S3-2	870.99	C, 85.50; H, 6.83; N, 6.43	16
BN-67	S1	S2-3	S3-3	983.21	C, 85.51; H, 7.69; N, 5.70	20
BN-68	S1	S2-3	S3-4	1039.32	C, 85.52; H, 8.05; N, 5.39	19
BN-69	S1	S2-3	S3-5	927.10	C, 85.51; H, 7.28; N, 6.04	17
BN-70	S1	S2-3	S3-6	927.10	C, 85.51; H, 7.28; N, 6.04	15

BN-71	S1	S2-3	S3-7	1053.34	C, 85.52; H, 8.13; N, 5.32	twenty three
BN-72	S1	S2-3	S3-8	1071.31	C, 82.96; H, 7.81; N, 5.23;	twenty one
BN-73	S1	S2-3	S3-9	955.15	C, 85.51; H, 7.49; N, 5.87	25
BN-74	S1	S2-3	S3-10	1375.96	C, 85.55; H, 9.60; N, 4.07	twenty one
BN-75	S1	S2-3	S3-11	1471.96	C, 79.97; H, 8.97; N, 3.81;	20
BN-76	S1	S2-3	S3-12	1023.19	C, 86.87; H, 6.60; N, 5.48	15
BN-77	S1	S2-3	S3-13	1135.40	C, 86.74; H, 7.37; N, 4.93	twenty two
BN-78	S1	S2-3	S3-14	1135.40	C, 86.74; H, 7.37; N, 4.93	twenty one
BN-79	S1	S2-3	S3-15	1175.38	C, 87.88; H, 6.43; N, 4.77	20
BN-80	S1	S2-3	S3-16	1175.38	C, 87.88; H, 6.43; N, 4.77	20
BN-81	S1	S2-3	S3-17	947.09	C, 86.24; H, 6.71; N, 5.92	twenty one
BN-82	S1	S2-3	S3-18	1059.31	C, 86.17; H, 7.52; N, 5.29	20
BN-83	S1	S2-3	S3-19	1059.31	C, 86.17; H, 7.52; N, 5.29	17
BN-84	S1	S2-3	S3-20	1115.41	C, 86.15; H, 7.86; N, 5.02	16
BN-85	S1	S2-3	S3-21	1003.20	C, 86.20; H, 7.13; N, 5.58	twenty three
BN-86	S1	S2-3	S3-22	1003.20	C, 86.20; H, 7.13; N, 5.58	15
BN-87	S1	S2-3	S3-23	1171.52	C, 86.12; H, 8.17; N, 4.78	20
BN-88	S1	S2-3	S3-24	1147.41	C, 83.74; H, 7.64; N, 4.88;	twenty one
BN-89	S1	S2-3	S3-25	1031.25	C, 86.19; H, 7.33; N, 5.43	20
BN-90	S1	S2-3	S3-26	1452.06	C, 86.03; H, 9.37; N, 3.86	20
BN-91	S1	S2-3	S3-27	1548.06	C, 80.69; H, 8.79; N, 3.62;	twenty one
BN-92	S1	S2-3	S3-28	1099.29	C, 87.41; H, 6.51; N, 5.10	20
BN-93	S1	S2-3	S3-29	1211.50	C, 87.24; H, 7.24; N, 4.62	twenty one
BN-94	S1	S2-3	S3-30	1211.50	C, 87.24; H, 7.24; N, 4.62	20
BN-95	S1	S2-3	S3-31	1251.48	C, 88.30; H, 6.36; N, 4.48	17
BN-96	S1	S2-3	S3-32	1251.48	C, 88.30; H, 6.36; N, 4.48	16
BN-97	S1	S2-4	S3-1	798.76	C, 87.22; H, 4.42; N, 7.01	20
BN-98	S1	S2-4	S3-2	950.95	C, 88.41; H, 4.56; N, 5.89	19
BN-99	S1	S2-4	S3-3	1001.10	C, 87.58; H, 5.74; N, 5.60	17
BN-100	S1	S2-4	S3-4	1119.28	C, 87.99; H, 6.03; N, 5.01	15
BN-101	S1	S2-4	S3-5	1007.06	C, 88.26; H, 5.10; N, 5.56	twenty three
BN-102	S1	S2-4	S3-6	1007.06	C, 88.26; H, 5.10; N, 5.56	twenty one
BN-103	S1	S2-4	S3-7	1175.38	C, 87.88; H, 6.43; N, 4.77	15

BN-104	S1	S2-4	S3-8	1151.27	C, 85.55; H, 5.87; N, 4.87;	twenty three
BN-105	S1	S2-4	S3-9	1035.11	C, 88.19; H, 5.36; N, 5.41	twenty one
NN-106	S1	S2-4	S3-10	1455.92	C, 87.45; H, 7.96; N, 3.85	25
BN-107	S1	S2-4	S3-11	1551.92	C, 82.04; H, 7.47; N, 3.61;	15
BN-108	S1	S2-4	S3-12	1103.15	C, 89.28; H, 4.66; N, 5.08	20
BN-109	S1	S2-4	S3-13	1215.36	C, 88.94; H, 5.56; N, 4.61	twenty one
BN-110	S1	S2-4	S3-14	1215.36	C, 88.94; H, 5.56; N, 4.61	20
BN-111	S1	S2-4	S3-15	1255.34	C, 89.94; H, 4.74; N, 4.46	20
BN-112	S1	S2-4	S3-16	1255.34	C, 89.94; H, 4.74; N, 4.46	twenty one
BN-113	S1	S2-4	S3-17	1027.05	C, 88.88; H, 4.61; N, 5.46	20
BN-114	S1	S2-4	S3-18	1139.27	C, 88.56; H, 5.57; N, 4.92	twenty one
BN-115	S1	S2-4	S3-19	1139.27	C, 88.56; H, 5.57; N, 4.92	20
BN-116	S1	S2-4	S3-20	1195.37	C, 88.42; H, 5.99; N, 4.69	17
BN-117	S1	S2-4	S3-21	1083.16	C, 88.71; H, 5.12; N, 5.17	16
BN-118	S1	S2-4	S3-22	1083.16	C, 88.71; H, 5.12; N, 5.17	20
BN-119	S1	S2-4	S3-23	1251.48	C, 88.30; H, 6.36; N, 4.48	19
BN-120	S1	S2-4	S3-24	1227.37	C, 86.12; H, 5.83; N, 4.56	17
BN-121	S1	S2-4	S3-25	1111.21	C, 88.63; H, 5.35; N, 5.04	15
BN-122	S1	S2-4	S3-26	1532.02	C, 87.81; H, 7.83; N, 3.66	twenty three
BN-123	S1	S2-4	S3-27	1628.02	C, 82.63; H, 7.37; N, 3.44	twenty one
BN-124	S1	S2-4	S3-28	1179.25	C, 89.63; H, 4.70; N, 4.75	twenty two
BN-125	S1	S2-4	S3-29	1291.46	C, 89.28; H, 5.54; N, 4.34	twenty one
BN-126	S1	S2-4	S3-30	1291.46	C, 89.28; H, 5.54; N, 4.34	20
BN-127	S1	S2-4	S3-31	1331.44	C, 90.21; H, 4.77; N, 4.21	20
BN-128	S1	S2-4	S3-32	1331.44	C, 90.21; H, 4.77; N, 4.21	twenty one
BN-129	S1	S2-5	S3-1	1155.14	C, 85.26; H, 4.10; N, 9.70	20
BN-130	S1	S2-5	S3-2	1307.34	C, 86.36; H, 4.24; N, 8.57	17
BN-131	S1	S2-5	S3-3	1419.56	C, 86.30; H, 5.04; N, 7.89	16
BN-132	S1	S2-5	S3-4	1475.66	C, 86.28; H, 5.40; N, 7.59	twenty three
BN-133	S1	S2-5	S3-5	1363.45	C, 86.33; H, 4.66; N, 8.22	15
BN-134	S1	S2-5	S3-6	1363.45	C, 86.33; H, 4.66; N, 8.22	20
BN-135	S1	S2-5	S3-7	1531.77	C, 86.25; H, 5.73; N, 7.32	twenty one
BN-136	S1	S2-5	S3-8	1507.66	C, 84.45; H, 5.28; N, 7.43	20

BN-137	S1	S2-5	S3-9	1391.50	C, 86.32; H, 4.85; N, 8.05	20
BN-138	S1	S2-5	S3-10	1812.31	C, 86.16; H, 7.06; N, 6.18	twenty one
BN-139	S1	S2-5	S3-11	1908.31	C, 81.82; H, 6.71; N, 5.87	20
BN-140	S1	S2-5	S3-12	1459.54	C, 87.23; H, 4.35; N, 7.68	twenty one
BN-141	S1	S2-5	S3-13	1571.75	C, 87.12; H, 5.07; N, 7.13	20
BN-142	S1	S2-5	S3-14	1571.75	C, 87.12; H, 5.07; N, 7.13	17
BN-143	S1	S2-5	S3-15	1611.73	C, 87.94; H, 4.44; N, 6.95	16
BN-144	S1	S2-5	S3-16	1611.73	C, 87.94; H, 4.44; N, 6.95	20
BN-145	S1	S2-5	S3-17	1383.44	C, 86.82; H, 4.30; N, 8.10	19
BN-146	S1	S2-5	S3-18	1495.65	C, 86.73; H, 5.05; N, 7.49	17
BN-147	S1	S2-5	S3-19	1495.65	C, 86.73; H, 5.05; N, 7.49	15
BN-148	S1	S2-5	S3-20	1551.76	C, 86.69; H, 5.39; N, 7.22	twenty three
BN-149	S1	S2-5	S3-21	1439.55	C, 86.77; H, 4.69; N, 7.78	twenty one
BN-150	S1	S2-5	S3-22	1439.55	C, 86.77; H, 4.69; N, 7.78	15
BN-151	S1	S2-5	S3-23	1607.87	C, 86.65; H, 5.70; N, 6.97	twenty three
BN-152	S1	S2-5	S3-24	1583.76	C, 84.94; H, 5.28; N, 7.08	twenty one
BN-153	S1	S2-5	S3-25	1467.60	C, 86.75; H, 4.88; N, 7.64	twenty two
BN-154	S1	S2-5	S3-26	1888.41	C, 86.50; H, 6.99; N, 5.93	20
BN-155	S1	S2-5	S3-27	1984.40	C, 82.32; H, 6.65; N, 5.65	20
BN-156	S1	S2-5	S3-28	1535.63	C, 87.60; H, 4.40; N, 7.30	twenty one
BN-157	S1	S2-5	S3-29	1647.85	C, 87.47; H, 5.08; N, 6.80	20
BN-158	S1	S2-5	S3-30	1647.85	C, 87.47; H, 5.08; N, 6.80	twenty one
BN-159	S1	S2-5	S3-31	1687.83	C, 88.24; H, 4.48; N, 6.64	20
BN-160	S1	S2-5	S3-32	1687.83	C, 88.24; H, 4.48; N, 6.64	17
BN-161	S1	S2-6	S3-1	1163.21	C, 84.67; H, 4.77; N, 9.63	twenty three
BN-162	S1	S2-6	S3-2	1315.40	C, 85.83; H, 4.83; N, 8.52	twenty one
BN-163	S1	S2-6	S3-3	1427.62	C, 85.82; H, 5.58; N, 7.85	twenty two
BN-164	S1	S2-6	S3-4	1483.73	C, 85.81; H, 5.91; N, 7.55	20
BN-165	S1	S2-6	S3-5	1371.51	C, 85.82; H, 5.22; N, 8.17	20
BN-166	S1	S2-6	S3-6	1371.51	C, 85.82; H, 5.22; N, 8.17	twenty one
BN-167	S1	S2-6	S3-7	1539.84	C, 85.80; H, 6.22; N, 7.28	20
BN-168	S1	S2-6	S3-8	1515.73	C, 84.00; H, 5.79; N, 7.39	twenty one
BN-169	S1	S2-6	S3-9	1399.57	C, 85.82; H, 5.40; N, 8.01	20

BN-170	S1	S2-6	S3-10	1820.38	C, 85.78; H, 7.48; N, 6.16	twenty one
BN-171	S1	S2-6	S3-11	1916.37	C, 81.48; H, 7.10; N, 5.85	20
BN-172	S1	S2-6	S3-12	1467.60	C, 86.75; H, 4.88; N, 7.64	20
BN-173	S1	S2-6	S3-13	1579.82	C, 86.67; H, 5.55; N, 7.09	twenty one
BN-174	S1	S2-6	S3-14	1579.82	C, 86.67; H, 5.55; N, 7.09	20
BN-175	S1	S2-6	S3-15	1619.80	C, 87.50; H, 4.92; N, 6.92	17
BN-176	S1	S2-6	S3-16	1619.80	C, 87.50; H, 4.92; N, 6.92	16
BN-177	S1	S2-6	S3-17	1391.50	C, 86.32; H, 4.85; N, 8.05	twenty three
BN-178	S1	S2-6	S3-18	1503.72	C, 86.27; H, 5.56; N, 7.45	15
BN-179	S1	S2-6	S3-19	1503.72	C, 86.27; H, 5.56; N, 7.45	20
BN-180	S1	S2-6	S3-20	1559.83	C, 86.24; H, 5.88; N, 7.18	twenty one
BN-181	S1	S2-6	S3-21	1447.61	C, 86.29; H, 5.22; N, 7.74	20
BN-182	S1	S2-6	S3-22	1447.61	C, 86.29; H, 5.22; N, 7.74	20
BN-183	S1	S2-6	S3-23	1615.93	C, 86.22; H, 6.18; N, 6.93	twenty one
BN-184	S1	S2-6	S3-24	1591.82	C, 84.51; H, 5.76; N, 7.04	20
BN-185	S1	S2-6	S3-25	1475.66	C, 86.28; H, 5.40; N, 7.59	twenty one
BN-186	S1	S2-6	S3-26	1896.47	C, 86.13; H, 7.39; N, 5.91	20
BN-187	S1	S2-6	S3-27	1992.47	C, 81.98; H, 7.03; N, 5.62	17
BN-188	S1	S2-6	S3-28	1543.70	C, 87.14; H, 4.90; N, 7.26	16
BN-189	S1	S2-6	S3-29	1655.91	C, 87.04; H, 5.54; N, 6.77	20
BN-190	S1	S2-6	S3-30	1655.91	C, 87.04; H, 5.54; N, 6.77	19
BN-191	S1	S2-6	S3-31	1695.89	C, 87.82; H, 4.93; N, 6.61	17
BN-192	S1	S2-6	S3-32	1695.89	C, 87.82; H, 4.93; N, 6.61	15
BN-193	S1	S2-1	S3-33	872.97	C, 82.55; H, 6.58; N, 9.63	twenty three
BN-194	S1	S2-1	S3-34	977.12	C, 83.59; H, 6.71; N, 8.60	twenty one
BN-195	S1	S2-1	S3-35	1185.42	C, 85.11; H, 6.89; N, 7.09	15
BN-196	S1	S2-1	S3-36	952.93	C, 85.71; H, 4.34; N, 8.82	twenty three
BN-197	S1	S2-1	S3-37	1009.04	C, 85.70; H, 4.89; N, 8.33	twenty one
BN-198	S1	S2-1	S3-38	1009.04	C, 85.70; H, 4.89; N, 8.33	twenty two
BN-199	S1	S2-1	S3-39	1177.36	C, 85.69; H, 6.25; N, 7.14	20
BN-200	S1	S2-1	S3-40	1177.36	C, 85.69; H, 6.25; N, 7.14	20
BN-201	S1	S2-1	S3-41	1177.36	C, 85.69; H, 6.25; N, 7.14	twenty one
BN-202	S1	S2-1	S3-42	1289.58	C, 85.69; H, 6.96; N, 6.52	20

BN-203	S1	S2-1	S3-43	1401.79	C, 85.68; H, 7.55; N, 6.00	twenty one
BN-204	S1	S2-1	S3-44	1401.79	C, 85.68; H, 7.55; N, 6.00	20
BN-205	S1	S2-1	S3-45	1065.14	C, 85.70; H, 5.39; N, 7.89	17
BN-206	S1	S2-1	S3-46	1065.14	C, 85.70; H, 5.39; N, 7.89	twenty three
BN-207	S1	S2-1	S3-47	1401.79	C, 85.68; H, 7.55; N, 6.00	twenty one
BN-208	S1	S2-1	S3-48	1465.79	C, 81.94; H, 7.22; N, 5.73	twenty two
BN-209	S1	S2-1	S3-49	1353.57	C, 81.64; H, 6.63; N, 6.21	20
BN-210	S1	S2-1	S3-50	1121.25	C, 85.70; H, 5.84; N, 7.50	20
BN-211	S1	S2-1	S3-51	1962.87	C, 85.67; H, 9.50; N, 4.28	twenty one
BN-212	S1	S2-1	S3-52	2154.86	C, 78.03; H, 8.65; N, 3.90	20
BN-213	S1	S2-1	S3-53	1257.32	C, 87.89; H, 4.57; N, 6.68	twenty one
BN-214	S1	S2-1	S3-54	1313.43	C, 87.79; H, 4.99; N, 6.40	20
BN-215	S1	S2-1	S3-55	1481.75	C, 87.54; H, 6.05; N, 5.67	16
BN-216	S1	S2-1	S3-56	1481.75	C, 87.54; H, 6.05; N, 5.67	20
BN-217	S1	S2-1	S3-57	1257.32	C, 87.89; H, 4.57; N, 6.68	19
BN-218	S1	S2-1	S3-58	1313.43	C, 87.79; H, 4.99; N, 6.40	17
BN-219	S1	S2-1	S3-59	1481.75	C, 87.54; H, 6.05; N, 5.67	15
BN-220	S1	S2-1	S3-60	1481.75	C, 87.54; H, 6.05; N, 5.67	twenty three
BN-221	S1	S2-1	S3-61	1561.71	C, 89.21; H, 4.71; N, 5.38	twenty one
BN-222	S1	S2-1	S3-62	1786.14	C, 88.76; H, 5.93; N, 4.71	twenty two
BN-223	S1	S2-1	S3-63	1561.71	C, 89.21; H, 4.71; N, 5.38	twenty one
BN-224	S1	S2-1	S3-64	2010.58	C, 88.41; H, 6.87; N, 4.18	20
BN-225	S1	S2-1	S3-65	682.68	C, 84.45; H, 5.76; N, 8.21	20
BN-226	S1	S2-1	S3-66	734.75	C, 85.00; H, 5.90; N, 7.63	twenty one
BN-227	S1	S2-1	S3-67	838.91	C, 85.90; H, 6.13; N, 6.68	20
BN-228	S1	S2-1	S3-68	722.66	C, 86.43; H, 4.32; N, 7.75	17
BN-229	S1	S2-1	S3-69	750.71	C, 86.40; H, 4.70; N, 7.46	16
BN-230	S1	S2-1	S3-70	750.71	C, 86.40; H, 4.70; N, 7.46	twenty three
BN-231	S1	S2-1	S3-71	834.87	C, 86.32; H, 5.67; N, 6.71	15
BN-232	S1	S2-1	S3-72	834.87	C, 86.32; H, 5.67; N, 6.71	20
BN-233	S1	S2-1	S3-73	834.87	C, 86.32; H, 5.67; N, 6.71	twenty one
BN-234	S1	S2-1	S3-74	890.98	C, 86.28; H, 6.22; N, 6.29	20
BN-235	S1	S2-1	S3-75	947.09	C, 86.24; H, 6.71; N, 5.92	20

BN-236	S1	S2-1	S3-76	778.77	C, 86.37; H, 5.05; N, 7.19	twenty one
BN-237	S1	S2-1	S3-77	778.77	C, 86.37; H, 5.05; N, 7.19	19
BN-238	S1	S2-1	S3-78	947.09	C, 86.24; H, 6.71; N, 5.92	17
BN-239	S1	S2-1	S3-79	947.09	C, 86.24; H, 6.71; N, 5.92	15
BN-240	S1	S2-1	S3-80	979.09	C, 83.42; H, 6.49; N, 5.72	twenty three
BN-241	S1	S2-1	S3-81	922.98	C, 83.29; H, 6.01; N, 6.07	twenty one
BN-242	S1	S2-1	S3-82	806.82	C, 86.34; H, 5.37; N, 6.94	twenty two
BN-243	S1	S2-1	S3-83	1227.63	C, 86.10; H, 8.46; N, 4.56	twenty one
BN-244	S1	S2-1	S3-84	1323.62	C, 79.85; H, 7.84; N, 4.23	20
BN-245	S1	S2-1	S3-85	874.85	C, 87.87; H, 4.49; N, 6.40	20
BN-246	S1	S2-1	S3-86	902.91	C, 87.80; H, 4.80; N, 6.21	twenty one
BN-247	S1	S2-1	S3-87	987.07	C, 87.61; H, 5.62; N, 5.68	20
BN-248	S1	S2-1	S3-88	987.07	C, 87.61; H, 5.62; N, 5.68	17
BN-249	S1	S2-1	S3-89	874.85	C, 87.87; H, 4.49; N, 6.40	16
BN-250	S1	S2-1	S3-90	902.91	C, 87.80; H, 4.80; N, 6.21	twenty three
BN-251	S1	S2-1	S3-90	987.07	C, 87.61; H, 5.62;; N, 5.68	15
BN-252	S1	S2-1	S3-92	987.07	C, 87.61; H, 5.62;; N, 5.68	20
BN-253	S1	S2-1	S3-93	1027.05	C, 88.88; H, 4.61; N, 5.46	twenty one
BN-254	S1	S2-1	S3-94	1139.27	C, 88.56; H, 5.57; N, 4.92	20
BN-255	S1	S2-1	S3-95	1027.05	C, 88.88; H, 4.61; N, 5.46	20
BN-256	S1	S2-1	S3-96	1139.27	C, 88.56; H, 5.57; N, 4.92	twenty one
BN-257	S1	S2-2	S3-33	929.08	C, 82.74; H, 7.05; N, 9.05	20
BN-258	S1	S2-2	S3-34	1033.23	C, 83.70; H, 7.12; N, 8.13	twenty one
BN-259	S1	S2-2	S3-35	1241.53	C, 85.13; H, 7.23; N, 6.77	20
BN-260	S1	S2-2	S3-36	1009.04	C, 85.70; H, 4.89; N, 8.33	17
BN-261	S1	S2-2	S3-37	1065.14	C, 85.70; H, 5.39; N, 7.89	16
BN-262	S1	S2-2	S3-38	1065.14	C, 85.70; H, 5.39; N, 7.89	20
BN-263	S1	S2-2	S3-39	1233.47	C, 85.69; H, 6.62; N, 6.81	19
BN-264	S1	S2-2	S3-40	1233.47	C, 85.69; H, 6.62; N, 6.81	17
BN-265	S1	S2-2	S3-41	1233.47	C, 85.69; H, 6.62; N, 6.81	15
BN-266	S1	S2-2	S3-42	1345.68	C, 85.69; H, 7.27; N, 6.25	twenty three
BN-267	S1	S2-2	S3-43	1457.90	C, 85.68; H, 7.81; N, 5.76	twenty one
BN-268	S1	S2-2	S3-44	1121.25	C, 85.70; H, 5.84; N, 7.50	15

BN-269	S1	S2-2	S3-45	1121.25	C, 85.70; H, 5.84; N, 7.50	twenty three
BN-270	S1	S2-2	S3-46	1457.90	C, 85.68; H, 7.81; N, 5.76	twenty one
BN-271	S1	S2-2	S3-47	1457.90	C, 85.68; H, 7.81; N, 5.76	25
BN-272	S1	S2-2	S3-48	1521.90	C, 82.08; H, 7.48; N, 5.52	twenty one
BN-273	S1	S2-2	S3-49	1409.68	C, 81.80; H, 6.94; N, 5.96	15
BN-274	S1	S2-2	S3-50	1177.36	C, 85.69; H, 6.25; N, 7.14	20
BN-275	S1	S2-2	S3-51	2018.98	C, 85.67; H, 9.64; N, 4.16	twenty one
BN-276	S1	S2-2	S3-52	2210.97	C, 78.23; H, 8.80; N, 3.80	20
BN-277	S1	S2-2	S3-53	1313.43	C, 87.79; H, 4.99; N, 6.40	20
BN-278	S1	S2-2	S3-54	1369.54	C, 87.70; H, 5.37; N, 6.14	twenty one
BN-279	S1	S2-2	S3-55	1537.86	C, 87.47; H, 6.36; N, 5.46	20
BN-280	S1	S2-2	S3-56	1537.86	C, 87.47; H, 6.36; N, 5.46	20
BN-281	S1	S2-2	S3-57	1313.43	C, 87.79; H, 4.99; N, 6.40	17
BN-282	S1	S2-2	S3-58	1369.54	C, 87.70; H, 5.37; N, 6.14	16
BN-283	S1	S2-2	S3-59	1537.86	C, 87.47; H, 6.36; N, 5.46	twenty three
BN-284	S1	S2-2	S3-60	1537.86	C, 87.47; H, 6.36; N, 5.46	15
BN-285	S1	S2-2	S3-61	1617.82	C, 89.09; H, 5.05; N, 5.19	twenty two
BN-286	S1	S2-2	S3-62	1842.25	C, 88.67; H, 6.18; N, 4.56	twenty one
BN-287	S1	S2-2	S3-63	1617.82	C, 89.09; H, 5.05; N, 5.19	20
BN-288	S1	S2-2	S3-64	1842.25	C, 88.67; H, 6.18; N, 4.56	19
BN-289	S1	S2-2	S3-65	738.79	C, 84.54; H, 6.41; N, 7.58	17
BN-290	S1	S2-2	S3-66	790.86	C, 85.05; H, 6.50; N, 7.08	15
BN-291	S1	S2-2	S3-67	895.01	C, 85.89; H, 6.64; N, 6.26	twenty three
BN-292	S1	S2-2	S3-68	778.77	C, 86.37; H, 5.05; N, 7.19	twenty one
BN-293	S1	S2-2	S3-69	806.82	C, 86.34; H, 5.37; N, 6.94	twenty two
BN-294	S1	S2-2	S3-70	806.82	C, 86.34; H, 5.37; N, 6.94	twenty one
BN-295	S1	S2-2	S3-71	890.98	C, 86.28; H, 6.22; N, 6.29	20
BN-296	S1	S2-2	S3-72	890.98	C, 86.28; H, 6.22; N, 6.29	20
BN-297	S1	S2-2	S3-73	890.98	C, 86.28; H, 6.22; N, 6.29	twenty one
BN-298	S1	S2-2	S3-74	947.09	C, 86.24; H, 6.71;; N, 5.92	20
BN-299	S1	S2-2	S3-75	1003.20	C, 86.20; H, 7.13; N, 5.58	17
BN-300	S1	S2-2	S3-76	834.87	C, 86.32; H, 5.67; N, 6.71	16
BN-301	S1	S2-2	S3-77	834.87	C, 86.32; H, 5.67; N, 6.71	twenty three

BN-302	S1	S2-2	S3-78	1003.20	C, 86.20; H, 7.13; N, 5.58	15
BN-303	S1	S2-2	S3-79	1003.20	C, 86.20; H, 7.13; N, 5.58	20
BN-304	S1	S2-2	S3-80	1035.20	C, 83.54; H, 6.91; N, 5.41	twenty one
BN-305	S1	S2-2	S3-81	979.09	C, 83.42; H, 6.49; N, 5.72	20
BN-306	S1	S2-2	S3-82	862.93	C, 86.30; H, 5.96; N, 6.49	20
BN-307	S1	S2-2	S3-83	1283.74	C, 86.08; H, 8.72; N, 4.36	twenty one
BN-308	S1	S2-2	S3-84	1379.73	C, 80.09; H, 8.11; N, 4.06	20
BN-309	S1	S2-2	S3-85	930.96	C, 87.73; H, 5.09; N, 6.02	twenty one
BN-310	S1	S2-2	S3-86	959.02	C, 87.67; H, 5.36; N, 5.84	15
BN-311	S1	S2-2	S3-87	1043.18	C, 87.51; H, 6.09; N, 5.37	20
BN-312	S1	S2-2	S3-88	1043.18	C, 87.51; H, 6.09; N, 5.37	twenty one
BN-313	S1	S2-2	S3-89	930.96	C, 87.73; H, 5.09; N, 6.02	20
BN-314	S1	S2-2	S3-90	959.02	C, 87.67; H, 5.36; N, 5.84	20
BN-315	S1	S2-2	S3-90	1043.18	C, 87.51; H, 6.09; N, 5.37	twenty one
BN-316	S1	S2-2	S3-92	1043.18	C, 87.51; H, 6.09; N, 5.37	20
BN-317	S1	S2-2	S3-93	1083.16	C, 88.71; H, 5.12; N, 5.17	20
BN-318	S1	S2-2	S3-94	1195.37	C, 88.42; H, 5.99; N, 4.69	17
BN-319	S1	S2-2	S3-95	1083.16	C, 88.71; H, 5.12; N, 5.17	16
BN-320	S1	S2-2	S3-96	1195.37	C, 88.42; H, 5.99; N, 4.69	twenty three
BN-321	S1	S2-3	S3-33	1097.40	C, 83.18; H, 8.17; N, 7.66	15
BN-322	S1	S2-3	S3-34	1201.55	C, 83.97; H, 8.14; N, 6.99	twenty two
BN-323	S1	S2-3	S3-35	1409.86	C, 85.19; H, 8.08; N, 5.96	twenty one
BN-324	S1	S2-3	S3-36	1177.36	C, 85.69; H, 6.25; N, 7.14	20
BN-325	S1	S2-3	S3-37	1233.47	C, 85.69; H, 6.62; N, 6.81	19
BN-326	S1	S2-3	S3-38	1233.47	C, 85.69; H, 6.62; N, 6.81	17
BN-327	S1	S2-3	S3-39	1401.79	C, 85.68; H, 7.55; N, 6.00	15
BN-328	S1	S2-3	S3-40	1401.79	C, 85.68; H, 7.55; N, 6.00	twenty three
BN-329	S1	S2-3	S3-41	1401.79	C, 85.68; H, 7.55; N, 6.00	twenty one
BN-330	S1	S2-3	S3-42	1514.01	C, 85.68; H, 8.06; N, 5.55	15
BN-331	S1	S2-3	S3-43	1626.22	C, 85.68; H, 8.49; N, 5.17	20
BN-332	S1	S2-3	S3-44	1289.58	C, 85.69; H, 6.96; N, 6.52	twenty one
BN-333	S1	S2-3	S3-45	1289.58	C, 85.69; H, 6.96; N, 6.52	20
BN-334	S1	S2-3	S3-46	1626.22	C, 85.68; H, 8.49; N, 5.17	20

BN-335	S1	S2-3	S3-47	1626.22	C, 85.68; H, 8.49; N, 5.17	twenty one
BN-336	S1	S2-3	S3-48	1690.22	C, 82.43; H, 8.17; N, 4.97	20
BN-337	S1	S2-3	S3-49	1578.00	C, 82.20; H, 7.73; N, 5.33	20
BN-338	S1	S2-3	S3-50	1345.68	C, 85.69; H, 7.27; N, 6.25	17
BN-339	S1	S2-3	S3-51	2187.30	C, 85.66; H, 10.00; N, 3.84	16
BN-340	S1	S2-3	S3-52	2379.29	C, 78.75; H, 9.19; N, 3.53	15
BN-341	S1	S2-3	S3-53	1481.75	C, 87.54; H, 6.05; N, 5.67	twenty three
BN-342	S1	S2-3	S3-54	1537.86	C, 87.47; H, 6.36; N, 5.46	twenty one
BN-343	S1	S2-3	S3-55	1664.10	C, 87.33; H, 6.97; N, 5.05	twenty two
BN-344	S1	S2-3	S3-56	1664.10	C, 87.33; H, 6.97; N, 5.05	twenty one
BN-345	S1	S2-3	S3-57	1481.75	C, 87.54; H, 6.05; N, 5.67	20
BN-346	S1	S2-3	S3-58	1537.86	C, 87.47; H, 6.36; N, 5.46	20
BN-347	S1	S2-3	S3-59	1706.18	C, 87.29; H, 7.15; N, 4.93	twenty one
BN-348	S1	S2-3	S3-60	1706.18	C, 87.29; H, 7.15; N, 4.93	20
BN-349	S1	S2-3	S3-61	1786.14	C, 88.76; H, 5.93; N, 4.71	17
BN-350	S1	S2-3	S3-62	2010.58	C, 88.41; H, 6.87; N, 4.18	16
BN-351	S1	S2-3	S3-63	1786.14	C, 88.76; H, 5.93; N, 4.71	twenty three
BN-352	S1	S2-3	S3-64	2235.01	C, 88.13; H, 7.62; N, 3.76	15
BN-353	S1	S2-3	S3-65	907.11	C, 84.74; H, 7.89; N, 6.18	20
BN-354	S1	S2-3	S3-66	959.19	C, 85.15; H, 7.88; N, 5.84	twenty one
BN-355	S1	S2-3	S3-67	1063.34	C, 85.85; H, 7.87; N, 5.27	20
BN-356	S1	S2-3	S3-68	947.09	C, 86.24; H, 6.71; N, 5.92	20
BN-357	S1	S2-3	S3-69	975.14	C, 86.22; H, 6.93; N, 5.75	twenty one
BN-358	S1	S2-3	S3-70	975.14	C, 86.22; H, 6.93; N, 5.75	20
BN-359	S1	S2-3	S3-71	1059.31	C, 86.17; H, 7.52; N, 5.29	twenty one
BN-360	S1	S2-3	S3-72	1059.31	C, 86.17; H, 7.52; N, 5.29	15
BN-361	S1	S2-3	S3-73	1059.31	C, 86.17; H, 7.52; N, 5.29	20
BN-362	S1	S2-3	S3-74	1115.41	C, 86.15; H, 7.86; N, 5.02	twenty one
BN-363	S1	S2-3	S3-75	1171.52	C, 86.12; H, 8.17; N, 4.78	20
BN-364	S1	S2-3	S3-76	1003.20	C, 86.20; H, 7.13; N, 5.58	20
BN-365	S1	S2-3	S3-77	1003.20	C, 86.20; H, 7.13; N, 5.58	twenty one
BN-366	S1	S2-3	S3-78	1171.52	C, 86.12; H, 8.17; N, 4.78	20
BN-367	S1	S2-3	S3-79	1171.52	C, 86.12; H, 8.17; N, 4.78	20

BN-368	S1	S2-3	S3-80	1203.52	C, 83.83; H, 7.96; N, 4.66	17
BN-369	S1	S2-3	S3-81	1147.41	C, 83.74; H, 7.64; N, 4.88	16
BN-370	S1	S2-3	S3-82	1031.25	C, 86.19; H, 7.33; N, 5.43	twenty three
BN-371	S1	S2-3	S3-83	1452.06	C, 86.03; H, 9.37; N, 3.86	15
BN-372	S1	S2-3	S3-84	1548.06	C, 80.69; H, 8.79; N, 3.62	twenty two
BN-373	S1	S2-3	S3-85	1099.29	C, 87.41; H, 6.51; N, 5.10	twenty one
BN-374	S1	S2-3	S3-86	1127.34	C, 87.37; H, 6.71; N, 4.97	20
BN-375	S1	S2-3	S3-87	1211.50	C, 87.24; H, 7.24; N, 4.62	19
BN-376	S1	S2-3	S3-88	1211.50	C, 87.24; H, 7.24; N, 4.62	17
BN-377	S1	S2-3	S3-89	1099.29	C, 87.41; H, 6.51; N, 5.10	15
BN-378	S1	S2-3	S3-90	1127.34	C, 87.37; H, 6.71; N, 4.97	twenty three
BN-379	S1	S2-3	S3-90	1211.50	C, 87.24; H, 7.24; N, 4.62	twenty one
BN-380	S1	S2-3	S3-92	1211.50	C, 87.24; H, 7.24; N, 4.62	15
BN-381	S1	S2-3	S3-93	1251.48	C, 88.30; H, 6.36; N, 4.48	20
BN-382	S1	S2-3	S3-94	1363.70	C, 88.08; H, 7.02; N, 4.11	twenty one
BN-383	S1	S2-3	S3-95	1251.48	C, 88.30; H, 6.36; N, 4.48	20
BN-384	S1	S2-3	S3-96	1363.70	C, 88.08; H, 7.02; N, 4.11	20
BN-385	S1	S2-4	S3-33	1177.36	C, 85.69; H, 6.25; N, 7.14	20
BN-386	S1	S2-4	S3-34	1281.51	C, 86.23; H, 6.37; N, 6.56	19
BN-387	S1	S2-4	S3-35	1489.82	C, 87.07; H, 6.56; N, 5.64	17
BN-388	S1	S2-4	S3-36	1257.32	C, 87.89; H, 4.57; N, 6.68	15
BN-389	S1	S2-4	S3-37	1313.43	C, 87.79; H, 4.99; N, 6.40	twenty three
BN-390	S1	S2-4	S3-38	1313.43	C, 87.79; H, 4.99; N, 6.40	twenty one
BN-391	S1	S2-4	S3-39	1481.75	C, 87.54; H, 6.05; N, 5.67	15
BN-392	S1	S2-4	S3-40	1481.75	C, 87.54; H, 6.05; N, 5.67	20
BN-393	S1	S2-4	S3-41	1481.75	C, 87.54; H, 6.05; N, 5.67	twenty one
BN-394	S1	S2-4	S3-42	1593.97	C, 87.41; H, 6.64; N, 5.27	20
BN-395	S1	S2-4	S3-43	1706.18	C, 87.29; H, 7.15; N, 4.93	20
BN-396	S1	S2-4	S3-44	1369.54	C, 87.70; H, 5.37; N, 6.14	twenty one
BN-397	S1	S2-4	S3-45	1369.54	C, 87.70; H, 5.37; N, 6.14	20
BN-398	S1	S2-4	S3-46	1706.18	C, 87.29; H, 7.15; N, 4.93	20
BN-399	S1	S2-4	S3-47	1706.18	C, 87.29; H, 7.15; N, 4.93	17
BN-400	S1	S2-4	S3-48	1770.18	C, 84.14; H, 6.89; N, 4.75	16

BN-401	S1	S2-4	S3-49	1657.96	C, 84.04; H, 6.38; N, 5.07	20
BN-402	S1	S2-4	S3-50	1425.64	C, 87.62; H, 5.73; N, 5.90	19
BN-403	S1	S2-4	S3-51	2267.26	C, 86.88; H, 8.94; N, 3.71	17
BN-404	S1	S2-4	S3-52	2459.25	C, 80.10; H, 8.24; N, 3.42	15
BN-405	S1	S2-4	S3-53	1561.71	C, 89.21; H, 4.71; N, 5.38	twenty three
BN-406	S1	S2-4	S3-54	1617.82	C, 89.09; H, 5.05; N, 5.19	twenty one
BN-407	S1	S2-4	S3-55	1786.14	C, 88.76; H, 5.93; N, 4.71	15
BN-408	S1	S2-4	S3-56	1786.14	C, 88.76; H, 5.93; N, 4.71	20
BN-409	S1	S2-4	S3-57	1561.71	C, 89.21; H, 4.71; N, 5.38	twenty one
BN-410	S1	S2-4	S3-58	1617.82	C, 89.09; H, 5.05; N, 5.19	20
BN-411	S1	S2-4	S3-59	1786.14	C, 88.76; H, 5.93; N, 4.71	20
BN-412	S1	S2-4	S3-60	1786.14	C, 88.76; H, 5.93; N, 4.71	twenty one
BN-413	S1	S2-4	S3-61	1866.10	C, 90.11; H, 4.81; N, 4.50	20
BN-414	S1	S2-4	S3-62	2090.54	C, 89.63; H, 5.83; N, 4.02	20
BN-415	S1	S2-4	S3-63	1866.10	C, 90.11; H, 4.81; N, 4.50	17
BN-416	S1	S2-4	S3-64	2090.54	C, 89.63; H, 5.83; N, 4.02	16
BN-417	S1	S2-4	S3-65	987.07	C, 87.61; H, 5.62; N, 5.68	20
BN-418	S1	S2-4	S3-66	1039.15	C, 87.84; H, 5.72; N, 5.39	19
BN-419	S1	S2-4	S3-67	1143.30	C, 88.25; H, 5.91; N, 4.90	17
BN-420	S1	S2-4	S3-68	1027.05	C, 88.88; H, 4.61; N, 5.46	15
BN-421	S1	S2-4	S3-69	1055.10	C, 88.79; H, 4.87; N, 5.31	twenty three
BN-422	S1	S2-4	S3-70	1055.10	C, 88.79; H, 4.87; N, 5.31	twenty one
BN-423	S1	S2-4	S3-71	1139.27	C, 88.56; H, 5.57; N, 4.92	15
BN-424	S1	S2-4	S3-72	1139.27	C, 88.56; H, 5.57; N, 4.92	20
BN-425	S1	S2-4	S3-73	1139.27	C, 88.56; H, 5.57; N, 4.92	twenty one
BN-426	S1	S2-4	S3-74	1195.37	C, 88.42; H, 5.99; N, 4.69	20
BN-427	S1	S2-4	S3-75	1251.48	C, 88.30; H, 6.36; N, 4.48	20
BN-428	S1	S2-4	S3-76	1083.16	C, 88.71; H, 5.12; N, 5.17	twenty one
BN-429	S1	S2-4	S3-77	1083.16	C, 88.71; H, 5.12; N, 5.17	20
BN-430	S1	S2-4	S3-78	1251.48	C, 88.30; H, 6.36; N, 4.48	20
BN-431	S1	S2-4	S3-79	1251.48	C, 88.30; H, 6.36; N, 4.48	17
BN-432	S1	S2-4	S3-80	1283.48	C, 86.09; H, 6.20; N, 4.37	20
BN-433	S1	S2-4	S3-81	1227.37	C, 86.12; H, 5.83; N, 4.56	19

BN-434	S1	S2-4	S3-82	1111.21	C, 88.63; H, 5.35; N, 5.04	17
BN-435	S1	S2-4	S3-83	1532.02	C, 87.81; H, 7.83; N, 3.66	15
BN-436	S1	S2-4	S3-84	1628.02	C, 82.63; H, 7.37; N, 3.44	twenty three
BN-437	S1	S2-4	S3-85	1179.25	C, 89.63; H, 4.70; N, 4.75	twenty one
BN-438	S1	S2-4	S3-86	1207.30	C, 89.54; H, 4.93; N, 4.64	15
BN-439	S1	S2-4	S3-87	1229.39	C, 88.91; H, 5.66; N, 4.56	20
BN-440	S1	S2-4	S3-88	1229.39	C, 88.91; H, 5.66; N, 4.56	twenty one
BN-441	S1	S2-4	S3-89	1179.25	C, 89.63; H, 4.70; N, 4.75	20
BN-442	S1	S2-4	S3-90	1207.30	C, 89.54; H, 4.93; N, 4.64	20
BN-443	S1	S2-4	S3-90	1229.39	C, 88.91; H, 5.66; N, 4.56	20
BN-444	S1	S2-4	S3-92	1229.39	C, 88.91; H, 5.66; N, 4.56	19
BN-445	S1	S2-4	S3-93	1331.44	C, 90.21; H, 4.77; N, 4.21	17
BN-446	S1	S2-4	S3-94	1443.66	C, 89.85; H, 5.52; N, 3.88	15
BN-447	S1	S2-4	S3-95	1331.44	C, 90.21; H, 4.77; N, 4.21	twenty three
BN-448	S1	S2-4	S3-96	1443.66	C, 89.85; H, 5.52; N, 3.88	twenty one
BN-449	S1	S2-5	S3-33	1533.75	C, 84.58; H, 5.59; N, 9.13	15
BN-450	S1	S2-5	S3-34	1637.90	C, 85.06; H, 5.72; N, 8.55	20
BN-451	S1	S2-5	S3-35	1846.20	C, 85.88; H, 5.95; N, 7.59	twenty one
BN-452	S1	S2-5	S3-36	1613.71	C, 86.34; H, 4.31; N, 8.68	20
BN-453	S1	S2-5	S3-37	1669.82	C, 86.32; H, 4.65; N, 8.39	20
BN-454	S1	S2-5	S3-38	1669.82	C, 86.32; H, 4.65; N, 8.39	twenty one
BN-455	S1	S2-5	S3-39	1838.14	C, 86.25; H, 5.54; N, 7.62	20
BN-456	S1	S2-5	S3-40	1838.14	C, 86.25; H, 5.54; N, 7.62	20
BN-457	S1	S2-5	S3-41	1838.14	C, 86.25; H, 5.54; N, 7.62	17
BN-458	S1	S2-5	S3-42	1950.36	C, 86.22; H, 6.05; N, 7.18	16
BN-459	S1	S2-5	S3-43	2062.57	C, 86.19; H, 6.50; N, 6.79	20
BN-460	S1	S2-5	S3-44	1725.92	C, 86.29; H, 4.96; N, 8.12	19
BN-461	S1	S2-5	S3-45	1725.92	C, 86.29; H, 4.96; N, 8.12	17
BN-462	S1	S2-5	S3-46	2062.57	C, 86.19; H, 6.50; N, 6.79	15
BN-463	S1	S2-5	S3-47	2062.57	C, 86.19; H, 6.50; N, 6.79	twenty three
BN-464	S1	S2-5	S3-48	2126.57	C, 83.59; H, 6.30; N, 6.59	twenty one
BN-465	S1	S2-5	S3-49	2014.35	C, 83.48; H, 5.85; N, 6.95	15
BN-466	S1	S2-5	S3-50	1782.03	C, 86.27; H, 5.26; N, 7.86	20

BN-467	S1	S2-5	S3-51	2623.65	C, 86.07; H, 8.18; N, 5.34	twenty one
BN-468	S1	S2-5	S3-52	2815.64	C, 80.20; H, 7.63; N, 4.97	20
BN-469	S1	S2-5	S3-53	1918.10	C, 87.67; H, 4.47; N, 7.30	20
BN-470	S1	S2-5	S3-54	1974.21	C, 87.61; H, 4.75; N, 7.09	twenty one
BN-471	S1	S2-5	S3-55	2142.53	C, 87.45; H, 5.50; N, 6.54	20
BN-472	S1	S2-5	S3-56	2142.53	C, 87.45; H, 5.50; N, 6.54	20
BN-473	S1	S2-5	S3-57	1918.10	C, 87.67; H, 4.47; N, 7.30	17
BN-474	S1	S2-5	S3-58	1974.21	C, 87.61; H, 4.75; N, 7.09	16
BN-475	S1	S2-5	S3-59	2142.53	C, 87.45; H, 5.50; N, 6.54	20
BN-476	S1	S2-5	S3-60	2142.53	C, 87.45; H, 5.50; N, 6.54	20
BN-477	S1	S2-5	S3-61	2222.49	C, 88.63; H, 4.58; N, 6.30	twenty one
BN-478	S1	S2-5	S3-62	2446.92	C, 88.36; H, 5.48; N, 5.72	20
BN-479	S1	S2-5	S3-63	2222.49	C, 88.63; H, 4.58; N, 6.30	20
BN-480	S1	S2-5	S3-64	2446.92	C, 88.36; H, 5.48; N, 5.72	20
BN-481	S1	S2-5	S3-65	1343.46	C, 85.83; H, 5.03; N, 8.34	19
BN-482	S1	S2-5	S3-66	1395.53	C, 86.07; H, 5.13; N, 8.03	17
BN-483	S1	S2-5	S3-67	1499.69	C, 86.50; H, 5.31; N, 7.47	15
BN-484	S1	S2-5	S3-68	1383.44	C, 86.82; H, 4.30; N, 8.10	twenty three
BN-485	S1	S2-5	S3-69	1411.49	C, 86.80; H, 4.50; N, 7.94	twenty one
BN-486	S1	S2-5	S3-70	1411.49	C, 86.80; H, 4.50; N, 7.94	15
BN-487	S1	S2-5	S3-71	1495.65	C, 86.73; H, 5.05; N, 7.49	20
BN-488	S1	S2-5	S3-72	1495.65	C, 86.73; H, 5.05; N, 7.49	twenty one
BN-489	S1	S2-5	S3-73	1495.65	C, 86.73; H, 5.05; N, 7.49	20
BN-490	S1	S2-5	S3-74	1551.76	C, 86.69; H, 5.39; N, 7.22	20
BN-491	S1	S2-5	S3-75	1607.87	C, 86.65; H, 5.70; N, 6.97	twenty one
BN-492	S1	S2-5	S3-76	1439.55	C, 86.77; H, 4.69; N, 7.78	20
BN-493	S1	S2-5	S3-77	1439.55	C, 86.77; H, 4.69; N, 7.78	20
BN-494	S1	S2-5	S3-78	1607.87	C, 86.65; H, 5.70; N, 6.97	17
BN-495	S1	S2-5	S3-79	1607.87	C, 86.65; H, 5.70; N, 6.97	16
BN-496	S1	S2-5	S3-80	1639.87	C, 84.96; H, 5.59; N, 6.83	20
BN-497	S1	S2-5	S3-81	1583.76	C, 84.94; H, 5.28; N, 7.08	19
BN-498	S1	S2-5	S3-82	1467.60	C, 86.75; H, 4.88; N, 7.64	17
BN-499	S1	S2-5	S3-83	1888.41	C, 86.50; H, 6.99; N, 5.93	15

BN-500	S1	S2-5	S3-84	1984.40	C, 82.32; H, 6.65; N, 5.65	twenty three
BN-501	S1	S2-5	S3-85	1535.63	C, 87.60; H, 4.40; N, 7.30	twenty one
BN-502	S1	S2-5	S3-86	1563.69	C, 87.57; H, 4.58; N, 7.17	15
BN-503	S1	S2-5	S3-87	1647.85	C, 87.47; H, 5.08; N, 6.80	20
BN-504	S1	S2-5	S3-88	1647.85	C, 87.47; H, 5.08; N, 6.80	twenty one
BN-505	S1	S2-5	S3-89	1535.63	C, 87.60; H, 4.40; N, 7.30	20
BN-506	S1	S2-5	S3-90	1563.69	C, 87.57; H, 4.58; N, 7.17	20
BN-507	S1	S2-5	S3-90	1647.85	C, 87.47; H, 5.08; N, 6.80	twenty one
BN-508	S1	S2-5	S3-92	1647.85	C, 87.47; H, 5.08; N, 6.80	20
BN-509	S1	S2-5	S3-93	1687.83	C, 88.24; H, 4.48; N, 6.64	20
BN-510	S1	S2-5	S3-94	1800.05	C, 88.08; H, 5.10; N, 6.23	17
BN-511	S1	S2-5	S3-95	1687.83	C, 88.24; H, 4.48; N, 6.64	16
BN-512	S1	S2-5	S3-96	1800.05	C, 88.08; H, 5.10; N, 6.23	20
BN-513	S1	S2-6	S3-33	1541.81	C, 84.13; H, 6.08; N, 9.08	20
BN-514	S1	S2-6	S3-34	1645.96	C, 84.65; H, 6.19; N, 8.51	twenty one
BN-515	S1	S2-6	S3-35	1854.27	C, 85.50; H, 6.36; N, 7.55	15
BN-516	S1	S2-6	S3-36	1621.77	C, 85.91; H, 4.79; N, 8.64	20
BN-517	S1	S2-6	S3-37	1677.88	C, 85.90; H, 5.11; N, 8.35	twenty one
BN-518	S1	S2-6	S3-38	1677.88	C, 85.90; H, 5.11; N, 8.35	20
BN-519	S1	S2-6	S3-39	1846.20	C, 85.88; H, 5.95; N, 7.59	20
BN-520	S1	S2-6	S3-40	1846.20	C, 85.88; H, 5.95; N, 7.59	twenty one
BN-521	S1	S2-6	S3-41	1846.20	C, 85.88; H, 5.95; N, 7.59	20
BN-522	S1	S2-6	S3-42	1958.42	C, 85.86; H, 6.43; N, 7.15	20
BN-523	S1	S2-6	S3-43	2070.64	C, 85.85; H, 6.86; N, 6.76	17
BN-524	S1	S2-6	S3-44	1733.99	C, 85.89; H, 5.41; N, 8.08	16
BN-525	S1	S2-6	S3-45	1733.99	C, 85.89; H, 5.41; N, 8.08	20
BN-526	S1	S2-6	S3-46	2070.64	C, 85.85; H, 6.86; N, 6.76	20
BN-527	S1	S2-6	S3-47	2070.64	C, 85.85; H, 6.86; N, 6.76	16
BN-528	S1	S2-6	S3-48	2134.63	C, 83.28; H, 6.66; N, 6.56	20
BN-529	S1	S2-6	S3-49	2022.42	C, 83.15; H, 6.23; N, 6.93	20
BN-530	S1	S2-6	S3-50	1790.10	C, 85.88; H, 5.69; N, 7.82	twenty one
BN-531	S1	S2-6	S3-51	2631.72	C, 85.80; H, 8.46; N, 5.32	15
BN-532	S1	S2-6	S3-52	2823.70	C, 79.97; H, 7.89; N, 4.96	20

BN-533	S1	S2-6	S3-53	1926.16	C, 87.30; H, 4.87; N, 7.27	twenty one
BN-534	S1	S2-6	S3-54	1982.27	C, 87.25; H, 5.14; N, 7.07	20
BN-535	S1	S2-6	S3-55	2150.60	C, 87.13; H, 5.86; N, 6.51	20
BN-536	S1	S2-6	S3-56	2150.60	C, 87.13; H, 5.86; N, 6.51	twenty one
BN-537	S1	S2-6	S3-57	1926.16	C, 87.30; H, 4.87; N, 7.27	20
BN-538	S1	S2-6	S3-58	1982.27	C, 87.25; H, 5.14; N, 7.07	20
BN-539	S1	S2-6	S3-59	2150.60	C, 87.13; H, 5.86; N, 6.51	17
BN-540	S1	S2-6	S3-60	2150.60	C, 87.13; H, 5.86; N, 6.51	16
BN-541	S1	S2-6	S3-61	2230.56	C, 88.31; H, 4.93; N, 6.28	20
BN-542	S1	S2-6	S3-62	2454.99	C, 88.06; H, 5.79; N, 5.71	20
BN-543	S1	S2-6	S3-63	2230.56	C, 88.31; H, 4.93; N, 6.28	17
BN-544	S1	S2-6	S3-64	2454.99	C, 88.06; H, 5.79; N, 5.71	16
BN-545	S1	S2-6	S3-65	1351.52	C, 85.32; H, 5.59; N, 8.29	20
BN-546	S1	S2-6	S3-66	1403.60	C, 85.57; H, 5.67;; N, 7.98	20
BN-547	S1	S2-6	S3-67	1507.75	C, 86.03; H, 5.82; N, 7.43	twenty one
BN-548	S1	S2-6	S3-68	1391.50	C, 86.32; H, 4.85; N, 8.05	20
BN-549	S1	S2-6	S3-69	1419.56	C, 86.30; H, 5.04; N, 7.89	20
BN-550	S1	S2-6	S3-70	1419.56	C, 86.30; H, 5.04; N, 7.89	20
BN-551	S1	S2-6	S3-71	1503.72	C, 86.27; H, 5.56; N, 7.45	19
BN-552	S1	S2-6	S3-72	1503.72	C, 86.27; H, 5.56; N, 7.45	17
BN-553	S1	S2-6	S3-73	1503.72	C, 86.27; H, 5.56; N, 7.45	15
BN-554	S1	S2-6	S3-74	1559.83	C, 86.24; H, 5.88; N, 7.18	twenty three
BN-555	S1	S2-6	S3-75	1615.93	C, 86.22; H, 6.18; N, 6.93	twenty one
BN-556	S1	S2-6	S3-76	1447.61	C, 86.29; H, 5.22; N, 7.74	15
BN-557	S1	S2-6	S3-77	1447.61	C, 86.29; H, 5.22; N, 7.74	20
BN-558	S1	S2-6	S3-78	1615.93	C, 86.22; H, 6.18; N, 6.93	twenty one
BN-559	S1	S2-6	S3-79	1615.93	C, 86.22; H, 6.18; N, 6.93	20
BN-560	S1	S2-6	S3-80	1647.93	C, 84.55; H, 6.06; N, 6.80	20
BN-561	S1	S2-6	S3-81	1591.82	C, 84.51; H, 5.76; N, 7.04	twenty one
BN-562	S1	S2-6	S3-82	1475.66	C, 86.28; H, 5.40; N, 7.59	20
BN-563	S1	S2-6	S3-83	1896.47	C, 86.13; H, 7.39; N, 5.91	20
BN-564	S1	S2-6	S3-84	1992.47	C, 81.98; H, 7.03; N, 5.62	17
BN-565	S1	S2-6	S3-85	1543.70	C, 87.14; H, 4.90; N, 7.26	16

BN-566	S1	S2-6	S3-86	1571.75	C, 87.12; H, 5.07; N, 7.13	20
BN-567	S1	S2-6	S3-87	1655.91	C, 87.04; H, 5.54; N, 6.77	19
BN-568	S1	S2-6	S3-88	1655.91	C, 87.04; H, 5.54; N, 6.77	17
BN-569	S1	S2-6	S3-89	1543.70	C, 87.14; H, 4.90; N, 7.26	15
BN-570	S1	S2-6	S3-90	1571.75	C, 87.12; H, 5.07; N, 7.13	twenty three
BN-571	S1	S2-6	S3-90	1655.91	C, 87.04; H, 5.54; N, 6.77	twenty one
BN-572	S1	S2-6	S3-92	1655.91	C, 87.04; H, 5.54; N, 6.77	15
BN-573	S1	S2-6	S3-93	1695.89	C, 87.82; H, 4.93; N, 6.61	20
BN-574	S1	S2-6	S3-94	1808.11	C, 87.69; H, 5.52; N, 6.20	twenty one
BN-575	S1	S2-6	S3-95	1695.89	C, 87.82; H, 4.93; N, 6.61	20
BN-576	S1	S2-6	S3-96	1808.11	C, 87.69; H, 5.52; N, 6.20	20
BN-577	S1	S2-7	S3-1	1610.97	C, 84.91; H, 7.47; N, 6.93	17
BN-578	S1	S2-7	S3-3	1875.15	C, 85.75; H, 6.71; N, 5.97	18
BN-579	S1	S2-7	S3-5	1819.09	C, 85.78; H, 7.51; N, 6.18	20
BN-580	S1	S2-7	S3-7	1987.28	C, 85.79; H, 8.01; N, 5.68	twenty one
BN-581	S1	S2-7	S3-9	1847.12	C, 85.77; H, 7.52; N, 6.07	20
BN-582	S1	S2-7	S3-97	2019.27	C, 84.47; H, 7.92; N, 5.57	17
BN-583	S1	S2-7	S3-98	2019.27	C, 84.40; H, 7.93; N, 5.53	16
BN-584	S1	S2-7	S3-99	2277.13	C, 83.36; H, 8.57; N, 4.92;	twenty three

Effect Example 1

The luminescent molecular structure adopted in the comparative effect example is as follows:

The compounds represented by formulae BN-1 to BN-584 are the molecular structures of the materials provided by the present disclosure (the specific molecular structures are shown above), and the compounds represented by BN-R-1 to BN-R-7 are the molecular structures of the comparative materials. Any compound represented by the formula BN-n (n=1-584) or BN-R-m (m=1-7) was used as the doped light-emitting material, and H-1 was used as the host material to prepare a doped film (thickness of 150±15nm), the doping concentration of the doped luminescent material is 3wt% (weight percent concentration), and then the doped films are respectively tested for the emission spectrum, and the test results are listed in Table 2.

The comparison between the luminescent peak positions of the luminescent compounds provided by the present disclosure and the luminescent peak positions of the corresponding comparative compounds listed in Table 2 shows that the luminescent peak positions of the luminescent compounds provided by the present disclosure are red-shifted by 7- to the luminescent peak positions of the corresponding comparative compounds. 62nm, that is, a shift of 7-62nm to long wavelengths. The above effect examples prove that the luminescence peak of the boron-nitrogen compound of the present disclosure has a significant red shift relative to its isomer, and the half-peak width of the luminescence spectrum is not significantly deteriorated (still narrow), so the luminescent molecule design provided by the present disclosure The principles and methods are effective in providing a luminescent material with a narrow emission peak in the green to red region.

Table 2. BN-n (n=1-584) emission spectrum test parameters.

Electroluminescent Device Examples

The molecular structures of some materials involved in the device effect embodiment are as follows:

The following uses the materials of the present disclosure to prepare electroluminescent device embodiments, and the specific device preparation process is as follows:

(1) Substrate treatment: transparent ITO glass is used as the base material for preparing the device, and then ultrasonically treated with 5% ITO lotion for 30 min, followed by distilled water (2 times), acetone (2 times), and isopropanol (2 times) ) ultrasonically washed, and finally the ITO glass was stored in isopropanol. Before each use, carefully wipe the surface of the ITO glass with acetone cotton balls and isopropyl alcohol cotton balls, rinse with isopropyl alcohol, dry, and then treat with plasma for 5 minutes for use. The fabrication of the device is accomplished by a combination of spin coating and vacuum evaporation.

(2) Preparation of hole injection layer and hole transport layer: First, spin-coat a layer of PEDOT:PSS (poly3,4-ethylenedioxythiophene):polystyrene sulfonate with a thickness of 20 nm on the surface of ITO, The material was purchased from Heraeus, Germany and used directly) as a hole injection layer, and then a 50nm-thick Poly-HTL was spin-coated on the hole injection layer as a hole transport layer. The ITO glass was annealed at 200°C for 30 minutes in a nitrogen-protected glove box (to cross-link the Poly-HTL).

(3) Preparation of light-emitting layer: Dissolve the host material and light-emitting material in xylene according to the ratio of 97wt%:3wt% (wt% is the weight percentage concentration) to prepare a solution with a concentration of 2wt%, and use the prepared solution by spin coating method. A light-emitting layer was prepared, and the thickness of the light-emitting layer was 50 nm.

(4) Preparation of electron transport layer, electron injection layer and metal electrode: The electron transport layer, electron injection layer and metal electrode are prepared by evaporation process. When the vacuum degree of the vacuum evaporation system reaches below 5×10 ^-4 Pa Evaporation, the deposition rate is determined by the Sainz film thickness meter, and the organic electron transport layer, the LiF electron injection layer and the metal Al electrode are sequentially deposited on the light-emitting layer by the vacuum evaporation process (see the following effect example for the specific device structure). Among them, the deposition rate of organic material is

The deposition rate of LiF is

The deposition rate of Al is

The current, voltage, brightness, luminescence spectrum and other characteristics of the device were tested synchronously with Photo Research PR 655 spectral scanning luminance meter and Keithley K 2400 digital source meter system. The performance test of the device was carried out at room temperature under ambient atmosphere. The external quantum efficiency (EQE) of the device is calculated from the current density, brightness and electro-spectrum combined with the visual function when the luminescence is Lambertian distribution.

Effect Example 2

In the organic electroluminescent device in Effect Example 2 (the structure is shown in Figure 1), PEDOT:PSS is used as the hole injection layer, Poly-HTL is used as the hole transport layer, and H1-48 is used as the hole transport layer in the light-emitting layer. Host materials, BN-1 to BN-584 were used as doped light-emitting materials (3 wt % doping concentration), TmPyPB was used as electron transport material, LiF was used as electron injection layer, and Al was used as metal cathode. Effect Example The structure of the organic electroluminescent device is [ITO/PEDOT:PSS(20nm)/Poly-HTL(50nm)//H1-48+3wt%BN-n/TmPyPB(50nm)/LiF(1nm)/Al( 100 nm)]. where n=1-584. The results of the effect examples are shown in Table 3. The electroluminescence device effect implementation data listed in Table 3 proves that the luminescent materials provided by the present disclosure can be used to prepare high-efficiency organic electroluminescence devices, and the electroluminescence spectrum has narrow band characteristics, and the electroluminescence spectrum is half of the The peak width is less than 60 nm.

Table 3. Main parameters of electroluminescence performance of BN-n (n=1-584).

Effect Example 3

In the organic electroluminescence device in Effect Example 3, in the organic electroluminescence device in Effect Example 2 (the structure is shown in FIG. 1 ), PEDOT:PSS is used as the hole injection layer, and Poly-HTL is used as the hole injection layer. The hole transport layer is used, and the mixture of H1-33 and TRZ-1 is used as the host material in the light-emitting layer (the weight mixing ratio of H1-33 and TRZ-1 is 1:1), and BN-1 to BN-584 are used as dopant materials respectively. A hetero light-emitting material (doping concentration of 3 wt %) was used, TmPyPB was used as an electron transport material, LiF was used as an electron injection layer, and Al was used as a metal cathode. Effect Example The organic electroluminescent device structure is [ITO/PEDOT:PSS(20nm)/Poly-HTL(50nm)/H1-33:TRZ-1+3wt%BN-n/TmPyPB(50nm)/LiF(1nm) /Al(100nm)]. where n=1-584. The results of the effect examples are shown in Table 4. The implementation data of electroluminescence device effects listed in Table 4 proves that the luminescent materials provided by the present disclosure can be used to prepare high-efficiency organic electroluminescence devices, and the electroluminescence spectrum has narrow-band characteristics, half of the electroluminescence spectrum. The peak width is less than 60 nm. The results of the effect examples are shown in Table 4.

Table 4. Main parameters of electroluminescence performance of BN-n (n=1-584).

The above descriptions are only exemplary embodiments of the present disclosure, and are not intended to limit the protection scope of the present disclosure, which is determined by the appended claims.

Claims (20)

1. A boron-nitrogen compound having the structure shown in formula I or II,

   

   Each occurrence of R ¹ is independently H, D (deuterium), fluorine, CN, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl substituted by one or more ^Ra , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more ^Ra , Diphenylamino, or diphenylamino substituted with one or more ^Ra ;

   E is a single key or

   

   Each occurrence of R ¹¹ and R ²² is independently H, D (deuterium), C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;

   R is:

   

   H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ substituted by one or more R ^d aryl, 5- to 18-membered heteroaryl, or 5- to 18-membered ^heteroaryl substituted with one or more R;

   Each occurrence of R ⁴ , R ⁵ and R ⁶ is independently H, D (deuterium), fluorine, CN, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₁₀ cycloalkane aryl, C ₆ -C ₁₄ aryl, C ₆ -C ₁₄ aryl substituted by one or more R ^d , 5- to 18-membered heteroaryl, or 5- to 18 substituted by one or more R ^d -membered heteroaryl;

   Each occurrence of R ^a is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₄ aryl substituted by one or more R ^b , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^b , diphenylamine group, or diphenylamino group substituted by one or more R ^b ;

   Each occurrence of R ^b is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl base, C ₆ -C ₁₄ aryl substituted by one or more R ^c , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^c , diphenylamine group, or diphenylamino group substituted by one or more R ^c ;

   Each occurrence of R ^c is independently D (deuterium), fluorine, CN, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₄ aryl substituted by one or more R ^d , 5- to 18-membered heteroaryl, 5- to 18-membered heteroaryl substituted by one or more R ^d , diphenylamine group, or diphenylamino group substituted by one or more R ^d ;

   Each occurrence of R ^d is independently D (deuterium), fluorine, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, or C ₆ -C ₁₄ aryl substituted by one or more R ^e ;

   Each occurrence of R ^e is independently D (deuterium), fluorine, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₀ cycloalkyl, or C ₆ -C ₁₄ aryl ;

   The above-mentioned alkyl groups, alkoxy groups, cycloalkyl groups, aryl groups, and heteroaryl groups are optionally substituted by one or more substituents selected from the group consisting of halogen, -CN, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, C ₁ -C ₁₂ haloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl, or 5- to 18-membered heteroaryl.
2. The boron-nitrogen compound of claim 1, wherein the frontier molecular orbital has the following characteristics:

   HOMO and LUMO are distributed alternately on the ring atoms of ring c11, ring c12, ring c13, ring c14, ring b1 of formula I and one B and two N which are connected to three of the rings at the same time. HOMO is distributed on the two Ns, and LUMO is distributed on the B atom, ring m1 and ring ph1;

   HOMO and LUMO are distributed alternately on the ring atoms of ring c21, ring c22, ring c23, ring c24, ring b2 of formula II and one B and two N which are connected to three of the rings at the same time. The HOMO is distributed on the two Ns, and the LUMO is distributed on the B atom, ring m2 and ring ph2.
3. The boron-nitrogen compound of claim 1,

   wherein E in formula I is a single bond or

   

   where in formula II

   

   for

   

   wherein in formulas I and II

   

   Any of the following groups:

   

   

   

   

   

   wherein in formulas I and II

   

   Any of the following groups:

   

   

   

   
4. The boron-nitrogen compound of claim 1, wherein R ¹¹ and R ²² are independently H or D (deuterium), and at least one of R ¹¹ and R ²² in pairs is hydrogen.
5. 4. The boron-nitrogen compound of claim ⁴ , wherein both R11 and ^R22 are hydrogen.
6. The boron nitrogen compound of claim 5, wherein each occurrence of R ¹ is independently H, F, CF ₃ , C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, cyclohexyl, adamantyl, phenyl , naphthyl, phenyl substituted by one or more ^Ra , carbazolyl, carbazolyl substituted by one or more ^Ra , diphenylamino, or diphenylamino substituted by one or more ^Ra , the R ^a is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ fluoroalkyl and C ₁ -C ₆ alkoxy.
7. The boron-nitrogen compound of claim 1, wherein,

   E is a single bond or a benzene ring;

   Each occurrence ^of R is independently H, methyl, tert-butyl, phenyl, 4-tolyl, 3-tolyl, 3,5-xylyl, 4-tert-butylphenyl, 3-tert- butylphenyl, 3,5-di-tert-butylphenyl, diphenylamine, bis(p-tolyl)amine, or bis(p-tert-butylphenyl)amine;

   R ¹¹ and R ²² are H;

   R is H or

   

   R ⁴ and R ⁶ are the same and are tert-butyl, phenyl, 4-tolyl, 3-tolyl, 3,5-xylyl, 4-tert-butylphenyl, 3-tert-butylphenyl, 3 ,5-di-tert-butylphenyl, 4-C ₁ -C ₁₀ alkoxyphenyl, 3-C ₁ -C ₁₀ alkoxyphenyl, or 3,5-diC ₁ -C ₁₀ alkoxy phenyl;

   ^R5 is H.
8. The boron-nitrogen compound of claim 1, which is any one of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
9. An organic electroluminescent composition comprising the boron-nitrogen compound of any one of claims 1-8.
10. The organic electroluminescent composition of claim 9, which further comprises a host material, the host material has electron and/or hole transport ability, and the triplet excited state energy of the host material is higher than the triplet excited state of the boron nitride compound energy.
11. The organic electroluminescent composition of claim 10, wherein the host material accounts for 99.7-70.0 wt % of the composition, and the boron-nitrogen compound accounts for 0.3-30.0 wt % of the composition.
12. The organic electroluminescent composition of claim 11, wherein the host material comprises one or more of the compounds represented by formulae (H-1) to (H-6),

    

    wherein X ₁ , Y ₁ and Z ₁ are CH or N, and at most one of X ₁ , Y ₁ and Z ₁ is N;

    wherein R ^1H and R ^2H are independently any of the following:

    

    wherein X ₂ , Y ₂ and Z ₂ are CH or N, and at most one of X ₂ , Y ₂ and Z ₂ is N;

    wherein R ^aH and R ^bH are independently H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkyl substituted C ₆ -C ₂₀ Aryl or C ₁ -C ₂₀ alkoxy substituted C ₆ -C ₂₀ aryl.
13. The organic electroluminescent composition of claim 12, wherein the host material comprises two compounds of the formulae (H-1) to (H-6), and the weight ratio of the two compounds is 1:5 to 5:1 .
14. The organic electroluminescent composition of claim 12, wherein the host material is 1-2 kinds of compounds H1-1 to H1-427, and when the host material is two kinds of compounds H1-1 to H1-427, the two The weight ratio of the compounds is 1:5 to 5:1,

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    
15. The organic electroluminescent composition of claim 12, wherein the host material further comprises any one of the 1,3,5-triazine derivatives represented by the formulae Trz1-A, Trz2-A and Trz3-A; and Trz1 -A, Trz2-A or Trz3-A represented by 1,3,5-triazine derivatives and compounds represented by H-1, H-2, H-3, H-4, H-5 and H-6 The weight ratio between 1:5 to 5:1,

    

    One or two of R ^1a , R ^1b , R ^2a , R ^2b , R ^3a and R ^3b are independently R ^Tz , and the rest are the same or different independently hydrogen, deuterium, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₆ -C ₁₈ aryl, C ₁ -C ₈ alkyl substituted C ₆ -C ₁₈ aryl or C ₁ -C ₈ alkoxy substituted C ₆ -C ₁₈ aryl group; R ^Tz is any one of the substituent groups shown in the following formula:

    

    

    
16. The organic electroluminescent composition of claim 15, wherein the host material comprises any one of the 1,3,5-triazine derivatives represented by formulae TRZ-1 to TRZ-56 and formulae H1-1 to H1- Any one of the carbazole or carboline derivatives shown in 427 is constituted; in the host material, the weight ratio between the 1,3,5-triazine derivative and the carbazole or carboline derivative is 1:5 to 5: 1,

    

    

    
17. An organic electroluminescence device, at least one of the light-emitting layer, electron injection layer, electron transport layer, hole transport layer, hole injection layer comprises the boron nitride compound of any one of claims 1-8 or the right The organic electroluminescent composition of any one of claims 9-16.
18. The organic electroluminescent device of claim 17, wherein the light-emitting layer comprises the boron nitride compound or the organic electroluminescent composition.
19. 18. An organic electroluminescent device according to claim 17 or 18, which is used in the preparation of an organic electroluminescent display or a lighting source.
20. A method for preparing the boron-nitrogen compound of claim 1, comprising the steps shown in the following reaction formulas (1) and (2):

    

    In the reaction formula (1), the carbazole skeleton-containing boron nitrogen core compound is used as the reactant, which is dissolved in an organic solvent, heated to reflux in the presence of a catalyst, and the para-hydrogen atom of the boron atom of the b benzene ring is activated. and replaced by boron ester;

    In the reaction formula (2), the electron-withdrawing group is introduced into the boron-nitrogen skeleton by using the Suzuki reaction, and the introduced electron-withdrawing group is located in the para position of the B atom of the b benzene ring in the boron-nitrogen skeleton;

    In the reaction formula (2), ArX is any one of the following three molecules:

    

    X is Br or Cl;

    R ¹ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ²² , R are as defined in claim 1 .

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