CN113831371A

CN113831371A - [3+2+1] coordination configuration iridium metal red light complex, preparation method thereof and organic electroluminescent device

Info

Publication number: CN113831371A
Application number: CN202111279868.6A
Authority: CN
Inventors: 吴远; 杨琛; 关韵芝; 伍成城
Original assignee: Shenzhen Purui Material Technology Co ltd
Current assignee: Shenzhen Purui Material Technology Co ltd
Priority date: 2021-10-29
Filing date: 2021-10-29
Publication date: 2021-12-24

Abstract

The invention belongs to the technical field of organic photoelectric materials. The invention discloses a [3+2+1] coordination configuration iridium metal red light complex, a preparation method thereof and an organic electroluminescent device, which have a structure shown in a formula (I). On one hand, the iridium metal complex realizes the emission wavelength of red light and near infrared light and higher quantum efficiency by cooperatively regulating a bidentate ligand and utilizing the action of a strong field ligand of the tridentate ligand and the monodentate ligand. On the other hand, the double-tooth chelating ligand structure is adjusted to be a rigid structure, so that the emission wavelength is further red-shifted to reach a near infrared light region, and the quantum efficiency is further improved. The iridium metal complex is applied to preparing a guest material of a light-emitting layer in an organic electroluminescent device. The invention also discloses an organic electroluminescent device, at least one functional layer contains the iridium metal complex, and the red-light OLED device is prepared by taking the complex as a guest material of a light-emitting layer.

Description

[3+2+1] coordination configuration iridium metal red light complex, preparation method thereof and organic electroluminescent device

Technical Field

The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. More particularly, it relates to a phosphorescent luminescent material containing metallic iridium (III) complex formed by [3+2+1] type coordination mode and a compound synthesis formula containing the series of complexes for preparing organic electroluminescent device.

Background

Organic Light Emitting Diodes (OLEDs) were first disclosed by Duncao et al (U.S. patent 4,356,429) and in Appl. Phys. Lett.1987,51,913. Since OLEDs have characteristics of wide viewing angle, ultra-thin, self-luminescence, low voltage, high efficiency, flexible display, and the like, they are a development trend of next generation display and illumination, and become one of display technologies with the most application prospects.

Fluorescent OLEDs emit light using only singlet states, with an Internal Quantum Efficiency (IQE) of only 25%, and triplet states generated in the device are wasted by non-radiative decay, which limits the commercialization of the OLED. In 1998, phosphorescent OLED devices were reported in light and ramification (Synthetic Metals 1998,94,245), Forrest and Thompson (Nature 1998,395,151), which utilize both singlet and triplet emission to achieve 100% IQE. Due to its high efficiency, phosphorescent OLEDs directly contribute to the commercialization of active matrix OLEDs (amoleds), and phosphorescent materials are also the main direction of OLED light emitting layer material development.

The red light material is one of the three primary colors of blue, green and red, and is an essential material for OLED display and illumination. But its development is a very challenging task. On the one hand, according to the energy gap rule (energy gap law; J.Am. chem. Soc.1982,104,630), the rate of nonradiative transition increases with decreasing energy level difference between the excited state and the ground state, and the narrower energy gap of the red light compound itself leads to lower luminescence quantum efficiency (PLQY). Therefore, the red shift and high efficiency of the emission wavelength in the research of the red light material are difficult to realize simultaneously, so that few red light materials with PLQY more than 50 percent reported so far are available; in additionOn the one hand, the smaller energy gap also makes the energy level matching between the host and the guest difficult, and it is difficult to obtain a device with high External Quantum Efficiency (EQE). For example, a widely used red phosphor (MDQ)₂Ir (acac) and (piq)₂The PLQY of Ir (acac) is only 0.48 and 0.20, respectively (Adv. Mater.2003,15,224; Adv. Mater.2003,15,884). Tsuboyama et al (J.Am.chem.Soc.2003,125,12971) report a series of cyclometalated iridium complexes in which Ir (piq)₃Has a maximum emission wavelength of 620nm and a PLQY of 0.26. Based on Ir (piq)₃The maximum EQE of the constructed OLED device is 10.3%, and the Power Efficiency (PE) is 6.58cd m^-1The CIE color coordinates are (0.68, 0.32). Cheng et al used a red phosphorescent iridium complex with a PLQY of 0.55 (tmq)₂Ir (acac) produces OLED red devices. The device shows good performance, the maximum EQE is 25.9 percent, and the maximum current efficiency (current efficiency) is 37.3cd A^-1PE is 32.9lm W^-1Maximum luminance of 25926 cd m^-2The CIE color coordinates are (0.67,0.33) and the color is the standard red recommended by the National Television System Committee (NTSC). Sting and Zheng et al (RSC adv.2017,7,37021) synthesized a series of deep red phosphorescent materials, popIr1, popIr2, popIr3 and popIr 4. The maximum emission wavelengths of these compounds were 645, 650, 634 and 639nm, respectively, and the PLQY was 24.8%, 18.3%, 31.2% and 40.6%, respectively. Its fluorine modified popIr4 had the highest electron mobility with a maximum EQE of 17.8%.

Preparation of phosphorescent Metal complexes, typically [2+ 2] formed by chelating a Central Metal with three bidentate ligands]Coordination-configuration metal complex molecules, e.g. the classical phosphorescent materials FIrpic, Ir (ppy)₃And Ir (piq)₂(acac). Quarterly first et al reported a series of [3+3 ] ligands consisting of two tridentate ligands with iridium (III)]The coordination configuration metal complex molecules have strong rigidity and stability, wherein PLQY of a blue light material Cz-5 reaches 96.2%, the performance of an OLED device prepared from the coordination configuration metal complex molecules reaches 18.7% of EQE, and CIE color coordinates are (0.145, 0.218) (chem.Eur.J.2019,25,15375); in addition, a red light material (pz)^Phpy^Bph^B) PLQY of Ir (pziqph) of up to 100%, prepared therewithThe performance of the OLED device reaches EQE_max28.17% with CIE color coordinates (0.63, 0.37) (inorg. chem.2019,58,10944). Haga et al synthesized three neutral [3+2+1] s using a tridentate ligand N ^ C ^ N and a bidentate ligand N ^ C]Coordination configuration iridium (III) complex [ Ir (N ^ C ^ N) (N ^ C) (X)]These compounds exhibited maximum emission wavelengths at 77K in the 447-460nm range (Inorg. chem.2008,47,7154). Wong et al (Inorg. chem.2012,51,8693) synthesized a series of positively charged [3+2+1] using a tridentate NHC ligand C ^ C ^ C and a bidentate ligand N ^ N]Coordination configuration osmium (III) complex [ Os (C ^ C ^ C) (N ^ N) (CO)]⁺. Similar positively charged [3+2+1] were also reported by Wong et al (Sci. Rep.2015,5,15394)]Coordination configuration iridium (III) complex [ Ir (C ^ C ^ C) (N ^ N) (H)]⁺The maximum emission wavelength of these compounds is 577-604nm, and the PLQY is 0.0245% -0.109%.

Therefore, in the prior OLED technology, the red phosphorescent metal complex used in the light emitting layer has the following technical difficulties: 1, the luminous quantum efficiency of the red luminescent material of the metal iridium (III) complex is generally low; 2, the emission peak of the red luminescent material of the metal iridium (III) complex is not easy to be adjusted to a near infrared region (the main wavelength peak is more than 680 nm).

Disclosure of Invention

The present invention is directed to overcoming the above-mentioned deficiencies of the prior art and providing a process for the formation of [3+2+1] using a tridentate chelating ligand, a bidentate chelating ligand and a monodentate ligand]Iridium (III) complex of type coordination configuration: (L)_A)Ir(L_B)(L_C) Wherein Ir is a group VIIIB, 6 th period transition metal iridium, the total oxidation state of which is + 3; l is_AIs a tridentate ligand, the total oxidation state of which is-1; l is_BIs a bidentate ligand, the total oxidation state of which is-1; l is_CIs a monodentate ligand having a total oxidation state of-1, said iridium (III) complex being neutral and having the following structure of formula (I):

wherein the content of the first and second substances,

each A¹-A⁵Independently selected from C, N;

each A⁶-A⁸，A¹⁰-A¹⁴，A¹⁶-A¹⁷Independently selected from C, N, S, O;

each A⁹，A¹⁵Independently selected from C, N;

R^A，R¹may be the same or different and are independently selected from hydrogen, halogen, CF₃，–CN，–OR’，–Si(R’)₃，–N(R’)₂，–SR’，–P(R’)₂，–C(O)R’，–C(O)OR’，–C(O)NR’，–SOR’，–SO₂R’，–SO₃R’，–P(O)(R’)₂，–P(O)(OR’)R’，–P(O)(OR’)₂C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' in the same group, which may be the same or different, is independently selected from: hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl;

or the like, or, alternatively,

R^Aany two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkylC3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl;

R²selected from C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl, -C (O) R ", -C (O) OR", -C (O) NR "; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R”)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' in the same group may be the same or different and is independently selected from: hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl;

R^B，R^Cindependently selected from: -O (R '"), -N (R'")₂，–SO(R”’)，–SO₂(R”’)，–P(R”’)₂，–PO(R”’)₂，–PO(OR”’)(R”’)，–PO(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C1-C40 alkoxy, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' "in the same group, which may be the same or different, are independently selected from: hydrogen, halogen, C1-C40 alkyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocyclyl, C3-C40 aryl, C3-C40 heteroaryl, wherein the heteroatom is N, S, O;

or the like, or, alternatively,

R^Band R^CAny two adjacent groups thereof form a 5-to 7-membered aryl or heteroaryl group with the ring atoms to which they are attached, an 8-to 10-membered fused bisA cyclic aryl or heteroaryl group, or a fused 11-to 14-membered tricyclic aryl or heteroaryl group, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl;

the R is^dSelected from-O (R '"), -N (R'")₂，–SO(R”’)，–SO₂(R”’)，–P(R”’)₂，–PO(R”’)₂，–PO(OR”’)(R”’)，–PO(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C1-C40 alkoxy, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' "in the same group, which may be the same or different, are independently selected from: hydrogen, halogen, C1-C40 alkyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocyclyl, C3-C40 aryl, C3-C40 heteroaryl, wherein the heteroatom is N, S, O;

or the like, or, alternatively,

or R^dAny two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR "’，–N(R”’)₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl;

n is 0,1, 2 or 3; m is 0,1, 2;

t is 1 or 2; when t is 1, the atoms contained in t are selected from C, N, O and S; when t is 2, two atoms contained in the t are respectively and independently selected from C, N, O and S;

o is 1 or 2;

p and q are independently integers from 0 to 4;

monodentate ligand L_CSelected from: cl, Br, I, CN, OCN, SCN and C1-C40 alkyl, C1-C40 alkoxy, C1-C40 acyloxy, C5-C40 aryl, C5-C40 heterocyclic aryl, C2-C40 alkynyl.

Preferably, the complex of formula (I) wherein R^A，R¹May be the same OR different and is independently selected from hydrogen, halogen, -CN, -OR ', -Si (R')₃，–N(R’)₂，–SR’，–P(R’)₂，–C(O)R’，–C(O)OR’，–SOR’，–SO₂R', C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; r' in the same group, which may be the same or different, is independently selected from: hydrogen, -CN, halogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl;

R²selected from C1-C20 alkyl, C2-C20 alkenylC2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl, -C (O) R ', -C (O) OR'; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R”)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; r' in the same group may be the same or different and is independently selected from: hydrogen, -CN, halogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl.

Further preferably, wherein, the ligand L_AIs specifically selected from L_A1To L_A21Any one of which has the following structure:

preferably, the complex of formula (I) wherein the ligand L_BIn, R^B，R^CIndependently selected from: -O (R '"), -Si (R'")₃，–N(R”’)₂，–SO₂(R”’)，–P(R”’)₂C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; r' "in the same group, which may be the same or different, are independently selected from: hydrogen, halogen, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocyclyl, C3-C20 aryl, C3-C20 heteroaryl, wherein the heteroatom is N, S or O.

or the like, or, alternatively,

R^Band R^CAny two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl;

the R is^dSelected from-O (R '"), -N (R'")₂，–SO(R”’)，–SO₂(R”’)，–P(R”’)₂，–PO(R”’)₂，–PO(OR”’)(R”’)，–PO(OR”’)₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl;

the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl, wherein the heteroatoms are N, S and O;

or the like, or, alternatively,

or R^dAny two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl;

further preferred are the complexes of formula (I), wherein the ligand L_BA ligand selected from the group consisting of:

preferably, the formula (A)I) Complexes in which the monodentate ligand L_CSelected from: cl, Br, I, CN, OCN, SCN, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 acyloxy, C6-C12 aryl, C6-C12 heteroaryl, C2-C8 alkynyl.

The invention relates to a complex of formula (II) for an OLED luminescent material:

wherein L is_CY＝Br^-(L_C1)，CN^-(L_C2)，I^-(L_C3)；

Preferably, the complex of formula (II) for an OLED light-emitting material is selected in particular from the following compounds:

the invention further relates to a process for the preparation of the complex of formula (I), as follows:

with [ H ]_x+1L_A]Br_xIridium metal precursor and HL_BObtaining an iridium (III) complex shown as a formula (Ir-a) by a one-pot method; further subjecting L of an iridium (III) complex represented by the formula (Ir-a)_C1Reacting M (L) by metathesis_C)_yMonodentate ligand L of_CSubstitution onto iridium metal gives an iridium (III) complex represented by the formula (I).

Wherein x is 1, 2;

wherein said M (L)_C)_yIs said monodentate ligand L_CSalts with a metal M, the oxygen of said metal MThe valence is +1/+2, and the metal M is selected from Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Cu, Ag, Au, Zn, Cd and Hg, wherein y is 1, 2.

Preferably, the one-pot process comprises the steps used for the preparation of formula (Ir-a): the ith step is that_x+1L_A]Br_xAdding iridium metal precursor and alkali into solvent, removing solvent at the end of reaction and directly making reaction of step ii without separation, wherein step ii is specifically described as adding HL_BAnd heated to the selected temperature of the reaction.

Wherein, the iridium metal precursor is bis (1, 5-cyclooctadiene) iridium chloride (I) dimer, which is abbreviated as: [ Ir (cod) Cl]₂The base is an organic base (e.g. triethylamine, NEt)₃) The reaction temperature in step i was 90 ℃ and the reaction solvent was acetonitrile (MeCN), the solvent used in step ii was 2-ethoxyethanol (2-EtOEtOH) and the reaction temperature was 150 ℃.

Further preferably, the metal salt used in the second step for preparing formula (I) is a silver salt, and the solvent is N, N-dimethylformamide.

The invention also relates to a preparation method of the iridium (III) complex shown in the formula (II), which comprises the following steps:

the ith step: in which an iridium (III) complex of the formula (IV-1) in which L is_C1To a 25mL chlike tube (Schlenk tube) with magnetons under nitrogen blanket was added 1mmol [ H ═ Br₃L_A1]Br₂0.5mmol of Iridium metal precursor [ Ir (cod) Cl ]]₂And 20mL of acetonitrile, nitrogen is introduced by means of a needle and the solution is degassed for 5 minutes, 2mL of triethylamine is added and the reaction is stopped after heating to 90 ℃ for 12 hours, after the organic solvent has been removed under reduced pressure, 1mmol of HL is added under the protection of nitrogen_BAnd 10mL of 2-ethoxyethanol, and the mixture was heated to 150 ℃ and stirred overnight. Stopping reaction, cooling to room temperature, removing solvent under reduced pressure, separating and purifying by silica gel column chromatography, and collecting mobile phase from dichloromethane to dichloromethane/ethyl acetate (volume ratio of 50:1) to obtain crude product with luminescence, and drying if passing through¹After H NMR characterization, the crude product is confirmed to be a target product of the iridium (III) complex shown in the formula (IV-1), and can be directly used;

step ii: synthesis of an Iridium (III) Complex of the formula (II) in which L_C2＝CN，

Adding the formula (IV-1) into a two-mouth bottle with magnetons under the protection of nitrogen, and adding 2 times of equivalent of silver salt AgL_CAnd 20mL of N, N-dimethylformamide, heating the reaction solution to 90 ℃, stopping the reaction after two hours, removing the N, N-dimethylformamide under reduced pressure to obtain a luminescent crude product, separating by silica gel column chromatography, and obtaining a target product formula (II) by using dichloromethane to dichloromethane/ethyl acetate (the volume ratio is 10:1) as a mobile phase.

The invention also relates to an electroluminescent device comprising:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

and an organic layer disposed between the anode and the cathode, the organic layer comprising a light emitting device prepared from the complex of formula (I) or formula (II).

Preferably, the organic layer comprises various types of charge transport layers and a light-emitting layer, and the light-emitting layer comprises a host material and the complex of formula (I) or formula (ii) as claimed in the claims as a light-emitting material for the light-emitting layer.

Preferably, the device emits light in a characteristic wavelength band (from ultraviolet light to near infrared light) emitted by the complex of formula (I) or formula (ii), or the device is passed through a device manufacturing process, wherein the manufacturing process comprises stacking a plurality of light-emitting layers, doping other light-emitting material means, wherein any light-emitting layer emits mixed light using the complex of formula (I) or formula (ii).

The term "halogen" in the present invention refers to F, Cl, Br, I.

The terms "alkyl", "alkoxy", "haloalkyl" and any of the present inventionSubstituents containing "alkyl" moieties include branched or straight chain alkyl groups, preferably C, optionally bearing at least one substituent, optionally interrupted by at least one heteroatom_1–C₄₀Alkyl radical, C₁–C₂₀Alkyl, more preferably C₁–C₈Alkyl, particularly preferably C₁–C₆Alkyl groups, for example: methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, n-hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl and the like. Furthermore, alkyl is optionally substituted with one or more substituents, preferably halogen, more preferably F, C₁–C₂₀Haloalkyl, C₁–C₈Haloalkyl, C₁–C₄Haloalkyl, most preferably CF₃Perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl.

The term "alkenyl" according to the present invention includes branched or straight-chain alkenyl groups, preferably C, optionally carrying at least one substituent, optionally interrupted by at least one heteroatom_2–C₄₀Alkenyl radical, C₁–C₂₀Alkenyl is more preferably C₂–C₈Alkenyl, particularly preferably C₂–C₆Alkenyl radicals, for example: ethenyl, propenyl, butenyl, pentenyl, and the like.

The term "alkynyl" according to the invention includes branched or straight-chain alkynyl groups, preferably C, optionally interrupted by at least one heteroatom, optionally bearing at least one substituent_2–C₄₀Alkynyl, C₁–C₂₀Alkynyl is more preferably C₂–C₈Alkynyl, particularly preferably C₂–C₆Alkynyl groups, for example: ethynyl, propynyl, butynyl, pentynyl and the like.

The term "cycloalkyl" in the present invention includes substituted or unsubstituted saturated cycloalkyl groups, which may comprise a monocyclic ring of 4 to 8, preferably 5 to 6 ring atoms or a polycyclic ring system of 6 to 40, preferably 6 to 20, 6 to 13, more preferably 9 to 13 ring atoms, specific examples including: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, bicyclo [2.2.1] heptyl, bicyclo [2,2,2] octyl, but are not limited thereto.

The term "heterocycloalkyl group" in the present invention means a cycloalkyl group containing 1 to 4 heteroatoms selected from N, O, S as cycloalkyl skeleton atoms and carbon atoms as the remaining cycloalkyl skeleton atoms, and the heterocycloalkyl group may be a 3-, 4-, 5-, 6-, 7-or 8-membered monocyclic heterocycloalkyl group or a polycyclic system having 6 to 40, preferably 6 to 20, 6 to 13, more preferably 9 to 13 ring atoms, and specific examples include: morpholinyl, thiomorpholinyl, but not limited thereto.

The term "aryl" in the present invention refers to an organic group derived from an aromatic hydrocarbon by removal of one hydrogen atom, and may comprise a single ring of 4 to 8, preferably 5 to 6 ring atoms or a fused ring system of 6 to 40, preferably 6 to 20, 6 to 13, more preferably 9 to 13 ring atoms. Specific examples include: phenyl, naphthyl, diphenyl, anthracenyl, tetrahydronaphthyl, indenyl, fluorenyl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, tetracenyl, fluoranthenyl, and the like, but are not limited thereto.

The term "heteroaryl" in the present invention refers to an aryl group containing 1 to 4 heteroatoms selected from N, O, S, P as aromatic ring backbone atoms, and carbon atoms as the remaining aromatic ring backbone atoms. Heteroaryl groups may be 5-, 6-, 7-or 8-membered monocyclic heteroaryl groups or polycyclic heteroaryl groups fused to one or more phenyl rings, which may be partially saturated, which may contain from 6 to 40, preferably from 6 to 20, more preferably from 9 to 13 ring atoms. Specific examples include monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like; polycyclic heteroaryl groups such as benzofuranyl, benzothienyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenanthridinyl, and benzodioxolyl, but are not limited thereto.

The term "carboxy" in the context of the present invention refers to "R^a-COO- ", wherein R is^aRefers to alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, each group defined as set forth above.

The term "substituted" in the present invention means optionally substituted with at least one substituent, specifically including but not limited to: mono-substituted, di-substituted, tri-substituted, tetra-substituted, penta-substituted, and the like.

The dotted line connecting the iridium metal and the ligand used in the general structural formula of the present invention refers to a coordinate covalent bond, including but not limited to a single bond, a double bond, and the like.

Compared with the prior art, the [3+2+1] coordination configuration iridium metal complex can achieve the following excellent technical effects: 1, the bidentate chelating ligand is a chromophore of the metal complex, the emission peak of the complex can be effectively adjusted by adjusting the ligand, and the range covers green light, yellow light, orange light, red light and near infrared light regions; 2, compared with the [2+2+2] coordination configuration iridium metal complex, the single bidentate chelate ligand is utilized, so that charge transfer competition among ligands can be effectively reduced (red light materials mostly belong to ligand center-ligand charge transfer), and the reduction of quantum yield loss is realized; 3, utilizing tridentate ligand with N-heterocyclic carbene (N-NHC: a strong sigma electron donor and a weak pi electron acceptor), which can effectively change the metal component proportion of the molecular front track of the metal complex, thereby realizing the adjustment of the molecular luminescence wavelength and the quantum efficiency; 4, the monodentate negative monovalent ligand with strong ligand field can also effectively change the metal components of the front orbit of the metal complex molecule, thereby realizing the adjustment of the luminous wavelength and the quantum efficiency of the molecule; compared with the prior [3+2+1] coordination configuration iridium metal complex, the bidentate chelate ligand in the [3+2+1] coordination configuration iridium metal complex adopts a rigid structure, so that the ligands cannot rotate, the emission wavelength is further red-shifted to reach a near infrared region, and the quantum efficiency is further improved. Therefore, the invention can realize the light emission of green light, yellow light, orange light, red light and near infrared light by utilizing a single chromophore, and solves the technical problems of low quantum efficiency, difficult realization of near infrared light and the like of a red light material through the strong field ligand action of the synergetic tridentate chelating ligand and monodentate ligand and through the color matching process of the single bidentate ligand.

The preparation method of the complex successfully realizes the synthesis of the complex with generally high yield through screening equivalent weight, temperature, catalyst and solvent conditions. And the involved core reactions are conventional metal catalytic coupling reactions, high-toxicity and high-explosion dangerous reactants are not adopted, the repeatability is good, the construction efficiency is high, and the synthesis reference is realized.

The electroluminescent device has the advantages of high quantum yield, realization of near-infrared wavelength emission, wide wavelength coverage range, high energy conversion rate and the like due to the adoption of the [3+2+1] coordination configuration iridium metal complex.

Drawings

Fig. 1 to 4 are solution-state photophysical spectrograms of application examples Ir1a, Ir1b, Ir2a, Ir2b, Ir2c, Ir2d, Ir3a, Ir3b, Ir4a, Ir4b, Ir5a, Ir6a and Ir6 b.

Fig. 5 is a perspective view of an X-ray single crystal diffraction structure using example Ir2 b.

FIG. 6 is a thermogravimetric analysis of the application examples Ir2a, Ir2b and Ir2 d.

FIG. 7 is a schematic diagram of the structure of various types of materials used to fabricate device 1 using example Ir2 b.

FIG. 8 is a graph of the electroluminescence spectrum of a device 1 prepared using example Ir2 b.

Detailed Description

The material and the method are as follows:

all starting materials are commercially available materials. The reagents used for synthesis and photophysics are analytically pure and chromatographically pure reagents, respectively. Hydrogen (400 MHz) and fluorine (376 MHz) NMR spectra were measured using an Avance 400 Bruker FT type NMR spectrometer. The UV-Vis spectra were determined using a Hewlett-Packard 8452A diode array UV-Vis spectrophotometer. The steady state emission spectrum in solution at 298K was determined using a SPEX 1681 Fluorolog-3 spectrometer. Wherein the solution for photophysical testing is subjected to high vacuum for more than five times of freezing-air extraction-unfreezing circulation air extraction to remove air. Emission quantum yield was determined using a Hamamatsu C11347 Quantaurus-QY type absolute quantum yield tester.

Synthesis examples:

synthesis of tridentate ligand precursors: dibromo 1, 1' - (1, 3-phenyl) bis (3-butyl-1H-imidazol-3-ium) salt, { [ H ] -)₃L_A1]Br₂}：

A100 mL round bottom flask with stirrer was charged with 1, 3-dibromobenzene (2.36g,10mmol), imidazole (4.08g,60mmol), cuprous iodide (95mg,0.5mmol), potassium carbonate (25.3g,0.183mol) and dimethylsulfoxide (60mL), respectively. After the mixture was reacted at 150 ℃ for two days, the reaction was cooled to 60 ℃ and filtered through celite, and the organic product was extracted by washing with ethyl acetate (30mL × 3). The organic solutions were combined and ethyl acetate was removed by rotary evaporation and dimethyl sulfoxide was removed by distillation under reduced pressure. The organic product was dissolved in dichloromethane (200mL) and the organic phase was washed with water (30 mL. times.3). The organic phase was dried over anhydrous magnesium sulfate, filtered and rotary-distilled to leave a white solid as the objective 1, 3-bisimidazol-1-ylbenzene (yield: 2.09g, yield: 99%).¹H NMR (400 mhz, deuterated chloroform): δ 7.93(s,2H),7.63(t, J8.0 Hz,1H),7.45(s,2H),7.42(d, J1.9 Hz,1H),7.35(s,2H),7.27(s,2H) ppm.

To a 25mL Hirak tube (Schlenk tube) with magnetons were added 1, 3-bisimidazol-1-ylbenzene (5.8g,27.6mmol), n-bromobutane (18.9g,138mmol) and acetonitrile (15 mL). The solution was heated to 90 ℃ under nitrogen with constant stirring. After 12 hours the acetonitrile was removed by rotary evaporation, the solid residue was dissolved in 50mL ethanol, concentrated to a volume of about 5mL,20mL of diethyl ether was added. The white precipitate was collected quickly as the desired product (yield: 10.7g, yield: 80%).¹H NMR (400 mhz, deuterated chloroform): δ 11.51(s,2H),9.13(t, J ═ 1.9Hz,2H),9.06(d, J ═ 2.2Hz,1H),8.38(dd, J ═ 8.3,2.1Hz,2H),7.67(t, J ═ 8.2Hz,1H),7.52(d, J ═ 1.8Hz,2H),4.48(t, J ═ 7.4Hz,4H),2.05(p, J ═ 7.4Hz,4H),1.46(dt, J ═ 14.8,7.4Hz,4H),1.03(t, J ═ 7.4Hz,6H) ppm, and [ H ] in the literature₃L_A1]Br₂The reported values are consistent.

The preparation method of the compound of the present invention is not limited, and the following complexes are typically but not limited, and the synthetic route and the preparation method thereof are as follows:

example 1

Synthesis of Iridium Complex (L)_A1)Ir(L_B1)(L_C1) Synthesis of example Ir1 a:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A1]Br₂(218mg,0.45mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂150mg,0.225mmol) and acetonitrile (20 mL). Nitrogen was introduced using a needle and the solution was degassed for 5 minutes, after which triethylamine (2mL) was added and heated to 90 ℃ and the reaction stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B1(104mg,0.45mmol) and 2-ethoxyethanol (20 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by separation and purification by silica gel column chromatography, and the mobile phase was changed from dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (115mg,0.14mmol), yield: 31 percent.¹H NMR (400 mhz, deuterated chloroform): δ 10.74(s,1H),9.38(d, J6.8 Hz,1H),8.98(d, J3.0 Hz,1H),8.59(d, J7.9 Hz,1H),8.00(d, J8.0 Hz,1H), 7.89-7.71 (m,2H),7.46(d, J2.0 Hz,2H), 7.28-7.21 (m,3H),7.08(t, J7.7 Hz,1H),6.66(d, J2.1 Hz,2H),6.39(d, J7.5 Hz,1H), 3.25-2.85 (m,4H), 1.22-1.15 (m,1H),2H),0.77–0.55(m,4H),0.48–0.38(m,2H),0.36(t,J＝6.7Hz,6H)ppm。

Example 2

Synthesis of Iridium Complex (L)_A1)Ir(L_B1)(L_C2) Synthesis of example Ir1 b:

adding (L) into a two-mouth bottle with magnetons under the protection of nitrogen_A1)Ir(L_B1)(L_C1) (33mg,0.04mmol), silver cyanide (16mg,0.12mmol) and N, N-dimethylformamide (20 mL). The reaction solution was heated to 100 ℃ and the reaction was stopped after 2 hours. The N, N-dimethylformamide was removed under reduced pressure to obtain a luminescent solid. The product was isolated by column chromatography on silica gel using dichloromethane to dichloromethane/ethyl acetate (volume ratio 5:1) as the mobile phase to give the desired product (30mg,0.04mmol), yield: 99 percent.¹H NMR (400 mhz, deuterated chloroform) × 10.43(d, J ═ 2.9Hz,1H),9.31(dd, J ═ 8.0,1.6Hz,1H),8.96(d, J ═ 2.9Hz,1H),8.57(d, J ═ 7.9Hz,1H),8.03(d, J ═ 8.0Hz,1H), 7.88-7.69 (m,2H),7.49(d, J ═ 2.0Hz,2H),7.32(dd, J ═ 8.6,7.0Hz,1H),7.22(d, J ═ 7.7Hz,2H),7.12(t, J ═ 7.6Hz,1H),6.70(d, J ═ 2.0, 6H), 7.34H, 3.34H, 4.6H, 31.6H, 1H, 4 (m-6H), 4.31H, 1H, 4 (m-6H), 4.6H, 1H).

Example 3

Synthesis of Iridium Complex (L)_A1)Ir(L_B2)(L_C1) Synthesis of example Ir2 a:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A1]Br₂(145mg,0.3mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂100mg,0.15mmol) and acetonitrile (20 mL). Nitrogen was introduced using a needle and the solution degassed for 5 minutes, after which triethylamine (2mL) was added and heated to 90 deg.CThe reaction was stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B2(84mg,0.3mmol) and 2-ethoxyethanol (20 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by column chromatography on silica gel and mobile phase using dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (117mg,0.13mmol), yield: 44 percent.¹H NMR (400 mhz, deuterated chloroform) × 11.31(dd, J ═ 8.7,1.4Hz,1H), 9.71-9.30 (m,1H),8.48(td, J ═ 8.5,1.4Hz,2H), 8.15-7.88 (m,3H),7.78(pd, J ═ 7.1,1.6Hz,2H),7.46(d, J ═ 2.1Hz,2H), 7.30-7.24 (m,1H),7.24(s,1H),7.22(d, J ═ 1.9Hz,1H), 7.07-6.95 (m,1H),6.64(d, J ═ 2.1Hz,2H),6.41(dd, J ═ 7.6,0.9, 3.9, 3.95 (m,1H),6.64(d, J ═ 2.1Hz,2H),6.41(dd, J ═ 7.6, 0.06, 0.9, 3.5, 13.5H), 13.06 (dd, 13.06, 13.5H), 13.5H, 13.7.06, 13.06, 13.7.7.7.7.7.7.7.7.7.7.7.7.7.7.6.6.6.7.7.6.7.7.7.7.7.6.7.6.7.7.7.6.6.7.7.7.7.7.7.7.6, 7.7.7.6, 7.7.7.7.7.7.7.7.7.6, 1H, 2.7.7.7.7.7.7.7.7.7.7.7.7.6, 1H, 2.7.6, 1H, 2H, 2.7, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H, 1H, 2H.

Example 4

Synthesis of Iridium Complex (L)_A1)Ir(L_B2)(L_C2) Synthesis of example Ir2 b:

adding (L) into a two-mouth bottle with magnetons under the protection of nitrogen_A1)Ir(L_B2)(L_C1) (175mg,0.2mmol), silver cyanide (58mg,0.4mmol) and N, N-dimethylformamide (20 mL). The reaction solution was heated to 100 ℃ and the reaction was stopped after 2 hours. The N, N-dimethylformamide was removed under reduced pressure to obtain a luminescent solid. Chromatography on silica gel with mobile phase from dichloromethane to dichloromethane/ethyl acetate (5: 1 by volume) gave the title product (134mg,0.16mmol) in yield: 82 percent.¹H NMR (400 mhz, deuterated chloroform) × 10.66(d, J ═ 8.9Hz,1H), 9.51-9.45 (m,1H),8.49(dd, J ═ 18.6,8.1Hz,2H),8.14(t, J ═ 7.9Hz,1H),7.99(t, J ═ 7.7Hz,2H), 7.86-7.70 (m,2H),7.49(d, J ═ 2.0Hz,2H), 7.44-7.32 (m,1H),7.24(d, J ═ 7.8Hz,2H),7.07(t, J ═ 7.6Hz,1H),6.68(d, J ═ 2.1Hz,2H),6.38(d, J ═ 7.3, 1H), 3.91.91.05H, 2H),2.89–2.75(m,2H),1.21–1.04(m,2H),0.78–0.59(m,2H),0.24–0.15(m,6H),0.17–0.03(m,4H)。

example 5

Synthesis of Iridium Complex (L)_A21)Ir(L_B2)(L_C3) Synthesis of example Ir2 c:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A21]I₂(2.96g,6.0mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂2g,3.0mmol) and acetonitrile (100 mL). Nitrogen was introduced using a needle and the solution was degassed for 5 minutes, after which triethylamine (10mL) was added and heated to 90 ℃ and the reaction stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B2(1.68g,6.0mmol) and 2-ethoxyethanol (100 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by silica gel column chromatography, and the mobile phase was separated and purified using dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (1.96g,2.34mmol), yield: 39 percent.¹H NMR (400 mhz, deuterated chloroform): δ 11.23(dd, J7.3, 2.5Hz,1H),9.55 to 9.36(m,1H),8.48(dd, J7.9, 1.9Hz,2H),8.08 to 7.90(m,3H),7.88 to 7.67(m,2H),7.62 to 7.38(m,3H),7.25 to 7.08(m,1H),7.11 to 6.95(m,2H),6.65(d, J2.0 Hz,2H),6.27(d, J7.6 Hz,1H),2.82(s,6H) ppm.

Example 6

Synthesis of Iridium Complex (L)_A21)Ir(L_B2)(L_C2) Synthesis of example Ir2 d:

adding (L) into a two-mouth bottle with magnetons under the protection of nitrogen_A21)Ir(L_B2)(L_C3) (480mg,0.58mmol), silver cyanide (200mg,1.5 mmol)l) and N, N-dimethylformamide (20 mL). The reaction solution was heated to 100 ℃ and the reaction was stopped after 2 hours. The N, N-dimethylformamide was removed under reduced pressure to obtain a luminescent solid. Chromatography on silica gel with mobile phase from dichloromethane to dichloromethane/ethyl acetate (5: 1 by volume) gave the title product (275mg,0.374mmol) in yield: 65 percent.¹H NMR (400 mhz, deuterated chloroform): δ ═ 10.51 to 10.38(m,1H),9.48(d, J ═ 7.7Hz,1H),8.55 to 8.44(m,2H),8.12(dd, J ═ 8.7,6.8Hz,1H),8.00(dd, J ═ 7.5,3.5Hz,2H),7.92 to 7.72(m,2H),7.49(d, J ═ 2.1Hz,2H),7.43 to 7.34(m,1H),7.29 to 7.21(m,2H),7.09(t, J ═ 7.6Hz,1H),6.68(d, J ═ 2.0Hz,2H),6.35(d, J ═ 7.3, 1H), 6.73 (s, ppm).

Example 7

Synthesis of Iridium Complex (L)_A1)Ir(L_B5)(L_C1) Synthesis of example Ir3 a:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A1]Br₂(290mg,0.6mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂200mg,0.3mmol) and acetonitrile (20 mL). Nitrogen was introduced using a needle and the solution was degassed for 5 minutes, after which triethylamine (2mL) was added and heated to 90 ℃ and the reaction stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B5(185mg,0.6mmol) and 2-ethoxyethanol (20 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by silica gel column chromatography, and the mobile phase was separated and purified using dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (150mg,0.17mmol), yield: 27 percent.¹H NMR (400 MHz, DMSO-d)₆):δ＝9.78(s,1H),9.71–9.52(m,1H),8.93(dd,J＝21.3,7.8Hz,1H),8.76(s,1H),8.63–8.44(m,2H),8.38–8.24(m,1H),8.23–8.04(m,2H),8.04–7.83(m,2H),7.85–7.46(m,2H),7.49–7.12(m,2H),6.58–6.17(m,1H),3.32–3.09(m,4H),2.98(d,J＝20.3Hz,6H),1.36–1.13(m,2H),0.54–0.00(m,12H)ppm。

Example 8

Synthesis of Iridium Complex (L)_A1)Ir(L_B5)(L_C2) Synthesis of example Ir3 b:

adding (L) into a two-mouth bottle with magnetons under the protection of nitrogen_A1)Ir(L_B5)(L_C1) (100mg,0.11mmol), silver cyanide (30mg,0.22mmol) and N, N-dimethylformamide (20 mL). The reaction solution was heated to 100 ℃ and the reaction was stopped after 2 hours. The N, N-dimethylformamide was removed under reduced pressure to obtain a luminescent solid. Chromatography on silica gel with mobile phase from dichloromethane to dichloromethane/ethyl acetate (5: 1 by volume) gave the title product (10mg,0.012mmol) in: 11 percent.¹H NMR (400 MHz, DMSO-d)₆):δ＝10.82(s,1H),9.62(dd,J＝7.9,1.7Hz,1H),8.90(dd,J＝8.2,1.4Hz,1H),8.62(s,1H),8.43(d,J＝2.1Hz,2H),8.39–8.25(m,1H),8.10(dtd,J＝17.5,7.1,1.5Hz,2H),7.82(d,J＝7.9Hz,2H),7.63(t,J＝7.9Hz,1H),7.51(d,J＝2.1Hz,2H),7.27(t,J＝7.6Hz,1H),6.47(dd,J＝7.3,0.9Hz,1H),3.19(ddt,J＝18.4,12.6,7.1Hz,4H),2.97(s,3H),2.91(s,3H),1.29–1.15(m,2H),0.60(q,J＝6.6,5.1Hz,2H),0.39–0.23(m,8H),0.17–0.05(m,2H)ppm。

Example 9

Synthesis of Iridium Complex (L)_A1)Ir(L_B19)(L_C1) Synthesis of example Ir4 a:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A1]Br₂(290mg,0.6mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂200mg,0.3mmol) and acetonitrile (20 mL). Nitrogen was introduced using a needle and the solution was degassed for 5 minutes, after which time three was addedEthylamine (2mL) was heated to 90 ℃ and the reaction was stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B19(190mg,0.6mmol) and 2-ethoxyethanol (20 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by silica gel column chromatography, and the mobile phase was separated and purified using dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (42mg,0.046mmol), yield: 7 percent.¹H NMR (400 mhz, deuterated chloroform) × 11.61(dd, J ═ 13.3,8.6Hz,1H),9.42(dd, J ═ 7.8,1.6Hz,1H), 8.49-8.40 (m,1H),8.25(dd, J ═ 10.3,8.2Hz,1H),7.93(d, J ═ 7.7Hz,1H), 7.86-7.70 (m,2H),7.47(d, J ═ 2.1Hz,2H), 7.33-7.29 (m,1H), 7.26-7.22 (m,1H), 7.20-7.15 (m,1H),7.01(t, J ═ 7.7, 1H),6.67(d, J ═ 2.1, 6.43H), 6.7.0, 7.5 (ddh, 7.7, 1H), 7.5-7.7.7H, 1H, 7.7.7.7.7, 1H), 7.7.7.7.7.7.7, 1H, 6.7.7.7, 7.7H, 6.7.7, 7.7.7, 7H, 6.7, 7H, 7.7, 7.7.7.7, 7H, 7, 7.7H, 7H, 7.7, 7,3, 7H, 3, 7, 1H, 7, 1H, 3, 1H, 3, 1H, 3, 7, 8, 1H, 3, 1H, 3, 1H, 3, 1H, 3, and the like.¹⁹F NMR (376 mhz, deuterated chloroform) — δ -126.85(d, J-22.1 Hz), -130.48(d, J-22.4 Hz) ppm.

Example 10

Synthesis of Iridium Complex (L)_A1)Ir(L_B19)(L_C2) Synthesis of example Ir4 b:

adding (L) into a two-mouth bottle with magnetons under the protection of nitrogen_A1)Ir(L_B19)(L_C1) (40mg,0.044mmol), silver cyanide (12mg,0.088mmol), and N, N-dimethylformamide (20 mL). The reaction solution was heated to 100 ℃ and the reaction was stopped after 2 hours. The N, N-dimethylformamide was removed under reduced pressure to obtain a luminescent solid. Chromatography on silica gel with mobile phase from dichloromethane to dichloromethane/ethyl acetate (5: 1 by volume) gave the title product (23mg,0.027mmol) in yield: 61 percent.¹H NMR (400 mhz, deuterated chloroform): δ 10.90-10.76 (m,1H), 9.43-9.33 (m,1H), 8.50-8.41 (m,1H), 8.34-8.20 (m,1H), 8.03-7.92 (m,1H), 7.82-7.69 (m,2H), 7.50-7.43 (m,2H), 7.39-7.29 (m,1H),7.26–7.18(m,2H),7.14–7.00(m,1H),6.74–6.64(m,2H),6.43–6.31(m,1H),3.02–2.80(m,4H),1.18–1.01(m,2H),0.70–0.53(m,2H),0.25–0.06(m,10H)ppm。¹⁹F NMR (376 mhz, deuterated chloroform) — δ -125.45(d, J-21.8 Hz), -130.59(d, J-21.8 Hz) ppm.

Example 11

Synthesis of Iridium Complex (L)_A1)Ir(L_B20)(L_C1) Synthesis of example Ir5 a:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A1]Br₂(290mg,0.6mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂200mg,0.3mmol) and acetonitrile (20 mL). Nitrogen was introduced using a needle and the solution was degassed for 5 minutes, after which triethylamine (2mL) was added and heated to 90 ℃ and the reaction stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B20(280mg,0.6mmol) and 2-ethoxyethanol (20 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by separation and purification by silica gel column chromatography, and the mobile phase was changed from dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (20mg,0.019mmol), yield: 3 percent.¹H NMR (400 mhz, deuterated chloroform): δ 11.16-11.07 (m,1H), 9.53-9.12 (m,1H), 8.64-8.37 (m,1H),8.23(d, J ═ 7.8Hz,1H), 7.91-7.65 (m,2H), 7.56-7.38 (m,2H),7.21(d, J ═ 6.8Hz,2H), 7.04-6.91 (m,1H), 6.69-6.56 (m,2H),6.37(dd, J ═ 14.8,7.8Hz,1H), 3.17-2.83 (m,4H), 1.18-1.01 (m,2H), 0.71-0.49 (m,2H), 0.22-0.02 (m,10H), ppm.

Example 12

Synthesis of Iridium Complex (L)_A20)Ir(L_B2)(L_C1) Synthesis of example Ir6 a:

to a 25mL Hirak tube (Schlenk tube) with magnetons was added [ H ] under nitrogen₃L_A20]Br₂(313.4mg,0.6mmol), Iridium metal precursor ([ Ir (cod) Cl)]₂200mg,0.3mmol) and acetonitrile (20 mL). Nitrogen was introduced using a needle and the solution was degassed for 5 minutes, after which triethylamine (2mL) was added and heated to 90 ℃ and the reaction stopped after 12 hours. Removing organic solvent at low pressure, adding HL under the protection of nitrogen_B2(168mg,0.6mmol) and 2-ethoxyethanol (20 mL). The mixture was heated to 150 ℃ and stirred overnight. The reaction was stopped, cooled to room temperature and filtered. The solvent was removed under reduced pressure, followed by silica gel column chromatography, and the mobile phase was separated and purified using dichloromethane to dichloromethane/ethyl acetate (volume ratio 50:1) to obtain the objective product (27mg,0.029mmol), yield: 5 percent.¹H NMR (400 mhz, deuterated chloroform) × 11.30-11.19 (m,1H), 9.56-9.44 (m,1H), 8.58-8.39 (m,2H), 8.11-7.89 (m,3H), 7.86-7.72 (m,2H),7.52(d, J ═ 2.1Hz,2H),7.48(s,2H),7.01(t, J ═ 7.7Hz,1H),6.70(d, J ═ 2.1Hz,2H),6.29(dd, J ═ 7.6,0.8Hz,1H),3.01(dd, J ═ 57.0,13.3,10.7,5.6Hz,4H), 1.18-1.05 (m,2H), 0.77-0.60 (m, 25.05H), 0.05-10.05 (m, 2H).¹⁹F NMR (376 mhz, deuterated chloroform): δ -60.33(s) ppm.

Example 13

Synthesis of Iridium Complex (L)_A20)Ir(L_B2)(L_C2) Synthesis of example Ir6 b:

adding (L) into a two-mouth bottle with magnetons under the protection of nitrogen_A20)Ir(L_B2)(L_C1) (27mg,0.029mmol), silver cyanide (7.8mg,0.058mmol), and N, N-dimethylformamide (20 mL). The reaction solution was heated to 100 ℃ and the reaction was stopped after 2 hours. The N, N-dimethylformamide was removed under reduced pressure to obtain a luminescent solid. The mixture was subjected to silica gel column chromatography, and the mobile phase was separated from dichloromethane to dichloromethane/ethyl acetate (volume ratio 5:1) to obtain the objective product (13mg,0.15mmol), yield: 51 percent.¹H NMR (400 mhz, deuterated chloroform) × 10.65(dd, J ═ 9.0,1.2Hz,1H),9.47(dd, J ═ 7.8,1.7Hz,1H),8.48(ddd, J ═ 20.3,8.3,1.4Hz,2H),8.12(ddd, J ═ 8.7,6.8,1.6Hz,1H),7.99(ddd, J ═ 8.1,6.7,1.2, 2H),7.77(dtd, J ═ 18.4,7.1,1.5Hz,2H),7.53(d, J ═ 2.1Hz,2H),7.47(s,2H),7.07(t, J ═ 7.6, 1H), 6.71.7 (d, J ═ 2.1Hz,2H), 7.3.0.7.3H, 7.7.7.7.7.3, 7.7.7.7.7 (ddh), 7.7.3H, 7.7.7.7.7.7.7, 7.7.7, 7, 7.0, 7,3, 7.7.7.7.7.7, 7.7, 3, 0, 3, 0, 3, 0, 3, 0, 3, m, etc.¹⁹F NMR (376 mhz, deuterated chloroform): δ -60.43(s) ppm.

Examples photophysical test data for iridium (III) complexes:

absorption and emission spectrum data of the complexes Ir1a, Ir1b, Ir2a, Ir2b, Ir2c, Ir2d, Ir3a, Ir3b, Ir4a, Ir4b, Ir5a, Ir6a and Ir6b are shown in Table 1, and solution state spectrum data are obtained by dissolving a light-emitting material in a dichloromethane solution (the concentration is 2 × 10 unless otherwise specified) in the examples^-5M) measurement after air removal.

In the electronic vibration absorption spectrum of the iridium (III) complex in the solution state in all the examples, the ultraviolet absorption spectrum of less than 350nm shows a strong absorption band, and the molar extinction coefficient is more than 5 multiplied by 10³M^-1cm^-1Generally assigned to pi-pi transition of the ligand. A medium absorption band (molar extinction coefficient of 3X 10) of 350-480 nm³M^-1cm^-1To 2X 10⁴M^-1cm^-1) Metal to ligand charge transfer respectively assigned to singlet states: (¹MLCT) or singlet ligand center charge transition/ligand charge transfer ((ii)¹LC/¹LLCT). The absorption band increases with the conjugation system of the chromophore ligands¹LC/¹LLCT component is increased. Weak absorption band with wavelength greater than 450nm and molar extinction coefficient of 2X 10³M^-1cm^-1To 9X 10³M^-1cm^-1The weak absorption band of (a) is due to metal-to-ligand charge transfer of the triplet state: (³MLCT) and charge transition/ligand charge transfer of triplet ligand centers ((ii)³LC/³LLCT)。

In solution, the emission peak of the iridium (III) complex of the example covers the green to near infrared region (554- & 712 nm). Wherein, the highest peaks of the emission peaks of Ir2a and Ir4a are respectively positioned at 699nm and 712nm, and the quantum yields are respectively 0.32 and 0.15. The luminescence properties of the iridium (III) complexes Ir2b and Ir4b of the examples change after the substitution of the bromo group by cyano group: 1, blue shifting an emission peak, and blue shifting the highest peak to 632nm and 645nm respectively; 3, the quantum yield of Ir2b is obviously improved compared with that of Ir2a, namely improved from 0.32 to 1.00. The quantum yield of Ir4b is obviously improved compared with that of Ir4a, namely the quantum yield is improved from 0.15 to 0.80; the change in CIE (x, y) values in the chromaticity CIE coordinates (Commission internationale de L' E class coordinates) is evident, decreasing from (0.71,0.29) for Ir2a and (0.72,0.28) for Ir4a to (0.67,0.33) for Ir2b and (0.68,0.32) for Ir4b, respectively. Wherein the CIE (x, y) of the complex Ir2b is (0.67,0.33), the color is the standard red recommended by the National Television System Committee (NTSC), and the ultra-high quantum efficiency (1.00) of Ir2b makes the complex Ir2b have high potential for industrial application in OLEDs.

Fig. 1 to 4 are photophysical test charts, including absorption and emission spectra, of iridium (III) complex Ir1a, Ir1b, Ir2a, Ir2b, Ir2c, Ir2d, Ir3a, Ir3b, Ir4a, Ir4b, Ir5a, Ir6a and Ir6b, respectively. The test concentrations of the examples are all 2X 10^–5M, and all of them are subjected to air removal treatment, and the photophysical properties of each luminescent material are shown in Table 1:

TABLE 1

A single crystal of Ir2b (FIG. 5) suitable for X-ray diffraction analysis was obtained by slow evaporation of diethyl ether into a dilute solution of Ir2b in dichloromethane. The single crystal was monoclinic, space group was I2/c, and other single crystal data are shown in Table 2. As can be seen in FIG. 5, the iridium atom (Ir1) in the single crystal adopts an approximately regular octahedral configuration with 5 carbons, respectivelyThe atom coordinates with 1 nitrogen atom, wherein the nitrogen atom (N5) from the bidentate ligand forms an approximate linear included angle with the carbon atom (C4) on the benzene ring of the tridentate ligand, and the angle is 172.8 degrees; the cyano carbon (C41) of the monodentate ligand forms an approximately linear angle with the carbon atom (C21) of the bidentate ligand, the angle being 176.2 °; the carbon atoms (C1 and C10) of the two N-heterocyclic carbenes in the tridentate ligand form an obtuse angle, and the included angle is 155.1 degrees. Iridium-carbon (cyano) distance of

Distance of iridium to carbon (N-heterocyclic carbene)

And

distance of iridium to carbon (bidentate ligands)

Distance of iridium to nitrogen (bidentate ligands) is

The single crystal diffraction data of the iridium (III) complex Ir2b are shown in table 2:

TABLE 2

Examples thermogravimetric analysis data of iridium (III) complexes:

the thermal decomposition temperatures (95% by mass) of the iridium (III) complex were 412 ℃ (Ir2a), 427 ℃ (Ir2b) and 510 ℃ (Ir2d), respectively, and the thermogravimetric analysis thereof is shown in fig. 6. Therefore, the complex meets the pyrolysis deposition condition required by OLED film preparation.

Application example iridium (III) complex preparation device 1:

this example uses iridium (III) complex Ir2b as the phosphorescent dopant for the preparation of an electroluminescent device 1. The device structure is as follows: ITO/HI

/HT1

/HT2

/Ir2b:RH(3wt％；

)/ET

/Liq

/Al

The HI, HT1, HT2, ET and Liq (structure formula shown in figure 7) are respectively used as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL) and an Electron Injection Layer (EIL). All materials were subjected to continuous high vacuum thermal deposition without breaking vacuum. After the whole deposition process is finished, the test is directly carried out under the room temperature condition. The electroluminescence characteristics of the device are shown in table 3, each item of data of the device is tested and recorded by adopting Binchong C9920-12, and a power supply adopts Keithley 2400 equipment. The electroluminescence spectrum of the device 1 is shown in fig. 8.

TABLE 3

The structure of the device 1 of the example is as follows: ITO/HI

/HT1

/HT2

/Ir2b:RH(3wt％；

)/ET

/Liq

/Al

As indicated above, table 3 shows the device data for the preparation of OLED device 1 using example Ir2 b.

The results of table 3 and fig. 8 show that the [3+2+1] coordination configuration iridium metal complex designed in the invention can successfully prepare an OLED device and realize red light emission. The CIE color coordinates (0.67,0.32) of device 1 are close to the standard red color recommended by NTSC (0.67, 0.33). The electroluminescence spectrum of the organic electroluminescent device provided by the device 1 of the comparative example is shown in FIG. 8 and the physical spectrum 4 of the complex Ir2b used in this example. The luminescence spectrum of the electroluminescent material is approximately consistent with that of the phosphorescent material, so that the luminescent material is proved to be suitable for preparing luminescent devices by evaporation, and the luminescence of the obtained devices is basically from the complex designed by the invention.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. A kind of rice cakeFormation of [3+2+1] with tridentate, bidentate and monodentate ligands]Iridium (III) complex of type coordination configuration: (L)_A)Ir(L_B)(L_C) Wherein Ir is a group VIIIB, 6 th period transition metal iridium, the total oxidation state of which is + 3; l is_AIs a tridentate ligand, the total oxidation state of which is-1; l is_BIs a bidentate ligand, the total oxidation state of which is-1; l is_CIs a monodentate ligand having a total oxidation state of-1, said iridium (III) complex being neutral and having the following structure of formula (I):

wherein the content of the first and second substances,

each A¹-A⁵Independently selected from C, N;

each A⁹，A¹⁵Independently selected from C, N;

R^A，R¹may be the same or different and are independently selected from hydrogen, halogen, CF₃，–CN，–OR’，–Si(R’)₃，–N(R’)₂，–SR’，–P(R’)₂，–C(O)R’，–C(O)OR’，–C(O)NR’，–SOR’，–SO₂R’，–SO₃R’，–P(O)(R’)₂，–P(O)(OR’)R’，–P(O)(OR’)₂C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' in the same group, which may be the same or different, is independently selected from: hydrogen, -CN, halogen, C1-C40 alkylC2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl;

or the like, or, alternatively,

R^Aany two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl;

R^B，R^Cindependently selected from: -O (R '"), -N (R'")₂，–SO(R”’)，–SO₂(R”’)，–P(R”’)₂，–PO(R”’)₂，–PO(OR”’)(R”’)，–PO(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C1-C40 alkoxy, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroalkylAn aryl group; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' "in the same group, which may be the same or different, are independently selected from: hydrogen, halogen, C1-C40 alkyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocyclyl, C3-C40 aryl, C3-C40 heteroaryl, wherein the heteroatom is N, S, O;

or the like, or, alternatively,

R^Band R^CAny two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl;

the R is^dSelected from-O (R '"), -N (R'")₂，–SO(R”’)，–SO₂(R”’)，–P(R”’)₂，–PO(R”’)₂，–PO(OR”’)(R”’)，–PO(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C1-C40 alkoxy, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR' ",–N(R”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl; r' "in the same group, which may be the same or different, are independently selected from: hydrogen, halogen, C1-C40 alkyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocyclyl, C3-C40 aryl, C3-C40 heteroaryl, wherein the heteroatom is N, S, O;

or the like, or, alternatively,

R^dany two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 aryl, C3-C40 heteroaryl;

n is 0,1, 2 or 3; m is 0,1, 2;

o is 0,1 or 2;

p and q are independently integers from 0 to 4;

2. The iridium (III) complex as claimed in claim 1, wherein R^A，R¹May be the same OR different and is independently selected from hydrogen, halogen, -CN, -OR ', -Si (R')₃，–N(R’)₂，–SR’，–P(R’)₂，–C(O)R’，–C(O)OR’，–SOR’，–SO₂R', C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; r' in the same group, which may be the same or different, is independently selected from: hydrogen, -CN, halogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl;

R²selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl, -C (O) R ', -C (O) OR'; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR ', -N (R')₂，–Si(R”)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; r' in the same group may be the same or different and is independently selected from: hydrogen, -CN, halogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl.

3. The complex of formula (I) according to claim 1, wherein the ligand L_AIs selected from L_A1To L_A21Any one of which has the following structure:

4. the complex of formula (I) according to claim 1, wherein the ligand L_BIn, R^B，R^CIndependently selected from: -O (R '"), -Si (R'")₃，–N(R”’)₂，–SO₂(R”’)，–P(R”’)₂C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl; the above alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl groups are optionally substituted with one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C6-C20 heteroaryl; r' "in the same group, which may be the same or different, are independently selected from: hydrogen, halogen, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocyclyl, C3-C20 aryl, C3-C20 heteroaryl, wherein the heteroatom is N, S, O;

or the like, or, alternatively,

the alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl are optionally substituted with one or more substituents independently selected from the group consisting of: halogen, -CN, -OR '", -N (R'")₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl, wherein the heteroatoms are N, S and O;

or the like, or, alternatively,

R^dany two adjacent groups thereof form a 5-7 membered aryl or heteroaryl group, an 8-10 membered fused bicyclic aryl or heteroaryl group, or an 11-14 membered fused tricyclic aryl or heteroaryl group with the ring atoms to which they are attached, which may be substituted with any one or more substituents independently selected from: halogen, -CN, -OR '", -N (R'")₂，–SR”’，–P(R”’)₂，–C(O)R”’，–C(O)OR”’，–C(O)NR”’，–SOR”’，–SO2R”’，–SO3R”’，–P(O)(R”’)₂，–P(O)(OR’)R”’，–P(O)(OR”’)₂，–Si(R”’)₃C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 aryl, C3-C20 heteroaryl.

5. The complex of formula (I) according to claim 1, wherein the ligand L_BA ligand selected from the group consisting of:

6. the complex of formula (I) according to claim 1, wherein the monodentate ligand L_CSelected from: cl, Br, I, CN, OCN, SCN, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 acyloxy, C6-C12 aryl, C6-C12 heteroaryl, C2-C8 alkynyl.

7. An iridium (III) complex for an OLED light-emitting material, the iridium (III) complex having the following structure of formula (II):

wherein L is_CY＝Br^-(L_C1)，CN^-(L_C2)，I^-(L_C3)；

8. The complex of formula (II) as claimed in claim 7 for use in an OLED light-emitting material, selected in particular from the following compounds:

9. a process for preparing the iridium (III) complex as claimed in claims 1 to 6, which comprises:

with [ H ]_x+1L_A]Br_xIridium metal precursor and HL_BObtaining an iridium (III) complex shown as a formula (Ir-a) by a one-pot method; further subjecting L of an iridium (III) complex represented by the formula (Ir-a)_C1Reacting M (L) by metathesis_C)_yMonodentate ligand L of_CSubstituting iridium metal to obtain an iridium (III) complex shown as a formula (I);

wherein x is 1, 2;

wherein said M (L)_C)_yIs said monodentate ligand L_CA salt with a metal M having an oxidation state of +1/+2 valency, said metal M being selected from the group consisting of Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Cu, Ag, Au, Zn, Cd and Hg, wherein y is 1, 2.

10. The process of claim 9, wherein the one-pot process comprises the steps used to prepare formula (Ir-a): the ith step is that_x+1L_A]Br_xAdding iridium metal precursor and alkali into solvent, removing solvent at the end of reaction and directly making reaction of step ii without separation, wherein step ii is specifically described as adding HL_BAnd heated to the selected temperature of the reaction.

Wherein, the iridium metal precursor is bis (1, 5-cyclooctadiene) iridium chloride (I) dimer, which is abbreviated as: [ Ir (cod) Cl]₂The base being organicBases (e.g. triethylamine, NEt)₃) The reaction temperature in step i was 90 ℃ and the reaction solvent was acetonitrile (MeCN), the solvent used in step ii was 2-ethoxyethanol (2-EtOEtOH) and the reaction temperature was 150 ℃.

11. The method of claim 10, wherein the metal salt used in the second step of preparing formula (I) is a silver salt and the solvent is N, N-dimethylformamide.

12. A process for preparing an iridium (III) complex of formula (II) as claimed in claim 7, which comprises the steps of:

the ith step: in which an iridium (III) complex of the formula (IV-1) in which L is_C1To a 25mL chlike tube (Schlenk tube) with magnetons under nitrogen blanket was added 1mmol [ H ═ Br₃L_A1]Br₂0.5mmol of Iridium metal precursor [ Ir (cod) Cl ]]₂And 20mL of acetonitrile, nitrogen is introduced by means of a needle and the solution is degassed for 5 minutes, 2mL of triethylamine is added and the reaction is stopped after heating to 90 ℃ for 12 hours, after the organic solvent has been removed under reduced pressure, 1mmol of HL is added under the protection of nitrogen_BAnd 10mL of 2-ethoxyethanol, the mixture was heated to 150 ℃ and stirred overnight. Stopping reaction, cooling to room temperature, removing solvent under reduced pressure, separating and purifying by silica gel column chromatography, and collecting mobile phase from dichloromethane to dichloromethane/ethyl acetate (volume ratio of 50:1) to obtain crude product with luminescence, and drying if passing through¹After H NMR characterization, the crude product is confirmed to be a target product of the iridium (III) complex shown in the formula (IV-1), and can be directly used;

Adding the formula (IV-1) into a two-mouth bottle with magnetons under the protection of nitrogen, and adding 2 times of equivalent of silver salt AgL_CAnd 20mL of N, N-dimethylformamide, heating the reaction mixture to 90 deg.C, stopping the reaction after two hours, and removing under reduced pressureAnd (3) obtaining a luminescent crude product by using N, N-dimethylformamide, separating by using silica gel column chromatography, and obtaining a target product shown in the formula (II) by using dichloromethane to dichloromethane/ethyl acetate (the volume ratio is 10:1) as a mobile phase.

13. An electroluminescent device comprising:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

and an organic layer disposed between the anode and the cathode, the organic layer comprising a light emitting device prepared from a complex of formula (I) or formula (ii) as defined in claims 1 to 8.

14. The light-emitting device according to claim 13, wherein the organic layer comprises each type of charge transport layer and a light-emitting layer, and the light-emitting layer comprises a host material and the complex of formula (I) or formula (ii) according to claims 1 to 8 as a light-emitting material for the light-emitting layer.

15. The light emitting device of claim 14, wherein the device emits light in a characteristic wavelength band (from ultraviolet to near infrared) emitted by the formula (I) or formula (ii) complex of claims 1-8, or the device is passed through a device fabrication process comprising stacking a plurality of light emitting layers, doping with other light emitting materials, wherein any of the light emitting layers emits mixed light using the formula (I) or formula (ii) complex of claims 1-8.