CN114181263A - Monocarborane anion platinum complex-containing blue light material and preparation method and application thereof - Google Patents

Monocarborane anion platinum complex-containing blue light material and preparation method and application thereof Download PDF

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CN114181263A
CN114181263A CN202111566925.9A CN202111566925A CN114181263A CN 114181263 A CN114181263 A CN 114181263A CN 202111566925 A CN202111566925 A CN 202111566925A CN 114181263 A CN114181263 A CN 114181263A
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monocarborane
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沈云军
杨峰杰
邱慧
张玉贞
边贺东
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Guangxi University for Nationalities
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Abstract

A platinum complex blue light material containing monocarborane anions is characterized in that the monocarborane anions are introduced into a cyclometalated platinum complex with carbazole pyridine and bis-carbene as ligands to realize intramolecular charge balance; compared with the existing platinum blue light material, the preparation method of the platinum blue light complex is simple, the product is easy to purify, the yield is higher, and the platinum blue light complex has better practicability; the introduction of borane anions with a three-dimensional large-volume structure can effectively inhibit a non-radiative decay heat production path, and is beneficial to the improvement of the luminescent performance of the platinum complex. Based on the good solubility of the complex in an organic solvent, the blue light material-doped organic electroluminescent device is successfully prepared by adopting a solution method with lower cost, the device has narrower electroluminescent spectrum and good luminous purity, most of the spectrum is positioned in a deep blue region, and the luminous peak value is 448 nm. The application of the platinum complex containing carborane anions in a luminescent device provides a new way for designing and developing high-efficiency blue phosphorescent materials.

Description

Monocarborane anion platinum complex-containing blue light material and preparation method and application thereof
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of photoelectric materials, and particularly relates to a monocarborane anion platinum complex containing blue-light emitting material and application thereof in an organic light emitting device.
[ background of the invention ]
Organic Light Emitting Diodes (OLEDs), which are currently considered as the best candidates for next-generation flat panel display and solid state lighting technologies, are used as a key material in OLED display, i.e., OLED organic light emitting materials, which have many advantages over previous LEDs, such as unique advantages of fast response, high resolution, softness, and the like. Full-color display and white light illumination of the OLED require three primary colors of red, green and blue, but the blue-light metal platinum complex which has high efficiency, high color purity and can be processed by solution is less. Due to the requirement of the properties of the blue light material, the energy gaps of the LUMO and HOMO of the molecular front orbitals must be large enough to emit blue light, but high-energy molecules are often unstable, and how to obtain a high-performance blue light material through ligand design remains the focus and difficulty of research on OLEDs. Through the development of the last ten years, the research space of the blue light complex in the application field of molecular structure and optical function is narrower and narrower at present, so that the introduction of an organic unit with a novel structure and electronic properties becomes an innovative strategy for developing a phosphorescent material with excellent performance.
The caged carborane is an atomic cluster compound consisting of carbon atoms and boron atoms, has quite high thermal stability, and the most representative of the caged carborane is electrically neutral dicarboborane C with an icosahedral structure2B10H12The study of the caged borane molecules in the field of luminescent materials has received extensive attention in the last decade. Research results show that when the bulky cage structure is introduced into the metal complex, the energy gap and the phosphorescence efficiency of the luminescent material can be adjusted, the intermolecular interaction can be obviously reduced, and solid triplet-triplet annihilation is inhibited. Monocarborane anion CB11H12And neutral C2B10H12Are isoelectric, which theoretically have the same purpose. Although both clusters have large steric hindrance and significant chemical and thermal stability, the former is unique in that it has a negative charge. However, due to the limitation of raw material synthesis, few reports exist in the literature on the construction of metal complex luminescent materials by using monocarborane anions, and particularly, few studies on the application of carborane compounds to OLEDs are available. Therefore, the application of the monocarbodecane anion to develop the metal platinum complex blue-light luminescent material with excellent performance has very important research value.
[ summary of the invention ]
Aiming at the problems, the invention provides a preparation method of a monocarborane anion platinum complex-containing blue light emitting material and application of the monocarborane anion platinum complex-containing blue light emitting material in an organic electroluminescent device, so as to solve the problems of complex synthesis of the existing blue phosphorescent material, low color purity of the device, high manufacturing cost and the like.
The invention discloses a bivalent platinum complex containing monocarborane anions, which has the following structural general formula:
Figure BDA0003422100700000021
wherein, -R is the following group: c4～12The linear alkyl group of (1); r1And R2respectively-CB11H11And H, when R1When is H, R2is-CB11H11When R is1When is H, R2is-CB11H11，R3is-CH3Any one of H, tertiary butyl and aryl; n is 1-6, X is C or N, when the ligand is benzimidazole or imidazole ligand, X is C, and when the ligand is triazole, X is N; -CB11H11Is a monocarborane anion, and has the following structure:
Figure BDA0003422100700000022
the invention provides a preparation method of a monocarborane anion platinum complex blue-ray material, which comprises the following steps:
s1, adding a metal organic compound I into a solvent I, heating a silicone oil pot to 60 ℃, stirring by using a magnetic stirrer, adding silver trifluoromethanesulfonate under the condition of keeping out of the sun, and continuously stirring for one hour, wherein the metal organic compound I has the following structural formula:
Figure BDA0003422100700000031
s2 adding compound II and alkali in N2And (3) carrying out reaction under protection to obtain a reaction mixture, wherein the reaction temperature is 60 ℃, the reaction time is 12h, and the compound II has the following structural formula:
Figure BDA0003422100700000032
s3, cooling the mixture to room temperature, filtering the solid with diatomite to obtain a reaction solution, removing all the solvent I in vacuum, and then separating and purifying in a column chromatography separation mode to obtain a novel divalent platinum complex containing monocarborane functionalization, namely a monocarborane anion platinum complex blue-light material.
In particular, the first solvent is dichloromethane and tetrahydrofuran, and the base is potassium tert-butoxide.
In particular, the molar ratio of compound I to compound II is 1:1.1 to 1.2, and the ratio of compound I to solvent I is 1 mmol: 80 to 150 mL.
In particular, the compound I in S1 is prepared by the following method:
s11 adding compound III and platinum compound into solvent II, in N2The temperature is raised to 110 ℃, and the mixture is stirred and reacted for 10 hours, so as to obtain a first mixture, wherein the structural formula of the compound III is as follows:
Figure BDA0003422100700000041
s12 removing solvent II from the mixture I by distillation under reduced pressure, extracting the obtained solid with dichloromethane, extracting the organic phase with distilled water three times, drying the organic phase with anhydrous magnesium sulfate, removing dichloromethane by rotary evaporation, purifying by column chromatography and drying to obtain compound I.
Specifically, the platinum compound is platinum acetylacetonate, and the second solvent is dimethyl sulfoxide.
In particular, the molar ratio of compound III to platinum compound is 1:1.1 to 1.2.
In particular, the compound II is prepared by the following method:
s21, placing carborane into a reaction flask, pumping out air in the reaction flask by using a vacuum pump, and introducing N2In N at2Adding a solvent III, adding n-butyllithium into the reaction solution at the temperature of 0 ℃, stirring for reaction for 1.5h, then adding cuprous iodide, and stirring for reaction for 45 min;
s22, adding a palladium catalyst, a phosphorus ligand and a compound IV, and stirring and reacting for 20-24 hours at room temperature, wherein the compound IV has the following structural formula:
Figure BDA0003422100700000042
and (3) after the reaction of S23, filtering the solid with kieselguhr to obtain a second reaction solution, removing the third solvent in vacuum, dissolving the obtained solid with diethyl ether, extracting the organic phase with hydrochloric acid for three times, taking the organic phase, performing rotary evaporation to obtain a solid, adding water to dissolve the solid, adjusting the pH value with alkali until the aqueous solution is alkaline, performing cation exchange to obtain a solid product, and performing column chromatography separation and purification to obtain a compound II.
In particular, said X1Is a halogen group, the solvent III is tetrahydrofuran, the palladium catalyst is palladium acetate, the phosphorus ligand is tri (di-methoxyphenyl) phosphine, and the molar ratio of carborane to the compound IV or the compound V is 1: 1.1.
The invention also provides application of the monocarborane anion platinum complex containing blue light material in an organic electroluminescent device, wherein a light emitting layer in the organic electroluminescent device contains the monocarborane anion platinum complex blue light material.
The invention has the following beneficial effects: the invention provides a preparation method of a monocarborane anion platinum complex-containing blue-light material with a relatively simple synthetic route and high yield, and by introducing a monocarborane anion ligand with a large steric hindrance and a three-dimensional structure, the interaction among molecules is effectively reduced, so that triplet state-triplet state annihilation is inhibited; by introducing a double-carbene strong field ligand, the non-radiative decay is greatly reduced, and the luminescence is effectively blue-shifted; the finally prepared platinum complex blue light material has the advantages of narrow emission spectrum, high stability and the like, and the preparation of the low-cost organic light-emitting device can be realized by adopting a solution processing technology.
[ description of the drawings ]
FIG. 1 shows a compound S of the present invention1A crystal structure diagram;
FIG. 2 shows a compound S of the present invention2A crystal structure diagram;
FIG. 3 shows a compound S of the present invention1，S2An ultraviolet absorption spectrum chart;
FIG. 4 shows a compound S of the present invention1，S2(ii) solution emission spectra;
FIG. 5 shows a compound S of the present invention1，S2Solid state emission spectroscopy;
FIG. 6 shows a compound S of the present invention1，S2PMMA emission spectrum;
FIG. 7 shows a compound S of the present invention1，S2Electroluminescence spectrum.
FIG. 8 is a voltage current density characteristic of an OLED device of the present invention.
FIG. 9 is a voltage-luminance characteristic of an OLED device of the present invention.
FIG. 10 is a diagram of the energy level and chemical structure of an OLED device according to the present invention.
[ detailed description ] embodiments
The following description will be further clearly and completely made on the preparation method of the monocarborane anion platinum complex containing blue light material and the application thereof in the organic electroluminescent device mainly by combining the attached drawings and the specific embodiment. The complex belongs to a novel bivalent platinum complex containing monocarborane functionalization, and has the following structural general formula:
Figure BDA0003422100700000061
wherein, -R is the following group: c4～12The linear alkyl group of (1); r1And R2respectively-CB11H11And H, when R1When is H, R2is-CB11H11When R is1When is H, R2is-CB11H11，R3is-CH3Any one of H, tertiary butyl and aryl; n is 1-6, X is C or N, when the ligand is benzimidazole or imidazole ligand, X is C, and when the ligand is triazole, X is N; -CB11H11Is a monocarborane anion, and has the following structure:
Figure BDA0003422100700000062
the invention also provides a preparation method of the monocarborane anion platinum complex blue-ray material, which comprises the following steps:
s1, adding a metal organic compound I into a solvent I, heating a silicone oil pot to 60 ℃, stirring with a magnetic stirrer, adding silver trifluoromethanesulfonate under the condition of keeping out of the sun, and continuously stirring for one hour, wherein the solvent I is dichloromethane or tetrahydrofuran, and the metal organic compound I has the following structural formula:
Figure BDA0003422100700000071
s2 adding compound II and alkali in N2Reacting under protection to obtain a reaction mixture, wherein the reaction temperature is 60 ℃, the reaction time is 12h, and obtaining a mixtureThe base is potassium tert-butoxide, and the structural formula of the compound II is as follows:
Figure BDA0003422100700000072
s3, cooling the mixture to room temperature, filtering the solid with diatomite to obtain a reaction solution, removing all the solvent I in vacuum, and then separating and purifying in a column chromatography separation mode to obtain a novel divalent platinum complex containing monocarborane functionalization, namely a monocarborane anion platinum complex blue-light material.
In particular, the molar ratio of compound I to compound II is 1:1.1 to 1.2, and the ratio of compound I to solvent I is 1 mmol: 80 to 150 mL.
In the invention, the compound I in S1 is prepared by the following method:
s11 adding compound III and platinum compound into solvent II, in N2The temperature is raised to 110 ℃, and the reaction is stirred for 10 hours, so that a first mixture is obtained, wherein the platinum compound is platinum acetylacetonate, the second solvent is dimethyl sulfoxide, and the molar ratio of the compound III to the platinum compound is 1: 1.1-1.2, and the compound III has the following structural formula:
Figure BDA0003422100700000081
s12 removing solvent II from the mixture I by distillation under reduced pressure, extracting the obtained solid with dichloromethane, extracting the organic phase with distilled water three times, drying the organic phase with anhydrous magnesium sulfate, removing dichloromethane by rotary evaporation, purifying by column chromatography and drying to obtain compound I.
In the invention, the compound II in S2 is prepared by the following method:
s21, placing carborane into a reaction flask, pumping out air in the reaction flask by using a vacuum pump, and introducing N2In N at2Adding solvent III into the reaction solution at 0 deg.CN-butyllithium is stirred and reacted for 1.5h, then cuprous iodide is added, and the mixture is stirred and reacted for 45min, wherein the solvent III is tetrahydrofuran;
s22, adding a palladium catalyst, a phosphorus ligand and a compound IV, stirring and reacting for 20-24 h at room temperature, wherein the palladium catalyst is palladium acetate, the phosphorus ligand is tris (2-methoxyphenyl) phosphine, and the compound IV has the following structural formula:
Figure BDA0003422100700000082
and (3) after the reaction of S23, filtering the solid with kieselguhr to obtain a second reaction solution, removing the third solvent in vacuum, dissolving the obtained solid with diethyl ether, extracting the organic phase with hydrochloric acid for three times, taking the organic phase, performing rotary evaporation to obtain a solid, adding water to dissolve the solid, adjusting the pH value with alkali until the aqueous solution is alkaline, performing cation exchange to obtain a solid product, and performing column chromatography separation and purification to obtain a compound II.
In particular, said X1Is a halogen group, and the molar ratio of the carborane to the compound IV or the compound V is 1: 1.1.
Specifically, the synthesis process for preparing the monocarborane anion platinum complex blue-light emitting material from the compound III and the compound IV is as follows:
Figure BDA0003422100700000091
the preparation method is simple, the reaction condition is mild, and the practicability is good. In order that the invention may be more clearly understood, the invention is further illustrated by the following description taken in conjunction with the specific examples.
Example 1
This example provides a platinum Complex S containing a Monocarborane anion1The structural formula is as follows:
Figure BDA0003422100700000092
platinum complex S containing monocarborane anion1The synthetic route of (2) is as follows:
Figure BDA0003422100700000101
the preparation method comprises the following specific steps:
1) place platinum acetylacetonate (2g,5.09mmol) in a 250ml two-neck round-bottom flask, transfer 5ml of dimethyl sulfoxide to the flask under nitrogen, dissolve ligand III-1 (2.47g, 5.49mmol) in 20ml of dimethyl sulfoxide, slowly add dropwise to the reaction system, and mix in N2Reflux for 10 hours. After cooling the reaction mixture to room temperature and removing all solvents by distillation under reduced pressure, the solid was dissolved in dichloromethane, extracted 3 times, the organic phase was dried over magnesium sulfate, the organic solvent was dried by spinning, and the resulting crude product was isolated and purified by column chromatography to give compound i-1 as a white solid.
2) Carborane (600mg,3.0mmol) was dissolved in 25ml of anhydrous tetrahydrofuran under a nitrogen atmosphere, and stirred, n-butyllithium was added, after a reaction period, cuprous iodide (628mg, 3.3mmol) was added, and after a reaction period, palladium acetate (80mg, 0.33mmol), tris (2-methoxyphenyl) phosphonium (348mg, 1mmol), compound IV-1(772mg, 3.3mmol) were added and reacted under a nitrogen atmosphere. And after the reaction is finished, filtering the solid, carrying out vacuum spin-drying on the obtained filtrate, dissolving the solid by using ether, extracting by using hydrochloric acid, carrying out spin-drying on an organic phase, carrying out cation exchange to obtain a solid crude product, and carrying out column chromatography separation and purification to obtain the final product (II-1).
3) I-1 (100mg, 0.15mmol) was dissolved in a mixed solution of 12ml of dichloromethane and 6ml of tetrahydrofuran under a nitrogen atmosphere, silver trifluoromethanesulfonate (81mg, 0.32mmol) was added in the absence of light, and the mixture was stirred at 60 ℃ for 1 hour, whereupon formation of a precipitate was observed. Compound II-1 (70mg, 0.16mmol) was added thereto and stirred for 0.5h, potassium tert-butoxide (34mg, 0.30mmol) was added thereto, and the mixture was stirred under nitrogen at 60 ℃ for 5 h. Filtering the solid, spin-drying the obtained filtrate, purifying the crude product by using a silica gel chromatographic column to obtain the final platinum complex S containing the monocarborane anion1。
Example 2
This example provides a platinum Complex S containing a Monocarborane anion2The structural formula is as follows:
Figure BDA0003422100700000111
the specific preparation procedure is as described in example 1, except that compound IV-1 is replaced by compound IV-2.
Platinum complex S containing monocarborane anion2The synthetic route of (2) is as follows:
Figure BDA0003422100700000112
example 3
Using the solution method, the platinum Complex S obtained in example 11The incorporation of the complex as a luminescent material into a host material produces a deep blue organic electroluminescent device, which is attributed to the high quantum yield of the complex in thin films and the solubility in common organic solvents. The energy level diagram and chemical structure of the organic material are shown in fig. 5. The device comprises ITO/PEDOT, PSS (45nm)/S1, PYD2(60nm)/DPEPO (10nm)/TPBI (40nm)/LiF (1nm)/Al (100nm) in sequence, poly (ethylene dioxythiophene), poly (styrene sulfonate) (PEDOT: PSS) is used as a hole injection/transmission layer, and bis [2- (diphenylphosphino) phenyl group]Ether oxide (DPEPO) and 1,3, 5-tris (1-phenyl-1 hydro-benzo [ d ]]Imidazol-2-yl) benzene (TPBi) acts as a hole/exciton blocking layer and an electron transport layer, respectively. S1Doped as an emissive dopant in PYD2 with doping concentrations varying from 12 wt% to 20 wt%.
TABLE 1 platinum-based Complex S at different doping concentrations1Critical performance of the OLED
Figure BDA0003422100700000121
Remarking: [ a ] A]The maximum brightness. [ b ] a]A maximum value. [ c ] is]At 100cd m-2In CIE coordinates. [ d]At 100cdm-2The maximum of the electroluminescence spectrum. [ g ]]100cdm-2Half-peak width of the electroluminescence spectrum.
As shown in fig. 7, when the concentration of the dopant was increased from 12 wt% to 20 wt%, no shift of the electroluminescence spectrum was observed, indicating that the borane anion having a three-dimensional bulky structure effectively suppresses the interaction between the complex molecules. The maximum value of the device EL spectrum is 448nm, the full width at half maximum (FWHM) value is 60nm, deep blue emission with CIE coordinates (0.17,0.15) is generated, and other material emission peaks do not exist in the spectrum, which indicates that the device structure is reasonably designed, and effective energy transfer is realized between hosts and objects.
From the above, it can be seen that: the organic electroluminescent material, namely the monocarborane anion platinum complex-containing blue light emitting material has good electroluminescent performance and good solubility in an organic solvent, can be applied to the preparation of OLED light emitting devices by a solution method, and can be seen to be improved in phosphorescence efficiency and color purity to different degrees compared with the known OLED material by combining with figures 1-9 and table 1.
Fig. 8 is a voltage-current density characteristic curve of an OLED device prepared by using the platinum complex of the present invention, fig. 9 is a voltage-luminance characteristic curve of the OLED device, fig. 10 is an energy level and chemical structure diagram of the OLED device, and it can be seen from fig. 8-10 that when the monocarborane anion platinum complex-containing blue light material prepared by the present invention is applied to an organic electroluminescent device (OLED device), the voltage-current density and voltage-luminance thereof meet the requirements of the device itself, and are even superior to the OLED device prepared by the existing solution method.
The above examples are preferred embodiments of the present invention, and are described in detail and specific, but should not be construed as limiting the scope of the claims. It should be noted that any suitable modification, replacement, improvement and the like made by those skilled in the art without departing from the principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. A monocarborane anion platinum complex-containing blue light material is characterized by having the following structural general formula:
Figure FDA0003422100690000011
wherein, -R is the following group: c4～12The linear alkyl group of (1); r1And R2respectively-CB11H11And H, when R1When is H, R2is-CB11H11When R is1When is H, R2is-CB11H11，R3is-CH3Any one of H, tertiary butyl and aryl; n is 1-6, X is C or N, when the ligand is benzimidazole or imidazole ligand, X is C, and when the ligand is triazole, X is N; -CB11H11Is a monocarborane anion, and has the following structure:
Figure FDA0003422100690000012
2. a method for preparing a monocarborane anion-containing platinum complex blue light emitting material of claim 1, comprising the steps of:
s1, adding a metal organic compound I into the first solvent, heating a silicone oil pot to 60 ℃, stirring with a magnetic stirrer, adding silver trifluoromethanesulfonate under the condition of keeping out of the sun, and continuously stirring for one hour, wherein the metal organic compound I has the following structural formula:
Figure FDA0003422100690000021
s2 adding compound II and alkali in N2And (3) carrying out reaction under protection to obtain a reaction mixture, wherein the reaction temperature is 60 ℃, the reaction time is 12h, and the compound II has the following structural formula:
Figure FDA0003422100690000022
s3, cooling the mixture to room temperature, filtering the solid with diatomite to obtain a reaction solution, removing all the solvent I in vacuum, and then separating and purifying in a column chromatography separation mode to obtain a novel divalent platinum complex containing monocarborane functionalization, namely a monocarborane anion platinum complex blue-light material.
3. The method for preparing the monocarborane anion platinum complex blue-ray material as claimed in claim 2, wherein the solvent I is dichloromethane or tetrahydrofuran, and the base is potassium tert-butoxide.
4. The preparation method of the monocarborane anion platinum complex blue-ray material as claimed in claim 2, wherein the molar ratio of the compound I to the compound II is 1: 1.1-1.2, and the ratio of the compound I to the solvent I is 1 mmol: 80-150 mL.
5. The method for preparing the monocarborane anion platinum complex blue-ray material as claimed in claim 2, wherein the compound I in S1 is prepared by the following steps:
s11 adding compound III and platinum compound into solvent II, in N2The temperature is raised to 110 ℃, and the mixture is stirred and reacted for 10 hours, so as to obtain a first mixture, wherein the structural formula of the compound III is as follows:
Figure FDA0003422100690000031
s12 removing solvent II from the mixture I by distillation under reduced pressure, extracting the obtained solid with dichloromethane, extracting the organic phase with distilled water three times, drying the organic phase with anhydrous magnesium sulfate, removing dichloromethane by rotary evaporation, purifying by column chromatography and drying to obtain compound I.
6. The method for preparing the monocarborane anion platinum complex blue-ray material as claimed in claim 5, wherein the platinum compound is platinum acetylacetonate, and the solvent II is dimethyl sulfoxide.
7. The method for preparing the monocarborane anion platinum complex blue light emitting material as claimed in claim 5, wherein the molar ratio of the compound III to the platinum compound is 1: 1.1-1.2.
8. The method for preparing the monocarborane anion platinum complex blue-ray material as claimed in claim 2, wherein the compound II in S2 is prepared by the following steps:
s21 carborane is put into a reaction flask, the air in the reaction flask is pumped out by a vacuum pump, and N is introduced2In N at2Adding a solvent III, adding n-butyllithium into the reaction solution at the temperature of 0 ℃, stirring for reaction for 1.5h, then adding cuprous iodide, and stirring for reaction for 45 min;
s22, adding a palladium catalyst, a phosphorus ligand and a compound IV, and stirring and reacting for 20-24 hours at room temperature, wherein the compound IV has the following structural formula:
Figure FDA0003422100690000032
and (3) after the reaction of S23, filtering the solid with kieselguhr to obtain a second reaction solution, removing the third solvent in vacuum, dissolving the obtained solid with diethyl ether, extracting the organic phase with hydrochloric acid for three times, taking the organic phase, performing rotary evaporation to obtain a solid, adding water to dissolve the solid, adjusting the pH value with alkali until the aqueous solution is alkaline, performing cation exchange to obtain a solid product, and performing column chromatography separation and purification to obtain a compound II.
9. The method for preparing a monocarborane anion-containing platinum complex blue-emitting material according to claim 8, wherein X is1Is a halogen radicalThe solvent III is tetrahydrofuran, the palladium catalyst is palladium acetate, the phosphorus ligand is tri (2-methoxyphenyl) phosphine, and the molar ratio of the monocarborane to the compound IV is 1: 1.1.
10. An application of a blue light material containing a monocarborane anion platinum complex, which is characterized in that the blue light material containing the monocarborane anion platinum complex is applied to an organic electroluminescent device, and a light-emitting layer in the organic electroluminescent device contains the monocarborane anion platinum complex as claimed in any one of claims 1 to 9.
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