CN115947760A - Pinene pyrimidine tetradentate platinum (II) and palladium (II) complex and preparation method and application thereof - Google Patents
Pinene pyrimidine tetradentate platinum (II) and palladium (II) complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex, a preparation method and application thereof, wherein the complex is an asymmetric chiral tetradentate complex of a pinene-based pyrimidine ligand, and the structural general formula of the complex is a compound represented by the following formula (I) and formula (II):
wherein R is one of N-carbazolyl, N-diphenylamino, N-phenothiazinyl, N-phenoxazinyl, N-dimethylazinyl, 2, 6-dimethyl substituted phenoxy, 2, 6-diisopropyl substituted phenoxy and hexahydropyridyl. The pinene provided by the inventionThe pyrimidine tetradentate platinum (II) and palladium (II) complex has excellent photoelectric properties, stability, film forming property, solubility and other properties, is simple and convenient to prepare, has low cost, has aggregation state luminescence and piezochromism properties, and can be used as a luminescent layer to be applied to electroluminescent devices or applied to the fields of sensors, anti-counterfeiting, storage and display.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex as well as a preparation method and application thereof.
Background
The electrophosphorescent materials mainly containing heavy metal complexes are the most active in the current organic electroluminescence research. Having d 6 And d 8 Heavy metal atoms such as platinum (Pt), iridium (Ir) and osmium (Os) in an electronic structure cause the mixing of a singlet state and a triplet state due to the strong spin-orbit coupling effect, thereby shortening the phosphorescence life, increasing the intersystem crossing capability, causing the transition of a forbidden triplet excited state to a ground state to be partially allowed, leading the phosphorescence to be smoothly emitted, improving the luminous efficiency and leading the internal quantum efficiency to reach 100 percent. The materials can be widely applied to the fields of stress sensing, information storage, trademark anti-counterfeiting, luminescent devices and the like.
The current research on phosphorescent metal complexes has mainly focused on iridium (III), platinum (II) and palladium (II). Among them, the platinum (II) and palladium (II) complexes can be designed as bidentate, tridentate and tetradentate due to the square planar structure, and these changes can significantly affect the photophysical properties of the complexes, especially the rigid tetradentate ligands attract a lot of attention because the rigid structure can inhibit the vibration and rotation around the metal ions, reduce the non-radiative decay, and have good stability. Of these, palladium (II) complexes generally exhibit much weaker strong spin-orbit coupling effects and lack spin-orbit coupling from T 1 →S 0 Effective radiation attenuation process. Therefore, most of them have a long decay life at room temperature, which results in concentration quenching and thus severe efficiencyAnd (4) decreasing. However, the problem of concentration quenching can be effectively improved by introducing a rigid group with large steric hindrance into the structure of the ligand, so that the luminous efficiency is greatly increased.
The luminescent material based on the pyrimidine is easy to synthesize and carry out chemical modification, has high electron affinity, luminous efficiency and excellent electrochemical and optical properties, and is applied to the fields of electronic devices such as OLED, OPV, OFET, chemical biosensors and the like, and the dinitrogen heterocyclic ring is used as a ligand to possibly synthesize an electrophosphorescent material with better performance. However, how to prepare a material with high complex solubility, low coordination reaction difficulty and high luminous efficiency is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to develop pinene pyrimidine tetradentate platinum (II) and palladium (II) complexes which have the advantages of excellent photoelectric property, stability, film forming property, solubility and the like, are simple and convenient to prepare, have aggregation state luminescence and piezochromic property, and have low cost, and the complexes can be applied to the fields of electroluminescent devices, sensors, electrochromic devices and the like.
The invention provides the following technical scheme:
in a first aspect, a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex is provided, the complex is an asymmetric chiral tetradentate complex of a pinene-based pyrimidine ligand, and the structural general formula of the complex is a compound represented by the following formula (I) and formula (II):
wherein R is one of N-carbazolyl, N-diphenylamino, N-phenothiazinyl, N-phenoxazinyl, N-dimethylazinyl, 2, 6-dimethyl substituted phenoxy, 2, 6-diisopropyl substituted phenoxy and hexahydropyridyl:
in a second aspect, there is provided a method for preparing the tetradentate platinum (II) and palladium (II) complex of pinene pyrimidine, comprising the following steps:
under the protection of nitrogen, dissolving potassium tetrachloroplatinate and pinene pyrimidine ligand in acetic acid, adding a catalyst, reacting at room temperature in a dark place, and then heating for reaction to obtain a pinene pyrimidine tetradentate platinum (II) complex shown as a formula (I);
under the protection of nitrogen, dissolving palladium acetate and a pinene pyrimidine ligand in acetic acid, adding a catalyst, reacting at room temperature in a dark place, and then heating to react to obtain the pinene pyrimidine tetradentate palladium (II) complex shown as the formula (II).
Further, the mole ratio of the raw materials used for preparing the pinene pyrimidine tetradentate platinum (II) complex is as follows: potassium tetrachloroplatinate: catalyst: pinene pyrimidine ligand: acetic acid =1.0 to 1.5:1 to 5:1:100 to 500.
Further, the mole ratio of the raw materials used for preparing the pinene pyrimidine tetradentate palladium (II) complex is as follows: palladium acetate: catalyst: pinene pyrimidine ligand: acetic acid =1.0 to 1.5:1 to 5:1:100 to 500.
Further, the catalyst is one of potassium acetate, sodium acetate and ammonium acetate.
Further, the preparation method of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex specifically comprises the following steps:
dissolving dichloropyrimidine and 3-methoxyphenylboronic acid in a mixed solution of an organic solvent and water in the presence of a palladium catalyst and alkali, and refluxing for 20-30 h to obtain a methoxypyrimidine derivative shown as a formula (1-1);
dissolving the methoxyl pyrimidine derivative in an organic solvent, adding a compound with an active group, and reacting at 20-50 ℃ for 10-20 h in the presence of alkali to obtain the pyrimidine derivative shown as the formula (1-2);
dissolving the pyrimidine derivative in acid, and refluxing for 40-50 h to obtain the hydroxy pyrimidine derivative shown as the formula (1);
dissolving m-bromoacetophenone as a raw material in pyridine, adding a pyridine solution of iodine, and reacting at 100-120 ℃ for 5-10 h to obtain a pyridine salt derivative shown as a formula (2-1);
dissolving the pyridine salt derivative, the olefine aldehyde derivative and the organic salt in an organic solvent, and refluxing for 10-20 h to obtain the bromo-pinene derivative shown as the formula (2);
dissolving hydroxyl pyrimidine derivatives shown as a formula (1) and bromo-pinene derivatives shown as a formula (2) in an organic solvent, and reacting for 20-40 h at 100-130 ℃ in the presence of cuprous iodide and alkali to obtain pinene pyrimidine chiral asymmetric tetradentate ligands shown as a formula (3);
under the protection of nitrogen, dissolving pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) and potassium tetrachloroplatinate in acetic acid, adding a catalyst, stirring at room temperature in a dark place for 6-12 h, heating to 120-150 ℃, and reacting for 18-72 h to obtain a pinene pyrimidine tetradentate palladium (II) complex shown in the formula (I);
under the protection of nitrogen, dissolving the pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) and palladium acetate in glacial acetic acid, adding a catalyst, stirring at room temperature in a dark place for 6-12 h, heating to 120-150 ℃ and reacting for 18-72 h to obtain the pinene pyrimidine tetradentate palladium (II) complex shown in the formula (II).
Further, the raw materials for preparing the methoxy pyrimidine derivatives shown in the formula (1-1) are calculated according to the molar parts: 1 part of dichloropyrimidine, 1-1.5 parts of 3-methoxyphenylboronic acid, 0.03-0.05 part of palladium catalyst, 3-5 parts of alkali, 10-50 parts of polar organic solvent and 5-25 parts of water; the palladium catalyst is one of palladium tetrakistriphenylphosphine, bis (triphenylphosphine) palladium dichloride and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride; the alkali is one of potassium carbonate, sodium tert-butoxide and potassium tert-butoxide; the organic solvent is one of toluene, N-N, dimethylformamide, tetrahydrofuran and 1, 4-dioxane.
Further, the raw materials for preparing the pyrimidine derivatives shown in the formula (1-2) are calculated according to the molar parts: 1 part of methoxyl pyrimidine derivatives, 10-50 parts of organic solvent, 1-2 parts of compounds with active groups and 3-10 parts of alkali; the organic solvent is one of toluene, N-dimethylformamide, tetrahydrofuran and 1, 4-dioxane; the base is one of sodium hydride and n-butyl lithium; r in the formula (1-2) is one of N-carbazolyl, N-diphenylamino, N-phenothiazinyl, N-phenoxazinyl, N-dimethylazinyl, 2, 6-dimethyl substituted phenoxy, 2, 6-diisopropyl substituted phenoxy and hexahydropyridyl.
Further, the raw materials for preparing the hydroxypyrimidine derivative shown as the formula (1) are calculated according to the molar parts: 1 part of a compound shown as a formula (1-2) and 40-100 parts of acid; the acid is one of hydrobromic acid and acetic acid.
Further, the raw materials for preparing the pyridine salt derivative shown as the formula (2-1) are calculated according to the molar parts: 1 part of bromoacetophenone, 10-50 parts of pyridine and 0.5-1 part of iodine.
Further, the raw materials for preparing the bromo-pinene derivative shown as the formula (2) are calculated according to the molar parts: 1 part of pyridine salt derivative, 1-1.5 parts of olefine aldehyde derivative, 2-3 parts of organic salt and 10-50 parts of organic solvent; the organic salt is one of ammonium acetate, sodium acetate and potassium acetate; the organic solvent is one of toluene, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, methanol, ethanol and dimethyl sulfoxide.
Further, the mole ratio of the raw materials used for preparing the pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) is as follows: a hydroxypyrimidine derivative represented by the formula (1): bromo-pinene derivatives represented by the formula (2): organic solvent: cuprous iodide: base =1:1:10 to 50:0.01 to 0.1:1 to 10; the organic solvent is one of toluene, dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran and 1, 4-dioxane; the alkali is one of potassium carbonate, sodium tert-butoxide, potassium phosphate and cesium carbonate.
In a third aspect, the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex is applied as a luminescent layer in an electroluminescent device, or applied in the fields of sensors, anti-counterfeiting, storage and display.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention applies pinene pyrimidine compounds with three-dimensional structures to tetradentate platinum (II) and palladium (II) complexes, obtains the tetradentate platinum (II) and palladium (II) complex phosphorescent materials with huge three-dimensional steric hindrance structures by introducing different substituents to modify aromatic rings on a main ligand, the tetradentate platinum (II) and palladium (II) complex phosphorescent materials have stronger aggregation state luminescence property, and are applied to a luminescent layer of an organic electroluminescent device, concentration quenching caused by aggregation among molecules can be effectively inhibited by utilizing the large three-dimensional steric hindrance of the pinene structures, the solubility of the complexes is effectively regulated by saturated aliphatic ring structures, and the efficient phosphorescent device is realized; meanwhile, the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex phosphorescent material can change the stacking structure among molecules through external force due to the introduction of a free rotatable substituent, so that the change of the luminescent color is realized, and the material has good piezochromic property and can be potentially applied to the fields of data recording, data storage, pressure sensing devices, pressure-sensitive devices and the like.
(2) According to the invention, a platinum and palladium core-coated large steric hindrance pinene structure containing a saturated aliphatic ring, an electron-deficient pyrimidine unit and different electron-donating structures are introduced on a ligand, so that an aggregation-induced luminescence effect is realized, a concentration quenching effect caused by long service life is effectively inhibited, the luminescence efficiency of a platinum and palladium (II) complex phosphorescent material is improved to the greatest extent, and a piezochromic effect is also realized; in the invention, the compound containing active groups is used for replacing halogen atoms, so that the solubility, the hole transmission capability and the thermal stability of the complex are further improved, and in addition, the introduction of the groups can generate a certain space effect, so that the interaction among luminescent centers of the complex is reduced, the self-quenching phenomenon of triplet excitons is reduced, and the luminescent performance of the material is improved.
(3) The pinene pyrimidine tetradentate platinum (II) and palladium (II) complex provided by the invention has the advantages of simple synthetic method and easy purification, and an electroluminescent device prepared from the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex provided by the invention has high internal and external quantum yield, high luminous brightness and high stability; in addition, because the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex has obvious aggregation state luminescence property and piezochromic property, the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex can also be applied to the fields of sensors, anti-counterfeiting, storage, display and the like.
Drawings
FIG. 1 is an ultraviolet absorption (UV) spectrum of phosphorescent platinum (II) complexes Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP in methylene chloride of example 22;
FIG. 2 is a fluorescence emission (PL) spectrum of a phosphorescent platinum (II) complex Pt-MDP in methylene chloride in example 22;
FIG. 3 is an emission (PL) spectrum of the phosphorescent palladium (II) complex Pd-MD in water/Tetrahydrofuran (THF) mixtures of various water ratios in example 22 (the percentages in the figure refer to the volume percentage of water in the water/THF mixture);
FIG. 4 is an emission (PL) spectrum of the phosphorescent palladium (II) complex Pd-MDP in water/Tetrahydrofuran (THF) mixtures of different water ratios of example 22 (the percentages in the figure refer to the volume percent of water in the water/THF mixture);
FIG. 5 is the piezochromic effect of the phosphorescent palladium (II) complex Pd-MDP of example 22;
FIG. 6 is a density functional theory calculation of phosphorescent platinum (II) complexes Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP in example 23;
FIG. 7 is a Cyclic Voltammetry (CV) curve of phosphorescent platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP in dichloromethane solution in example 24;
FIG. 8 is a view showing a structure of a device and molecular structures of other materials used in the device in example 25;
FIG. 9 is a graph of the electroluminescence spectrum (a), current density-voltage-luminance (b), luminance-current efficiency (c), and luminance-external quantum efficiency (d) of the electroluminescent device of example 25 based on the phosphorescent palladium (II) complex Pd-MD at doping concentrations of 5%, 10%, 15%, 20%, and 100%;
fig. 10 is a graph of electroluminescence spectrum (a), current density-voltage-luminance (b), luminance-current efficiency (c), and luminance-external quantum efficiency (d) of an electroluminescent device based on the phosphorescent palladium (II) complex Pd-MDP at doping concentrations of 5%, 10%, 15%, 20%, and 100% in example 25.
Detailed Description
The invention discloses a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex, a preparation method and application thereof, wherein the pinene and pyrimidine modified tetradentate platinum (II) and palladium (II) complex is connected through an oxygen atom. According to the tetradentate phosphorescent platinum and palladium (II) complex, a large steric hindrance pinene structure which wraps platinum and palladium cores and contains saturated aliphatic rings, an electron-deficient pyrimidine unit and different electron-donating structures are introduced on a ligand, so that an aggregation-induced luminescence effect is realized, a concentration quenching effect caused by long service life is effectively inhibited, the luminescence efficiency of a platinum and palladium (II) complex phosphorescent material is improved to the greatest extent, and a piezochromic effect is also realized. The preparation method and the obtained pinene-based pyrimidine tetradentate platinum (II) and palladium (II) complex have high internal and external quantum yield, high luminous brightness and high stability. The electroluminescent device has the advantages that the luminescent layer is a pinene-based pyrimidine tetradentate platinum (II) and palladium (II) complex, the luminescent layer is prepared by adopting an evaporation film-making method under specific conditions, the cost is low, the operation is simple, the chemical property is stable, the luminous brightness and the efficiency are high, and the realization of a high-efficiency electroluminescent device is facilitated.
In order to better understand the contents of the present invention, the following further describes the technical scheme of the present invention by specific examples and illustrations, which specifically include synthesis, property determination, titration experiment, etc. These examples are merely illustrative of the present invention and do not limit the present invention.
Example 1
Preparation of 4-chloro-6- (3-methoxyphenyl) pyrimidine ClM-PYP as intermediate of methoxypyrimidine.
3, 6-dichloropyrimidine (8.9g, 60mmol), 3-methoxyphenylboronic acid (10.9g, 72mmol), tetratriphenylphosphine palladium (2.4g, 1.6mmol), tetra-n-butylammonium bromide (1.9g, 6mmol) and potassium carbonate (24.8g, 180mmol) are weighed into a round-bottomed flask, evacuated and charged with nitrogen three times, under nitrogen, water (25mL, 1388mmol) and toluene (75mL, 706mmol) are injected, and the mixture is refluxed at 120 ℃ for 24h. To be reacted withCooling to room temperature, extracting with dichloromethane, collecting organic layer, drying, concentrating, and purifying with V PE :V EA Column chromatography of =20 to obtain 8g of 4-chloro-6- (3-methoxyphenyl) pyrimidine ClM-PP as a white solid with a yield of 68.2%. 1 H NMR(400MHz,CDCl 3 )δ9.03(s,1H),7.73(s,1H),7.68–7.64(m,1H),7.61(d,J＝8.2Hz,1H),7.43(t,J＝8.0Hz,1H),7.09(d,J＝8.2Hz,1H),3.90(s,3H)。
Example 2
Preparation of pyrimidine intermediate 10- (6- (3-methoxyphenyl) pyrimidin-4-yl) -10H-phenoxazine M-PYP.
Phenoxazine (4.6g, 25mmol) is weighed and put into a reaction flask, vacuumizing is carried out to replace nitrogen for 3-5 times, the reaction is placed in an ice bath at 0 ℃, tetrahydrofuran (40mL, 494mmol) is added under the protection of nitrogen, 2.5 mol/L n-butyllithium (11.3mL, 28.9 mmol) is dropwise added into the reaction flask at 0 ℃, and after 1h, a dried tetrahydrofuran solution of 4-chloro-6- (3-methoxyphenyl) pyrimidine ClM-PYP (5.5g, 25mmol) is dropwise added into the reaction flask. After the dropwise addition, the reaction was allowed to warm to room temperature naturally, stirred at room temperature overnight, quenched with saturated ammonium chloride solution, extracted with dichloromethane, dried, concentrated, and concentrated with V PE :V EA Column chromatography separation of =20 to obtain 6.2 g of light yellow solid 10- (6- (3-methoxyphenyl) pyrimidin-4-yl) -10H-phenoxazine M-PYP with a yield of 70.6%. 1 H NMR(400MHz,CDCl 3 )δ8.91(s,1H),7.80(d,J＝7.0Hz,2H),7.53(d,J＝9.9Hz,2H),7.45(d,J＝8.6Hz,1H),7.38(t,J＝7.9Hz,1H),7.20(d,J＝21.7Hz,6H),7.03(d,J＝7.8Hz,1H),3.90(s,3H)。
Example 3
Preparation of hydroxypyrimidine ligand 3- (6- (10H-benzoxazine-10-yl) pyrimidine-4-yl) phenol OH-PYP.
Weighing 10-(6- (3-methoxyphenyl) pyrimidin-4-yl) -10H-phenoxazin M-PYP (5g, 13.6 mmol) was placed in a round bottom flask, and hydrobromic acid (30mL, 1084mmol) and glacial acetic acid (100mL, 890mmol) were injected and refluxed at 120 ℃ for 2 days. After the reaction, the reaction solution was cooled to room temperature, and a large amount of ice water was added to the reaction solution to precipitate a yellowish brown solid, which was then filtered off. By V PE :V EA Column chromatography separation of =3 to obtain 3.4 g of 3- (6- (10H-benzoxazine-10-yl) pyrimidin-4-yl) phenol OH-PYP as a yellow solid with a yield of 71.4%. 1 H NMR(400MHz,DMSO)δ9.71(s,1H),8.86(s,1H),7.82(d,J＝7.7Hz,2H),7.51(s,1H),7.44–7.35(m,2H),7.32–7.21(m,7H),6.91(d,J＝7.9Hz,1H)。
Example 4
Preparation of bromo-pinene ligand (6R, 8R) -3- (3-bromophenyl) -pinene Br-DPTM.
M-bromoacetophenone (8.0 g,40.0 mmol) and pyridine (40mL, 497mmol) were placed in a three-necked flask, and a solution of iodine (5.1 g,20.0 mmol) in pyridine was added dropwise slowly at 105 ℃. After the dropwise addition, the reaction is carried out for 5h, the reaction is cooled to room temperature, the reaction product is filtered and dried in vacuum, and 14.0 g of yellow solid 1- (2- (3-bromophenyl) -2-oxoethyl) pyridin-1-onium iodide Br-OPPI is obtained, and the yield is 87.9%. The above-mentioned product, br-OPPI (4.1g, 10.0mmol), (1R) - (-) -myrtenal (1.8g, 12.0mmol), anhydrous ammonium acetate (1.5g, 20.0mmol) and DMF (10mL, 130mmol), was placed in a single-necked flask. Reacting at 120 ℃ for 12h, and concentrating. Adding water, extracting with dichloromethane, combining organic phases, washing with water, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering and concentrating to obtain a crude product, and performing column chromatography separation to obtain yellow powder (6R, 8R) -3- (3-bromophenyl) -pinene Br-DPTM 2.3g with the yield of 70.0%. 1 H NMR(400MHz,CDCl 3 )δ8.24(s,1H),8.16(s,1H),7.91(d,J＝8.3Hz,1H),7.52(s,2H),7.34(t,J＝7.9Hz,1H),3.05(s,2H),2.89(t,J＝5.5Hz,1H),2.81–2.69(m,1H),2.35(s,1H),1.45(s,3H),1.28(s,1H),0.69(s,3H)。
Example 5
Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-phenoxazine DTMP.
(6R, 8R) -3- (3-bromophenyl) -pinene Br-DPTM (327.0mg, 1.0mmol), 3- (6- (10H-benzoxazine-10-yl) pyrimidin-3-yl) phenol OH-PYP (353.0mg, 1.0mmol), cuI (19.0mg, 0.1mmol), cesium carbonate (977.0mg, 3.0mmol), 2-picolinic acid (0.3g, 2.0mmol) were weighed out and placed in a sealed tube, 5mL of DMSO (5mL, 500mmol) after being deoxygenated by blowing nitrogen gas was added, vacuum was conducted, nitrogen gas was charged three times, and reaction was carried out at 120 ℃ for 24 hours. After the reaction is finished, dichloromethane is used for extraction, anhydrous sodium sulfate is used for drying, and a developing agent is used for column chromatography separation to obtain 0.3g of pinene phenoxyl pyrimidine-10H-phenoxazine DTMP as yellow powder, wherein the yield is 50%. 1 H NMR(400MHz,DMSO)δ8.83(s,1H),8.18(s,1H),7.90(d,J＝8.0Hz,1H),7.75(d,J＝9.9Hz,4H),7.63(s,1H),7.52(d,J＝15.5Hz,3H),7.20(dd,J＝19.7,11.6Hz,9H),2.99(s,2H),2.86(s,1H),2.68(s,1H),2.29(s,1H),1.39(s,3H),1.14(s,1H),0.59(s,3H)。
Example 6
And (3) preparing the complex Pd-MD.
Pinene phenoxy pyrimidine-10H-phenoxazine DTMP (120.0mg, 0.2mmol), pd (OAc) were weighed 2 (42.0 mg, 0.22mmol), TBAB (8.0 mg, 0.1mmol) in a sealed tube, evacuated and charged with nitrogen. The acetic acid was bubbled with nitrogen for 10min, then acetic acid (10mL, 60mmol) was pumped and added into the sealed tube under the protection of nitrogen, stirred at room temperature for 12h, and then heated to 120 ℃ for reaction for 72h. After the reaction, the reaction solution was poured into a large amount of ice water, and a yellow solid was precipitated and filtered. By V PE :V DCM Performing column chromatography separation by using a developing solvent of = 2. 1 H NMR(400MHz,CDCl 3 )δ8.94(s,1H),8.18(s,1H),7.83(s,2H),7.74(s,1H),7.65(s,1H),7.48(s,1H),7.34–7.27(m,5H),7.21(d,J＝9.5Hz,6H),3.10(s,2H),2.99(s,1H),2.79(s,1H),2.38(s,1H),2.22(t,J＝7.6Hz,1H),2.01(s,1H),1.48(s,3H),0.71(s,3H)。
Example 7
Preparation of pyrimidine intermediate 9- (6- (3-methoxyphenyl) pyrimidin-4-yl) -9H-carbazole M-PYC.
Carbazole (4.2g, 25mmol) is weighed and put into a reaction flask, nitrogen is replaced for 3-5 times by vacuumizing, the reaction is placed in an ice bath at 0 ℃, tetrahydrofuran (40mL, 494mmol) is added under the protection of nitrogen, 2.5 mol/l n-butyllithium (11.3mL, 28.9mmol) is dropwise added into the reaction flask at 0 ℃, and after 1h, a dried tetrahydrofuran solution of 4-chloro-6- (3-methoxyphenyl) pyrimidine ClM-PYP (5.5g, 25mmol) is dropwise added into the reaction flask. After the dropwise addition, the reaction was allowed to warm naturally to room temperature and stirred at room temperature overnight, quenched with saturated ammonium chloride solution, extracted with dichloromethane, dried, concentrated, and concentrated with V PE :V EA Column chromatography separation of =20, yielding 5.3 g of 9- (6- (3-methoxyphenyl) pyrimidin-4-yl) -9H-carbazole M-PYC as a pale yellow solid with a yield of 60.8%. 1 H NMR(400MHz,CDCl 3 )δ9.12(d,J＝1.5Hz,1H),8.21–8.13(m,2H),7.67–7.59(m,3H),7.55–7.48(m,2H),7.40–7.27(m,5H),6.93(ddd,J＝8.0,2.2,1.2Hz,1H),3.83(s,3H)。
Example 8
And (3) preparing hydroxypyrimidine ligand 3- (6- (9H-carbazole-9-yl) pyrimidine-4-yl) phenol OH-PYC.
9- (6- (3-methoxyphenyl) pyrimidin-4-yl) -9H-carbazole M-PYC (5g, 14.2mmol) was weighed into a round-bottomed flask, and hydrobromic acid (30mL, 1084mmol) and glacial acetic acid (100mL, 890mmol) were injected and refluxed at 120 ℃ for 2 days. After the reaction, the reaction solution was cooled to room temperature, and a large amount of ice water was added to the reaction solution to precipitate a yellowish brown solid, which was then filtered off. By V PE :V EA Column chromatography separation of =3 to obtain 3.9g of 3- (6- (9H-carbazol-9-yl) pyrimidin-4-yl) phenol OH-PYC as a yellow solid with a yield of 81.7%. 1 H NMR(400MHz,CDCl 3 )δ9.12(d,J＝1.5Hz,1H),8.77(s,1H),8.21–8.13(m,2H),7.66–7.59(m,2H),7.55–7.45(m,2H),7.37(ddd,J＝7.4,6.2,1.3Hz,1H),7.33–7.28(m,3H),7.28–7.22(m,2H),6.81(ddd,J＝8.2,2.2,1.1Hz,1H)。
Example 9
Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-carbazole CPDT.
(6R, 8R) -3- (3-bromophenyl) -pinene Br-DPTM (327.0mg, 1.0mmol), 3- (6- (9H-carbazol-9-yl) pyrimidin-4-yl) phenol OH-PYC (339.0mg, 1.0mmol), cuI (19.0mg, 0.1mmol), cesium carbonate (977.0mg, 3.0mmol) and 2-picolinic acid (0.3g, 2.0mmol) are weighed and placed in a sealed tube, 5mL of DMSO (5mL, 50mmol) obtained after being deoxygenated by blowing nitrogen gas is added, the sealed tube is vacuumized and filled with nitrogen gas for three times, and the reaction is carried out at 120 ℃ for 24 hours. After the reaction is finished, dichloromethane is used for extraction, anhydrous sodium sulfate is used for drying, and a developing agent is used for column chromatography separation to obtain yellow powder pinene phenoxyl pyrimidine-10H-carbazole CPDT 0.34g, and the yield is 57.2%. 1 H NMR(400MHz,CDCl 3 )δ9.12(d,J＝1.4Hz,1H),8.20–8.14(m,2H),7.72(ddd,J＝8.6,2.3,1.2Hz,1H),7.66–7.59(m,3H),7.55–7.40(m,5H),7.40–7.30(m,5H),7.04(ddd,J＝7.8,2.2,1.2Hz,2H),3.21–3.08(m,2H),3.08–2.99(m,1H),2.31–2.19(m,1H),2.00–1.90(m,2H),0.97(d,J＝16.5Hz,6H)。
Example 10
And (3) preparing the Pt-CD complex.
Weighing pinene phenoxy pyrimidine-10H-carbazole CPDT (117.2mg, 0.2mmol) as main ligands and K 2 PtCl 4 (92.0 mg, 0.22mmol) was placed in a sealed tube, vacuum-pumped and charged with nitrogen. The acetic acid is blown with nitrogen for 10min, the acetic acid (10mL, 60mmol) is pumped out and added into a sealed tube under the protection of nitrogen, the mixture is stirred for 12h at room temperature, and the temperature is increased to 120 ℃ for reaction for 72h. After the reaction is finished, pouring the reaction liquid into a large amount of ice waterIn the reaction, a red solid was precipitated and filtered. By V PE :V DCM Column chromatography separation was performed using a developing solvent of = 2. 1 H NMR(400MHz,CDCl 3 )δ9.05(d,J＝0.8Hz,1H),8.20–8.14(m,2H),7.66–7.60(m,2H),7.48(d,J＝5.7Hz,3H),7.40–7.27(m,6H),6.91–6.85(m,1H),6.73(ddd,J＝18.5,7.7,1.3Hz,2H),6.60(dd,J＝7.7,1.3Hz,1H),3.11–2.90(m,3H),2.01–1.87(m,2H),1.78(dt,J＝12.0,7.8Hz,1H),0.97(d,J＝16.5Hz,6H)。
Example 11
And (3) preparing the complex Pd-CD.
Weighing main ligand pinene phenoxy pyrimidine-10H-carbazole CPDT (117.2mg, 0.2mmol), pd (OAc) 2 (42.0 mg, 0.22mmol), TBAB (8.0 mg, 0.1mmol) in a sealed tube, evacuated and charged with nitrogen. The acetic acid is blown with nitrogen for 10min, the acetic acid (10mL, 60mmol) is pumped out and added into a sealed tube under the protection of nitrogen, the mixture is stirred for 12h at room temperature, and the temperature is increased to 120 ℃ for reaction for 72h. After the reaction is finished, pouring the reaction liquid into a large amount of ice water, separating out orange-red solids, and performing suction filtration. By V PE :V DCM Column chromatography separation is carried out on the developing solvent of =2 to obtain bright orange powder Pd-DA of 28.3mg, and the yield is 20.5%. 1 H NMR(400MHz,CDCl 3 )δ8.87(d,J＝0.8Hz,2H),8.20–8.14(m,4H),7.82(dd,J＝8.2,1.4Hz,2H),7.66–7.60(m,4H),7.56–7.48(m,6H),7.44–7.28(m,15H),7.27(d,J＝1.0Hz,1H),6.67(ddd,J＝20.6,7.9,1.2Hz,4H),3.11–2.91(m,6H),2.01–1.87(m,4H),1.78(dt,J＝12.1,7.8Hz,2H),0.97(d,J＝16.5Hz,12H)。
Example 12
Preparation of pyrimidine intermediate 6- (3-methoxyphenyl) -N, N-diphenyl pyrimidine-4-amine M-NDA.
Diphenylamine (4.2g, 25mmol) is weighed and put into a reaction bottleAfter the nitrogen gas was replaced by evacuation 3 to 5 times, the reaction was placed in an ice bath at 0 ℃ and tetrahydrofuran (40mL, 494mmol) was added under nitrogen protection, 2.5 mol/l n-butyllithium (11.3 mL,28.9 mmol) was added dropwise to the reaction flask at 0 ℃ and after 1 hour, a dried tetrahydrofuran solution of 4-chloro-6- (3-methoxyphenyl) pyrimidine ClM-PYP (5.5 g, 25mmol) was added dropwise to the reaction flask. After the dropwise addition, the reaction was allowed to warm to room temperature naturally, stirred at room temperature overnight, quenched with saturated ammonium chloride solution, extracted with dichloromethane, dried, concentrated, and concentrated with V PE :V EA Column chromatography of =20 to give 5.7 g of 6- (3-methoxyphenyl) -N, N-diphenylpyrimidin-4-amine M-NDA as a pale yellow solid in 65.4% yield. 1 H NMR(400MHz,CDCl 3 )δ8.50(d,J＝1.5Hz,1H),7.64(ddd,J＝8.8,2.3,1.2Hz,1H),7.52(t,J＝2.2Hz,1H),7.36(dd,J＝8.7,7.9Hz,1H),7.29(tt,J＝7.6,1.6Hz,4H),7.20(d,J＝1.4Hz,1H),7.17–7.10(m,4H),7.04(tt,J＝7.8,1.5Hz,2H),6.93(ddd,J＝8.0,2.2,1.2Hz,1H),3.83(s,3H)。
Example 13
Preparation of hydroxyl pyrimidine ligand 3- (6- (diphenylamino) pyrimidine-4-yl) phenol OH-NDA.
6- (3-methoxyphenyl) -N, N-diphenylpyrimidin-4-amine M-NDA (5g, 14.2mmol) was weighed into a round-bottomed flask, and hydrobromic acid (30mL, 1084 mmol) and glacial acetic acid (100mL, 890mmol) were injected and refluxed at 120 ℃ for 2 days. After the reaction, the reaction solution was cooled to room temperature, and a large amount of ice water was added to the reaction solution to precipitate a yellowish brown solid, which was then filtered off. By V PE :V EA Column chromatography separation of =3:1 gave 4.4g of 3- (6- (diphenylamino) pyrimidin-4-yl) phenol OH-NDA as a yellow solid in 92.5% yield. 1 H NMR(400MHz,CDCl 3 )δ8.77(s,1H),8.51(d,J＝1.5Hz,1H),7.48(ddd,J＝8.4,2.2,1.2Hz,1H),7.33–7.23(m,6H),7.20(d,J＝1.5Hz,1H),7.17–7.10(m,4H),7.04(tt,J＝7.9,1.5Hz,2H),6.81(ddd,J＝8.2,2.2,1.1Hz,1H)。
Example 14
Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-diphenylamine DPNA.
(6R, 8R) -3- (3-bromophenyl) -pinene Br-DPTM (327.0mg, 1.0mmol), 3- (6- (diphenylamino) pyrimidin-4-yl) phenol OH-NDA (339.0mg, 1.0mmol), cuI (19.0mg, 0.1mmol), cesium carbonate (977.0mg, 3.0mmol) and 2-picolinic acid (0.3g, 2.0mmol) are weighed and placed in a sealed tube, 5mL of DMSO (5mL, 50mmol) obtained after deoxygenation by using nitrogen gas is added, vacuum is pumped and nitrogen gas is filled for three times, and the reaction is carried out at 120 ℃ for 24 hours. After the reaction is finished, dichloromethane is used for extraction, anhydrous sodium sulfate is used for drying, and yellow powder pinene phenoxyl pyrimidine-10H-diphenylamine DPNA is obtained by column chromatography separation of a developing agent, wherein the yield is 68.3%. 1 H NMR(400MHz,CDCl 3 )δ8.50(d,J＝1.5Hz,1H),8.22(s,1H),7.72(ddd,J＝8.6,2.3,1.2Hz,1H),7.63(ddd,J＝8.6,2.2,1.1Hz,1H),7.53–7.48(m,2H),7.48–7.37(m,3H),7.33–7.26(m,4H),7.20(d,J＝1.4Hz,1H),7.17–7.10(m,4H),7.04(dddd,J＝7.8,5.8,3.6,1.5Hz,4H),3.21–3.08(m,2H),3.08–2.99(m,1H),2.31–2.19(m,1H),2.02–1.90(m,2H),0.97(d,J＝16.5Hz,6H)。
Example 15
And (3) preparing the complex Pt-PN.
Weighing main ligand pinene phenoxy pyrimidine-10H-diphenylamine DPNA (117.2mg, 0.2mmol), K 2 PtCl 4 (92.0 mg, 0.22mmol) was placed in a sealed tube, evacuated, and charged with nitrogen. The acetic acid is blown with nitrogen for 10min, the acetic acid (10mL, 60mmol) is pumped out and added into a sealed tube under the protection of nitrogen, the mixture is stirred for 12h at room temperature, and the temperature is increased to 120 ℃ for reaction for 72h. After the reaction, the reaction solution was poured into a large amount of ice water, and a red solid was precipitated and filtered. By V PE :V DCM Column chromatography separation with a developing solvent of =2 was carried out to obtain Pt-PN32.8 mg as a red powder in a yield of 21%. 1 H NMR(400MHz,CDCl 3 )δ9.05(d,J＝0.8Hz,1H),7.48(d,J＝5.6Hz,2H),7.42(s,1H),7.40–7.26(m,6H),7.17–7.10(m,4H),7.04(tt,J＝7.7,1.5Hz,2H),6.91–6.85(m,1H),6.73(ddd,J＝18.5,7.7,1.3Hz,2H),6.64–6.59(m,1H),3.11–2.90(m,3H),2.01–1.87(m,2H),1.78(dt,J＝12.1,7.8Hz,1H),0.97(d,J＝16.5Hz,6H)。
Example 16
And (3) preparing the complex Pd-PN.
Weighing main ligands pinene phenoxypyrimidine-10H-diphenylamine DPNA (117.2mg, 0.2mmol) and Pd (OAc) 2 (42.0 mg, 0.22mmol), TBAB (8.0 mg, 0.1mmol) in a sealed tube, evacuated and charged with nitrogen. The acetic acid was bubbled with nitrogen for 10min, then acetic acid (10mL, 60mmol) was pumped and added into the sealed tube under the protection of nitrogen, stirred at room temperature for 12h, and then heated to 120 ℃ for reaction for 72h. After the reaction is finished, pouring the reaction liquid into a large amount of ice water, separating out orange red solid, and filtering. By V PE :V DCM Column chromatography separation is carried out on the developing solvent of = 2. 1 H NMR(400MHz,CDCl 3 )δ9.59(s,1H),8.87(d,J＝0.8Hz,1H),7.82(dd,J＝8.2,1.4Hz,1H),7.56–7.50(m,2H),7.44(s,1H),7.38(s,1H),7.33–7.25(m,7H),7.17–7.10(m,4H),7.04(tt,J＝7.7,1.5Hz,2H),6.67(ddd,J＝20.5,7.9,1.2Hz,2H),3.07(dd,J＝12.4,4.5Hz,1H),3.03–2.91(m,2H),2.02–1.87(m,2H),1.78(dt,J＝12.0,7.8Hz,1H),0.97(d,J＝16.5Hz,6H)。
Example 17
Preparation of pyrimidine intermediate 10- (6- (3-methoxyphenyl) pyrimidin-4-yl) -9, 9-dimethyl-9, 10-dihydroacridine M-PDD.
Weighing 9, 10-dihydro-9, 9-dimethylacridine (5.2g, 25mmol) and placing into a reaction flask, vacuumizing to replace nitrogen for 3-5 times, placing the reaction in an ice bath at 0 ℃, adding tetrahydrofuran (40mL, 494 mmol) under the protection of nitrogen, and heating at 0 DEG CNext, 2.5 mol/l n-butyllithium (11.3 mL,28.9 mmol) was added dropwise to the reaction flask, and after 1 hour, a solution of 4-chloro-6- (3-methoxyphenyl) pyrimidine ClM-PYP (5.5 g, 25mmol) in dry tetrahydrofuran was added dropwise to the reaction flask. After the dropwise addition, the reaction was allowed to warm to room temperature naturally, stirred at room temperature overnight, quenched with saturated ammonium chloride solution, extracted with dichloromethane, dried, concentrated, and concentrated with V PE :V EA Column chromatography of =20 to give 5.1g of 10- (6- (3-methoxyphenyl) pyrimidin-4-yl) -9, 9-dimethyl-9, 10-dihydroacridine M-PDD as a pale yellow solid in 52% yield. 1 H NMR(400MHz,CDCl 3 )δ8.46(d,J＝1.4Hz,1H),7.64(ddd,J＝8.8,2.3,1.2Hz,1H),7.51(t,J＝2.3Hz,1H),7.36(dd,J＝8.7,7.9Hz,1H),7.32–7.25(m,2H),7.23(d,J＝1.4Hz,1H),7.15–7.04(m,4H),6.96–6.90(m,3H),3.83(s,3H),1.61(s,6H)。
Example 18
Preparation of hydroxypyrimidine ligand 3- (6- (9, 9-dimethylacridin-10 (9H) -yl) pyrimidin-4-yl) phenol OH-PDD.
10- (6- (3-methoxyphenyl) pyrimidin-4-yl) -9, 9-dimethyl-9, 10-dihydroacridine M-PDD (5g, 12.7 mmol) was weighed into a round-bottom flask, and hydrobromic acid (30mL, 1084 mmol) and glacial acetic acid (100mL, 890mmol) were injected, followed by reflux at 120 ℃ for 2 days. After the reaction, the reaction solution was cooled to room temperature, and a large amount of ice water was added to the reaction solution to precipitate a yellowish brown solid, which was then filtered off. By V PE :V EA Column chromatography of =3 gave 4.3 g of 3- (6- (9, 9-dimethylacridin-10 (9H) -yl) pyrimidin-4-yl) phenol OH-PDD as a yellow solid in 88.5% yield. 1 H NMR(400MHz,CDCl 3 )δ8.77(s,1H),8.46(d,J＝1.4Hz,1H),7.48(ddd,J＝8.6,2.3,1.2Hz,1H),7.32–7.21(m,5H),7.15–7.04(m,4H),6.93(dt,J＝6.5,1.4Hz,2H),6.81(ddd,J＝8.2,2.2,1.1Hz,1H),1.61(s,6H)。
Example 19
Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-dimethyl acridine MPXP.
(6R, 8R) -3- (3-bromophenyl) -pinene Br-DPTM (327.0mg, 1.0mmol), 3- (6- (9, 9-dimethylacridin-10 (9H) -yl) pyrimidin-4-yl) phenol OH-PDD (379.0mg, 1.0mmol), cuI (19.0mg, 0.1mmol), cesium carbonate (977.0mg, 3.0mmol), 2-picolinic acid (0.3g, 2.0mmol) were weighed out and placed in a sealed tube, 5mL of DMSO (5mL, 50mmol) after being deoxygenated by bubbling nitrogen was added, vacuum was taken, nitrogen gas was filled three times, and reaction was carried out at 120 ℃ for 24 hours. After the reaction is finished, dichloromethane is used for extraction, anhydrous sodium sulfate is used for drying, and a developing agent is used for column chromatography separation to obtain yellow powder pinene phenoxyl pyrimidine-10H-dimethylacridine MPXP of 0.42 g, and the yield is 67.2%. 1 H NMR(400MHz,DMSO)δ8.76(s,1H),8.18(s,1H),7.91(d,J＝7.8Hz,1H),7.81(dd,J＝20.7,12.0Hz,4H),7.67(d,J＝7.8Hz,1H),7.59(s,1H),7.53(t,J＝9.4Hz,4H),7.43(s,1H),7.31(dt,J＝14.7,7.0Hz,4H),7.22(d,J＝8.1Hz,1H),7.13(d,J＝9.8Hz,1H),3.00(s,2H),2.84(s,1H),2.68(s,1H),2.28(s,1H),1.99(s,1H),1.45(s,6H),1.39(s,3H),0.59(s,3H)。
Example 20
And (3) preparing the complex Pt-MDP.
Weighing pinene phenoxypyrimidine-10H-dimethylacridine MPXP (125.2mg, 0.2mmol) as a main ligand,
K 2 PtCl 4 (92.0 mg, 0.22mmol) was placed in a sealed tube, vacuum-pumped and charged with nitrogen. The acetic acid is blown with nitrogen for 10min, the acetic acid (10mL, 60mmol) is pumped out and added into a sealed tube under the protection of nitrogen, the mixture is stirred for 12h at room temperature, and the temperature is increased to 120 ℃ for reaction for 72h. After the reaction, the reaction solution was poured into a large amount of ice water, and a red solid was precipitated and filtered. By V PE :V DCM Column chromatography separation was performed using a developing solvent of =2, whereby 20 mg of Pt-MDP was obtained as a red powder in a yield of 12.3%. 1 H NMR(400MHz,CDCl 3 )δ9.05(d,J＝0.8Hz,1H),7.50–7.42(m,3H),7.40–7.33(m,2H),7.32–7.25(m,2H),7.15–7.04(m,4H),6.94–6.85(m,3H),6.73(ddd,J＝18.5,7.7,1.3Hz,2H),6.61(dd,J＝7.7,1.4Hz,1H),3.11–2.90(m,3H),2.01–1.87(m,2H),1.78(dt,J＝12.1,7.8Hz,1H),1.61(s,6H),0.97(d,J＝16.5Hz,6H)。
Example 21
And (3) preparing the complex Pd-MDP.
Weighing main ligands pinene phenoxy pyrimidine-10H-dimethyl acridine MPXP (125.2mg, 0.2mmol), pd (OAc) 2 (42.0 mg, 0.22mmol), TBAB (8.0 mg, 0.1mmol) in a sealed tube, evacuated and charged with nitrogen. The acetic acid was bubbled with nitrogen for 10min, then acetic acid (10mL, 60mmol) was pumped and added into the sealed tube under the protection of nitrogen, stirred at room temperature for 12h, and then heated to 120 ℃ for reaction for 72h. After the reaction is finished, pouring the reaction liquid into a large amount of ice water, separating out orange-red solids, and performing suction filtration. By V PE :V DCM And (3) performing column chromatography separation on the developing solvent of 2 to obtain orange red powder Pd-MDP40.0 mg with the yield of 32%. 1 H NMR(400MHz,CDCl 3 )δ8.87(d,J＝0.8Hz,1H),7.82(dd,J＝8.2,1.4Hz,1H),7.56–7.50(m,2H),7.44(d,J＝19.4Hz,2H),7.32–7.25(m,5H),7.15–7.04(m,4H),6.91(ddd,J＝7.9,6.4,1.3Hz,2H),6.67(ddd,J＝20.5,7.9,1.2Hz,2H),3.11–2.91(m,3H),2.01–1.87(m,2H),1.78(dt,J＝12.1,7.8Hz,1H),1.61(s,6H),0.97(d,J＝16.5Hz,6H)。
Example 22
The photophysical properties of platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP in dichloromethane solution were tested.
The ultraviolet-visible light absorption spectrum and the emission spectrum of the phosphorescent platinum (II) complex Pt-MDP and the palladium (II) complexes Pd-MD and Pd-MDP are shown in the attached figures 1 to 4. The complexes Pt-MDP, pd-MD and Pd-MDP are respectively prepared into 1 × 10 -4 2.5mL of the complexes Pt-MDP, pd-MD and Pd-M are removed from the Dichloromethane (DCM) solution of mol/LThe DP solution was placed in a fluorescent cuvette and tested for its UV-VIS absorption spectrum and emission spectrum. The experimental result shows that the three complexes respectively absorb more strongly at 230nm-400nm mainly because 1 Pi-pi transition, while the complex has a weaker absorption at 400nm-450nm, mainly due to the charge transfer from the singlet metal to the ligand (c: (c)) 1 MLCT) and spin-forbidden triplet metal to ligand charge transfer ((ii) 3 MLCT). When light of 380nm is used as excitation wavelength, the maximum emission peak of the platinum (II) complex Pt-MDP is at 590nm as can be seen in FIG. 2, and FIG. 3 and FIG. 4 show that the palladium (II) complexes Pd-MD and Pd-MDP have aggregation-induced emission characteristics, and the emission spectra of the complexes in different volume ratios of water/THF mixed solutions are tested. They are insoluble in water, and thus when the volume ratio of water in the mixed solution is gradually increased, the water molecules are squeezed to cause aggregation, resulting in enhancement of luminescence. When the water/THF ratio in the solution reached 90%, the solution became noticeably darker in color; and when the solution is completely a good solvent under the irradiation of an ultraviolet lamp of 365nm, little or very weak light is emitted, and when the ratio of water is 90%, strong light emission can be observed. Since the distance between molecules is far and the space of bond is relatively free in the state of dilute THF, the ligand and the complex do not emit in a dilute good solvent. In the aggregated state, the intermolecular interaction force is enhanced, and the bond twist is restricted, so that a stronger emission is obtained in the aggregated state. The maximum emission peaks of the complexes Pd-MD and Pd-MDP in an aggregation state luminescence state are both about 570nm, and the complexes have excellent stability. The complex Pd-MDP shows a relatively obvious piezochromic effect, and when the complex is ground, the luminescence has a red shift phenomenon, as shown in figure 5.
Example 23
The density functional theory of the platinum (II) complex Pt-MDP and the palladium (II) complexes Pd-MD and Pd-MDP.
Density Functional Theory (DFT) calculations were performed on complexes Pt-MDP, pd-MD and Pd-MDP using Gauss 06 to investigate the photophysical properties of these light emitting materials. Calculations using the B3LYP method were performed, and for these three complexes, the HOMO distribution was mainly localized to the central atoms palladium (II) and phenyl-oxy-phenyl, and LUMO was mainly localized to the electron acceptor pyrimidine unit. FIG. 6 shows atomic orbital occupancy ratio profiles for the three materials, with the HOMO levels of Pt-MDP, pd-MD, and Pd-MDP at-4.77 eV, -4.97eV, and-4.94eV, and the LUMO levels at-1.56 eV, -1.54eV, and-1.49 eV, respectively. The theoretical energy level differences for the three complexes are 3.21ev,3.43ev and 3.45eV, respectively.
Example 24
Electrochemical properties of platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP.
To investigate the HOMO and LUMO energy level states and charge carrier injection properties of platinum (II) and palladium (II) complexes, we used Cyclic Voltammetry (CV) in dichloromethane solution as Ag/AgNO 3 The oxidation potential of this system was measured for the reference electrode and as shown in FIG. 7, it can be seen that all complexes have an oxidation peak in the 1-1.5V range. And according to the respective oxidation potential and reduction potential of the complex, the corresponding HOMO energy level and LUMO energy level can be calculated, and further the energy gap E of the platinum (II) complex Pt-MDP and the palladium (II) complexes Pd-MD and Pd-MDP can be obtained g (difference between HOMO level and LUMO level) was 2.3eV, 2.21eV, and 2.67eV, respectively.
Example 25
And (5) manufacturing an organic electroluminescent device.
The device of the present invention having palladium (II) complexes Pd-MD and Pd-MDP as the light-emitting layer may comprise: the structure of the device is shown in FIG. 8, wherein HAT-CN (10 nm)/TAPC (30 nm)/TCTA (10 nm)/MCP is x% Pd (25 nm)/TmPyPb (35 nm)/Liq (1 nm)/Al, and HAT-CN is used as a hole injection layer of the device; TAPC and TCTA are used as hole transport layers and have the function of adjusting energy level matching; MCP, wherein x% Pd is used as a light emitting layer, MCP is used as a main body material, and palladium (II) complexes with different concentrations are doped; tmPyPb as an electron transport layer; liq also plays a role in adjusting energy level, and finally Al is used as a cathode of the device. The organic electroluminescent device with Pd-MD as the light emitting layer has the best performance when the device is doped with 15wt%, the maximum current efficiency is 34.52cd/A, the power efficiency is 19.72lm/W, and the external quantum efficiency is 9.37%. In particular, the undoped device still maintains good efficiencies of 9.61cd/A, 5.45lm/W and 9.88%. The graphs of the electroluminescence spectrum, current density-voltage-brightness, brightness-current efficiency and brightness-external quantum efficiency of the electroluminescent device are shown in figure 9. FIG. 10 is a graph of the electroluminescence spectrum, current density-voltage-luminance, luminance-current efficiency, and luminance-external quantum efficiency of Pd-MDP at 5%, 10%, 15%, 20%, and 100% doping concentrations. The best performance of the device is that the maximum current efficiency is 42.44cd/A, the power efficiency is 24.24lm/W, and the external quantum efficiency is 14.18%. The undoped device still keeps good efficiency of 12.53cd/A, 7.88lm/W and 7.03 percent. The data show that the complex containing the pinene structure with large steric hindrance and the D-A structure can obtain an efficient device.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A pinene pyrimidine tetradentate platinum (II) and palladium (II) complex is characterized in that the complex is an asymmetric chiral tetradentate complex of a pinene-based pyrimidine ligand, and the structural general formula of the complex is a compound represented by the following formula (I) and formula (II):
wherein R is one of N-carbazolyl, N-diphenylamino, N-phenothiazinyl, N-phenoxazinyl, N-dimethylazinyl, 2, 6-dimethyl substituted phenoxy, 2, 6-diisopropyl substituted phenoxy and hexahydropyridyl.
2. A method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex of claim 1, which comprises the following steps:
under the protection of nitrogen, dissolving potassium tetrachloroplatinate and pinene pyrimidine ligand in acetic acid, adding a catalyst, reacting at room temperature in a dark place, and then heating for reaction to obtain a pinene pyrimidine tetradentate platinum (II) complex shown as a formula (I);
under the protection of nitrogen, dissolving palladium acetate and a pinene pyrimidine ligand in acetic acid, adding a catalyst, reacting at room temperature in a dark place, and then heating to react to obtain the pinene pyrimidine tetradentate palladium (II) complex shown as the formula (II).
3. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, wherein the molar ratio of the raw materials used for preparing the pinene pyrimidine tetradentate platinum (II) complex is as follows: potassium tetrachloroplatinate: catalyst: pinene pyrimidine ligand: acetic acid =1.0 to 1.5:1 to 5:1:100 to 500.
4. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, wherein the molar ratio of the raw materials used for preparing the pinene pyrimidine tetradentate palladium (II) complex is as follows: palladium acetate: catalyst: pinene pyrimidine ligand: acetic acid =1.0 to 1.5:1 to 5:1:100 to 500.
5. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, wherein the catalyst is one of potassium acetate, sodium acetate and ammonium acetate.
6. The preparation method of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, which is characterized by comprising the following steps:
dissolving a pyrimidine compound shown as a formula (1) and a pinene compound shown as a formula (2) in an organic solvent, and reacting for 20-40 h at 100-130 ℃ in the presence of cuprous iodide and alkali to obtain a pinene pyrimidine chiral asymmetric tetradentate ligand shown as a formula (3);
under the protection of nitrogen, dissolving pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) and potassium tetrachloroplatinate in acetic acid, adding a catalyst, stirring at room temperature in a dark place for 6-12 h, heating to 120-150 ℃, and reacting for 18-72 h to obtain a pinene pyrimidine tetradentate palladium (II) complex shown in the formula (I);
under the protection of nitrogen, dissolving the pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) and palladium acetate in glacial acetic acid, adding a catalyst, stirring at room temperature in a dark place for 6-12 h, heating to 120-150 ℃ and reacting for 18-72 h to obtain the pinene pyrimidine tetradentate palladium (II) complex shown in the formula (II).
7. The preparation method of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 6, wherein the molar ratio of the raw materials used for preparing the pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) is as follows: a pyrimidine compound represented by the formula (1): a pinene compound represented by the formula (2): organic solvent: cuprous iodide: base =1:1:10 to 50:0.01 to 0.1:1 to 10.
8. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 6, wherein the organic solvent used for preparing the pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) is one of toluene, dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran and 1, 4-dioxane.
9. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 6, wherein the base used for preparing the pinene pyrimidine chiral asymmetric tetradentate ligand shown in the formula (3) is one of potassium carbonate, sodium tert-butoxide, potassium phosphate and cesium carbonate.
10. The application of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex as claimed in claim 1, which is characterized in that the complex is used as a luminescent layer in electroluminescent devices or in the fields of sensors, anti-counterfeiting, storage and display.
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| CN113717231B (en) * | 2021-09-06 | 2023-12-15 | 海南师范大学 | AIE active force-induced light five-membered six-membered heterocyclic platinum complex, and preparation method and application thereof |
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