Phosphorescent PtM.SUB.3 .heterotetranuclear complex, preparation method and use thereof

Abstract

An ionic phosphorescent metal complex complex has a formula of [PtM.sub.3{(PR.sub.2CH.sub.2).sub.3P}(C?CR)(C?CR)(?Cl)].sup.2+ A.sup.n?.sub.2/n. M is selected from Au(I) and Ag(I). R, R and R are identical or different, and are independently selected from alkyl, alkenyl, alkynyl, aryl, and heteroaryl. Each of the alkyl, alkenyl, alkynyl, aryl, and heteroaryl may be substituted with one or more substituents selected from alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, halogenated alkyl, aryl, and heteroaryl. The substituent is optionally further substituted with one or more of the following groups: alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, halogenated alkyl, aryl, and heteroaryl. A.sup.n? is a monovalent or divalent anion, n is 1 or 2, ?represents bridging linkage. The organic light-emitting diode prepared by using the complex as the light-emitting layer dopant has an external quantum efficiency of 10% or more, and can be applied to the fields of flat panel display and daily lighting.

Claims

1. A phosphorescent PtM.sub.3 heterotetranuclear metal alkynyl complex of formula (I)
[PtM.sub.3{(PPh.sub.2CH.sub.2).sub.3P}(C?CR)(C?CR)(?Cl)].sup.2+A.sup.n?.sub.2n(I), wherein, M is Au(I) or Ag(I); R and R are identical or different, and are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, and heteroaryl; the substituted alkyl, alkenyl, alkynyl, aryl, and heteroaryl are substituted by substituents independently selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, halogenated alkyl, aryl, and heteroaryl; A.sup.n? is a monovalent or divalent anion; n is 1 or 2; and ?represents bridging linkage.

2. The complex according to claim 1, wherein the monovalent or divalent anion is selected from ClO.sub.4.sup.?, PF.sub.6.sup.?, SbF.sub.6.sup.?, BF.sub.4.sup.?, B(C.sub.6H.sub.5).sub.4.sup.?, CF.sub.3SO.sub.3.sup.?, and SiF.sub.6.sup.2?.

3. The complex according to claim 1, wherein the complex of formula (I) has one of the stereostructures shown below: ##STR00004## wherein a dash line represents a linking bond.

4. A preparation method of the complex according to claim 1, comprising: reacting (Ph.sub.2PCH.sub.2).sub.3P, Au(THT)Cl or [Ag(THT)]ClO.sub.4, (NH.sub.4)(A.sup.n?) and Pt(PPh.sub.3).sub.2(C?CR)(C?CR) in one or more chlorinated hydrocarbon solvents to obtain the complex of formula (I), wherein THT represents tetrahydrothiophene.

5. The preparation method according to claim 4, wherein the one or more chlorinated hydrocarbon solvents is dichloromethane.

6. An organic light-emitting diode, comprising a light-emitting layer, wherein the light-emitting layer comprises the complex according to claim 1.

7. The organic light-emitting diode according to claim 6, wherein the organic light-emitting diode comprises an anode layer, a hole injection layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer, wherein the light-emitting layer further comprises a substance with hole transport properties, a substance with electron transport properties, or both, wherein the substance with hole transport properties is one or more selected from 2,6-bis(3-(9-carbazolyl)phenyl)pyridine, mCP, CBP, and TCTA, and the substance with electron transport properties is 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl) benzene.

8. A flat panel display, comprising a plurality of the organic light-emitting diode according to claim 6.

9. A lighting device, comprising the organic light emitting diode according to claim 6.

10. The complex according to claim 1, wherein the R and R are identical or different, and are independently selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl,-aryl-heteroaryl,-heteroaryl-aryl, -aryl-aryl, and -heteroaryl-heteroaryl, wherein the substituted alkyl, substituted aryl, and substituted heteroaryl are substituted by substituents selected from alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, halogenated alkyl, aryl, and heteroaryl.

11. The complex according to claim 1, wherein the R and R are identical or different, and are independently selected from alkyl, aryl, carbazolyl, phenothiazinyl, quinazolinyl, arylcarbazolyl, carbazolylaryl, aryloimidazolyl, aryloimidazolylaryl; and each of the alkyl, aryl, carbazolyl, phenothiazinyl, quinazolinyl, and aryloimidazolyl is optionally further substituted with one or more substituents selected from alkyl, alkoxy, halogen, halogenated alkyl, aryl, carbazolyl, phenothiazinyl, quinazolinyl, NH-aryl, N(aryl).sub.2, aryloimidazolyl, and imidazolyl.

12. The complex according to claim 1, wherein the R and R are identical or different, and are independently selected from aryl, carbazolylaryl, alkylaryl, alkylcarbazolyl, arylcarbazolyl, carbazolylarylcarbazolyl, N-alkylphenothiazinyl, diarylaminoaryl, N-aryl-phenanthroimidazolyl aryl, and N-aryl-benzoimidazolyl aryl.

13. The organic light-emitting diode according to claim 7, wherein in the light-emitting layer, the complex accounts for 1-20% by weight of the light-emitting layer.

14. The organic light-emitting diode according to claim 7, wherein the anode is indium tin oxide (ITO) and the hole injection layer is poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid).

15. The organic light-emitting diode according to claim 7, wherein the substance with hole transport properties is one or more selected from 2,6-bis(3-(9-carbazolyl)phenyl)pyridine, mCP, CBP, and TCTA, and the substance with electron transport properties is 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl) benzene.

16. The organic light-emitting diode according to claim 7, wherein the electron transport layer is one or more selected from 3,3,5,5-tetra(3-pyridyl)-1,1:3,1-terphenyl, TPBi, BCP, and 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol- 2-yl) benzene.

17. The organic light-emitting diode according to claim 7, wherein the electron injection layer is LiF, and the cathode is A1.

18. The complex according to claim 3, wherein in ##STR00005## R is ##STR00006## and R is ##STR00007## or R is ##STR00008## and R is ##STR00009## or R is ##STR00010## and R is ##STR00011## or R is ##STR00012## and R is ##STR00013## or R is ##STR00014## and R is ##STR00015## or R is ##STR00016## and R is ##STR00017## or R is ##STR00018## and R is ##STR00019## or R is ##STR00020## and R is ##STR00021## or R is ##STR00022## and R is ##STR00023## and wherein in ##STR00024## R is ##STR00025## and R is ##STR00026## or R is ##STR00027## and R is ##STR00028## or R is ##STR00029## and R is ##STR00030## or R is ##STR00031## and R is ##STR00032## or R is ##STR00033## and R is ##STR00034##

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) To make the objectives, technical solutions and technical effects clearer, the present invention will be further illustrated in detail below in combination with the drawings and the examples. It should be understood that the examples described in the description are only to explain the invention and are not intended to limit the invention.

(2) In the following examples, Carb represents carbazolyl, 4-C.sub.6H.sub.4Carb-9 represents 4-(9-9H-carbazolyl)phenyl, Ph represents phenyl, C.sub.6H.sub.4Bu.sup.t-4 represents 4-tert-butyl-phenyl, 2-Carb-9-Ph represents 9-phenyl-9H-carbazol-2-yl, 3-CarbC.sub.6H.sub.4Carb-9 represents 4-(9H-carbazol-9-yl) phenyl-carbazol-3-yl, 3-PTZ-10-Et represents 10-ethyl-10H-phenothiazin-3-yl, 4-C.sub.6H.sub.4NPh.sub.2 represents 4-diphenylamino-phenyl, 4-C.sub.6H.sub.4-phenim represents 4-(1-phenyl-1H-phenanthro[9,10-D]imidazol-2-yl)-phenyl, 4-C.sub.6H.sub.4-2-benzimd-1-Ph represents 4-(1-phenyl-1H-benzo[d]imidazol-2-yl) phenyl, 3-Carb-9-Ph represents 9-phenyl-9H-carbazol-3-yl, 2-Carb-9-Et represents 9-ethyl-9H-carbazol-2-yl, and THT represents tetrahydrothiophene.

Example 1: Preparation of Complex 1

(3) To a solution (20 mL) of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2 (62.6 mg, 0.05 mmol) in dichloromethane, (Ph.sub.2PCH.sub.2).sub.3P (62.8 mg, 0.1 mmol), Au(THT) Cl (48 mg, 0.15 mmol), and NH.sub.4ClO.sub.4 (18 mg, 0.15 mmol) were added. The reaction mixture turned to light yellow after being stirred at room temperature for 8 hours. The main product was obtained and purified by silica gel column chromatography using CH.sub.2Cl.sub.2/MeOH (V/V=10: 0.5) as the eluent. Yield: 68%. .sup.1H NMR (CDCl.sub.3, ppm): 8.18 (d, 4H, J=7.72 Hz), 7.93-7.97 (m, 16H), 7.72 (d, 8H, J=6.88 Hz), 7.50-7.54 (m, 16H), 7.39-7.42 (m, 14H), 7.31-7.34 (m, 10H), 7.16 (t, 8H, J=7.52 Hz), 6.90 (d, 4H, J=8.36 Hz), 5.70 (d, 4H, J=8.32 Hz), 4.17 (br, 4H), 3.67 (br, 8H). .sup.31P NMR (CDCl.sub.3, ppm): 30.4 (t, 4P, JP-P=31.5 Hz), 22.7 (m, 2P, J.sub.P-P=25.0 Hz), 4.2 (t, 2P, J.sub.P-P=25.1 Hz, J.sub.Pt_P=2676 Hz). HRMS (ESI): Calculated according to C.sub.118H.sub.96Au.sub.3ClN.sub.2P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1305.1880; Found: 1305.1839. IR (KBr, cm.sup.?1): 2107w (C?C), 1100s (ClO.sub.4.sup.?).

Example 2: Preparation of Complex 2

(4) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-C.sub.6H.sub.4Bu.sup.t-4).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 72%. .sup.1H NMR (CDCl.sub.3, ppm): 7.89-7.93 (m, 8H), 7.74-7.77 (m, 8H, 7.66-7.70 (m, 8H), 7.49-7.52 (m, 14H), 7.31-7.34 (m, 14H), 7.02-7.05 (m, 8H, 6.54 (d, 4H, J=8.04 Hz), 5.41 (d, 4H, J=8.04 Hz), 4.08 (br, 4H), 3.85 (br, 4H), 3.54 (br, 4H) 0.98-1.2 (m, 18H). .sup.31P NMR (CDCl.sub.3, ppm): 29.1 (t, 4P, J.sub.P-P=32.6 Hz), 17.8 (m, 2P, J.sub.P-P=30.0 Hz), 4.8 (t, 2P, J.sub.P-P=27.1 Hz, J.sub.Pt-P=2694 Hz). HRMS (ESI): Calculated according to C.sub.102H.sub.98Au.sub.3ClN.sub.2P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1196.1927; Found: 1196.1976. IR (KBr, cm.sup.?1): 2105w (C?C), 1100s (ClO.sub.4.sup.?).

Example 3: Preparation of Complex 3

(5) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-2-PhCarb-9).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 70%. .sup.1H NMR (CDCl.sub.3, ppm): 8.01-8.03 (m, 8H), 7.74-7.77 (m, 1OH), 7.66-7.69 (m, 1OH), 7.51-7.55 (m, 12H), 7.43-7.49 (m, 12H), 7.37-7.41 (m, 16H), 6.95 (m, 1OH), 6.78 (d, 2H, J=8.4 Hz), 6.02 (s, 2H), 5.78 (d, 2H, J=8.4 Hz), 4.13 (br, 4H), 4.03 (br, 4H), 3.65 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 29.6 (t, 4P, J.sub.P-P=32.0 Hz), 18.1 (m, 2P, J.sub.P-P=30.6 Hz), 6.2 (t, 2P, J.sub.P-P=30.0 Hz, J.sub.Pt-P=2726 Hz). HRMS (ESI): Calculated according to C.sub.118H.sub.96Au.sub.3ClN.sub.2P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1305.1880; Found: 1305.1909. IR (KBr, cm.sup.?1): 2099w (C?C), 1100s (ClO.sub.4.sup.?).

Example 4: Preparation of Complex 4

(6) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-3-CarbC.sub.6H.sub.4Carb-9).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 55%. .sup.1H NMR (CDCl.sub.3, ppm): 8.23 (d, 4H, J=7.56 Hz), 8.04-8.07 (m, 8H), 7.87-7.90 (m, 6H), 7.76-7.81 (m, 18H), 7.58-7.61 (m, 1OH), 7.48-7.52 (m, 14H), 7.42-7.47 (m, 20H), 7.02-7.05 (m, 1OH), 6.95 (d, 4H, J=8.48 Hz), 6.05 (s, 2H), 5.91 (d, 2H, J=8.52 Hz), 4.16 (br, 4H), 4.06 (br, 4H), 3.68 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 29.7 (t, 4P, J.sub.P-P=32.5 Hz), 18.2 (m, 2P, J.sub.P-P=30.6 Hz), 6.2 (t, 2P, J.sub.P-P=27.4 Hz, J.sub.Pt-P=2706 Hz). HRMS (ESI): Calculated according to C.sub.142H.sub.110Au.sub.3ClN.sub.4P.sub.8Pt [M?2ClO.sub.4].sup.2+. 1470.7458; Found: 1470.7484. IR (KBr, cm.sup.?1): 2104w (C?C), 1100s (ClO.sub.4.sup.?).

Example 5: Preparation of Complex 5

(7) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-3-PTZ-10-Et) was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 70%. .sup.1H NMR (CDCl.sub.3, ppm): 7.87-7.89 (m, 8H), 7.74-7.77 (m, 8H), 7.66-7.69 (m, 8H), 7.48-7.51 (m, 12H), 7.36-7.39 (m, 12H), 7.12-7.15 (m, 16H), 6.95 (t, 2H, J=7.20 Hz), 6.86 (d, 2H, J=8.16 Hz), 6.18 (d, 2H, J=8.52 Hz), 5.35 (d, 2H, J=8.38 Hz), 5.04 (s, 2H), 4.04 (br, 4H), 3.93 (br, 4H), 3.84 (q, 4H, J=6.90 Hz),3.54 (br, 4H), 1.41 (t, 6H, J=6.84 Hz). .sup.31P NMR (CDCl.sub.3, ppm): 29.6 (t, 4P, J.sub.P-P=32.0 Hz), 18.4 (m, 2P, J.sub.P-P =29.4 Hz), 5.8 (t, 2P, J.sub.P-P=29.0 Hz, J.sub.Pt-P=2706 Hz). HRMS (ESI): Calculated according to C.sub.110H.sub.96Au.sub.3ClN.sub.2P.sub.8PtS.sub.2 [M?2ClO.sub.4].sup.2+: 1289.1600; Found: 1289.1571. IR (KBr, cm.sup.?1): 2099w (C?C), 1100s (ClO.sub.4).

Example 6: Preparation of Complex 6

(8) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4NPh.sub.2).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 70%. .sup.1H NMR (CDCl.sub.3, ppm): 7.89-7.91 (m, 16H), 7.61-7.66 (m, 8H), 7.49-7.51 (m, 12H), 7.29-7.32 (m, 12H), 7.29-7.32 (m, 8H), 7.20 (t, 4H, J=7.4 Hz), 7.05-7.09 (m, 12H), 7.02 (d, 8H, J=7.4 Hz), 6.36 (d, 4H, J=8.8 Hz), 5.40 (d, 4H, J=8.0 Hz), 4.05 (br, 4H), 3.56 (br, 4H), 3.51 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 30.4 (t, 4P, J.sub.P-P=31.6 Hz), 22.5 (m, 2P, J.sub.P-P=31.4 Hz), 3.7 (t, 2P, J.sub.P-P=29.9 Hz, J.sub.Pt-P=2696 Hz). HRMS (ESI): Calculated according to C.sub.118H.sub.100Au.sub.3ClN.sub.2P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1307.2036; Found: 1307.2065. IR (KBr, cm.sup.?1): 2096w (C?C), 1100s (ClO.sub.4).

Example 7: Preparation of Complex 7

(9) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4-phenim).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 70%. .sup.1H NMR (CDCl.sub.3, ppm): 8.87 (d, 2H, J=8.0 Hz), 8.80 (d, 2H, J=8.4 Hz), 8.74 (d, 2H, J=8.4 Hz), 7.86-7.91 (m, 6H), 7.83-7.84 (m, 10H), 7.68-7.72 (m, 8H), 7.59-7.61 (m, 12H), 7.51-7.56 (m, 22H), 7.43-7.46 (m, 2H), 7.30-7.36 (m, 12H), 7.13 (d, 2H, J=8.0 Hz), 7.04 (t, 6H, J=7.2 Hz), 6.96 (d, 4H, J=8.0 Hz), 5.33 (d, 4H, J=8.0 Hz), 4.06 (br, 4H), 3.57 (br, 4H), 3.48 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 30.4 (t, 4P, J.sub.P-P=31.4 Hz), 22.7 (m, 2P, J.sub.P-P=31.4 Hz), 4.1 (t, 2P, J.sub.P-P=30.1 Hz, J.sub.Pt-P=2670 Hz). HRMS (ESI): Calculated according to C.sub.136H.sub.106Au.sub.3ClN.sub.4P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1432.2302; Found: 1432.2273. IR (KBr, cm.sup.?1): 2101w (C?C), 1100s (ClO.sub.4.sup.?).

Example 8: Preparation of Complex 8

(10) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4-2-benzimd-1-Ph).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 70%. .sup.1H NMR (CDCl.sub.3, ppm): 7.89-7.91 (m, 8H), 7.80-7.82 (m, 10H), 7.57-7.61 (m, 12H), 7.45-7.49 (m, 18H), 7.34-7.36 (m, 6H), 7.26-7.29 (m, 20H), 6.99 (t, 6H, J=7.2 Hz), 6.94 (d, 4H, J=8.4 Hz), 5.30 (d, 4H, J=8.4 Hz), 4.07 (br, 4H), 3.54 (br, 4H), 3.46 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 30.4 (t, 4P, J.sub.P-P=31.4 Hz), 22.6 (m, 2P, J.sub.P-P=30.6 Hz), 3.9 (t, 2P, J.sub.P-P=29.8 Hz, J.sub.Pt-P=2686 Hz). HRMS (ESI): Calculated according to C.sub.120H.sub.98Au.sub.3ClN.sub.4P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1332.1989; Found: 1332.2010. IR (KBr, cm.sup.?1): 2092w (C?C), 1100s (ClO.sub.4.sup.?).

Example 9: Preparation of Complex 9

(11) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4-2-benzimd-1-Ph)(C?C-3-Carb-9-Ph) was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2. Yield: 70%. .sup.1H NMR (CDCl.sub.3, ppm): 8.02-8.06 (m, 4H), 7.80-7.82 (m, 16H), 7.65-7.69 (m, 8H), 7.51-7.55 (m, 1OH), 7.39-7.42 (m, 20H), 7.24-7.26 (m, 4H), 7.04-7.06 (m, 4H), 6.93-6.95 (m, 4H), 6.72 (d, 1H, J=8.4 Hz), 6.01 (s, 1H), 5.70 (d, 1H, J=8.0 Hz), 5.42 (d, 2H, J=8.0 Hz), 4.04 (br, 4H), 3.86 (br, 4H), 3.69 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 29.4 (t, 4P, J.sub.P-P=31.4 Hz), 17.9 (m, 2P, J.sub.P-P=31.4 Hz), 5.5 (t, 2P, J.sub.P-P=30.4 Hz, J.sub.Pt-P=2686 Hz). HRMS (ESI): Calculated according to C.sub.119H.sub.97Au.sub.3ClN.sub.3P.sub.8Pt [M?2ClO.sub.4].sup.2+1318.6934; Found: 1318.6961. IR (KBr, cm.sup.?1): 2104w (C?C), 1100s (ClO.sub.4.sup.?).

Example 10: Preparation of Complex 10

(12) The preparation method was the same as that in Example 1, except that Ag(THT)ClO.sub.4 was used instead of Au(THT)Cl. Yield: 76%. .sup.1H NMR (CDCl.sub.3, ppm): 8.20 (d, 4H, J=7.72 Hz), 7.87-7.91 (m, 8H), 7.69-7.72 (m, 14H), 7.48-7.51 (m, 1OH), 7.35-7.38 (m, 1OH), 7.29-7.33 (m, 18H), 7.20-7.23 (m, 12H), 6.66 (t, 4H, J=6.44 Hz), 5.19 (d, 4H, J=8.32 Hz), 4.17 (br, 4H), 3.46 (br, 8H). .sup.31P NMR (CDCl.sub.3, ppm): 19.3 (m, 2P, J.sub.Pt-P=2402 Hz), 9.6 (m, 1P, J.sub.P-P=37.2 Hz), 6.3 (m, 1P, J.sub.P-P=37.2 Hz), ?0.6 (m, 4P). HRMS (ESI): Calculated according to C.sub.118H.sub.96Ag.sub.3ClN.sub.2P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1172.0958; Found: 1172.0993. IR (KBr, cm.sup.?1): 2084w (C?C), 1098s (ClO.sub.4.sup.?).

Example 11: Preparation of Complex 11

(13) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?CC.sub.6H.sub.4Bu.sup.t-4).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2, and Ag(THT)ClO.sub.4 was used instead of Au(THT)Cl. Yield: 84%. .sup.1H NMR (CDCl.sub.3, ppm): 7.74-7.78 (m, 14H), 7.53-7.56 (m, 10H, 7.43-7.46 (m, 4H), 7.29-7.33 (m, 14H), 7.18-7.21 (m, 10H), 7.09-7.12 (m, 8H, 6.20 (d, 4H, J=8.08 Hz), 4.91 (d, 4H, J=8.04 Hz), 3.96 (br, 4H), 3.31 (br, 4H), 3.10 (br, 4H) 0.96-1.2 (m, 18H). .sup.31P NMR (CDCl.sub.3, ppm): 19.1 (m, 2P, J.sub.P-P=27.9 Hz, J.sub.Pt-P=2344 Hz), 9.0 (m, 1P, J.sub.P-P=37.8 Hz), 5.7 (m, 1P, J.sub.P-P=37.8 Hz), ?4.0 (m, 4P). IR (KBr, cm.sup.?1): 2082w (C?C), 1098s (ClO.sub.4).

Example 12: Preparation of Complex 12

(14) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-2-Carb-9-Et).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2, and Ag(THT)ClO.sub.4 was used instead of Au(THT)Cl. Yield: 75%. .sup.1H NMR (CDCl.sub.3, ppm): 7.81-7.84 (m, 8H), 7.72-7.75 (m, 6H), 7.64-7.67 (m, 8H), 7.37-7.40 (m, 6H), 7.38-7.41 (m, 6H), 7.32-7.36 (m, 12H), 7.24-7.27 (m, 6H), 7.19-7.22 (m, 12H), 7.07-7.10 (m, 1OH), 6.32 (d, 2H, J=8.52 Hz), 5.96 (s, 2H), 5.11 (d, 2H, J=8.12 Hz), 4.29 (q, 4H, J=7.16 Hz), 4.25 (br, 4H), 3.45 (br, 4H), 3.29 (br, 4H), 1.43 (t, 6H, J=7.12 Hz). .sup.31P NMR (CDCl.sub.3, ppm): 18.9 (m, 2P, J.sub.P-P=28.1 Hz, J.sub.Pt-P=2406 Hz), 9.3 (m, 1P, J.sub.P-P=37.3 Hz), 5.8 (m, 1P, J.sub.P-P=37.3 Hz), ?0.8 (m, 2P, J.sub.P-P=30.8 Hz), ?3.6 (m, 2P, J.sub.P-P=30.8 Hz). HRMS (ESI): Calculated according to C.sub.110H.sub.96Ag.sub.3ClN.sub.2P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1124.0958; Found: 1124.0975. IR (KBr, cm.sup.?1): 2071w (C?C), 1098s (ClO.sub.4.sup.?).

Example 13: Preparation of Complex 13

(15) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-3-CarbC.sub.6H.sub.4Carb-9).sub.2 was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2, and Ag(THT)ClO.sub.4 was used instead of Au(THT)Cl. Yield: 72%. .sup.1H NMR (CDCl.sub.3, ppm): 8.24 (d, 2H, J=7.72 Hz), 7.91-7.94 (m, 12H), 7.73-7.78 (m, 18H), 7.62-7.65 (m, 4H), 7.51-7.54 (m, 8H), 7.40-7.44 (m, 8H), 7.31-7.35 (m, 16H), 7.24-7.27 (m, 14H), 7.13-7.16 (m, 10H), 6.47 (d, 2H, J=8.60 Hz), 6.05 (s, 2H), 5.15 (d, 2H, J=7.76 Hz), 4.28 (br, 4H), 3.48 (br, 4H), 3.33 (br, 4H). .sup.31P NMR (CDCl.sub.3, ppm): 18.9 (m, 2P, J.sub.P-P=27.2 Hz, J.sub.Pt-P=2302 Hz), 9.3 (m, 2P, J.sub.P-P=37.6 Hz), 3.4 (m, 4P, J.sub.P-P=28.2 Hz). HRMS (ESI): Calculated according to C.sub.142H.sub.110Ag.sub.3ClN.sub.4P.sub.8Pt [M?2ClO.sub.4].sup.2+: 1337.1536; Found: 1337.1550. IR (KBr, cm.sup.?1): 2071w (C?C), 1098s (ClO.sub.4).

Example 14: Preparation of Complex 14

(16) The preparation method was the same as that in Example 1, except that Pt(PPh.sub.3).sub.2(C?C-3-PTZ-10-Et) was used instead of Pt(PPh.sub.3).sub.2(C?C-4-C.sub.6H.sub.4Carb-9).sub.2, and Ag(THT)ClO.sub.4 was used instead of Au(THT)Cl. Yield: 78%. .sup.1H NMR (CDCl.sub.3, ppm): 8.05 (d, 2H, J=7.76 Hz), 7.91-7.94 (m, 8H), 7.72-7.76 (m, 6H), 7.54-7.57 (m, 8H), 7.38-7.42 (m, 10H), 7.23-7.28 (m, 20H), 7.13-7.16 (m, 6H), 7.01-7.04 (m, 10H), 5.58 (s, 2H), 5.05 (d, 2H, J=8.12 Hz), 4.23 (br, 4H), 3.39 (q, 4H, J=6.92 Hz), 3.23 (br, 8H), 1.05 (t, 6H, J=7.16 Hz). .sup.31P NMR (CDCl.sub.3, ppm): 18.0 (m, 2P, J.sub.P-P=26.4 Hz, J.sub.Pt-P=2336 Hz), 9.1 (m, 1P, J.sub.P-P=31.4 Hz), 5.6 (m, 1P, J.sub.P-P=31.4 Hz), ?1.5 (m, 2P), -4.4 (m, 2P). HRMS (ESI): Calculated according to C.sub.110H.sub.96Ag.sub.3ClN.sub.2P.sub.8PtS.sub.2 [M?2ClO.sub.4].sup.2+: 1156.0678; Found: 1156.0700. IR (KBr, cm.sup.?1): 2092w (C?C), 1096s (ClO.sub.4).

Example 15: Measurement of photoluminescence performance

(17) The luminescent properties including excitation and emission spectra, luminescence lifetime, and luminescence quantum yield of complexes 1-14 prepared in Example 1-14 were measured on a Edinburgh FLS920 fluorescence spectrometer in dichloromethane solution, powder and doping film of 48.5% mCP: 48.5% OXD-7 (1:1): 3% complex of the present invention (weight ratio). An integrating sphere with a diameter of 142 mm was used to determine the luminescence quantum yield of the solid powder sample.

(18) The phosphorescence emission wavelength (?.sub.em), luminescence lifetime (?.sub.em) and quantum yield (?.sub.PL) of PtAu.sub.3 Complexes 1-9 and PtAg.sub.3 Complexes 10-14 are listed in Table 1.

(19) TABLE-US-00001 TABLE 1 Photoluminescence performance data of the PtM.sub.3 complexes 1-14 ?.sub.em (nm)/?.sub.em (?s)/?.sub.PL (%) Complex CH.sub.2Cl.sub.2 solution Solid powder Doped film .sup.[a] 1 524/2.53/1.1 570/3.41/5.1 512/4.90/90.5 2 528/2.13/2.6 544/2.39/2.8 522/3.37/68.3 3 550/2.88/2.6 575/3.60/7.8 543/5.11/88.4 4 565/2.37/9.7 592/3.49/9.3 559/4.64/89.3 5 648/1.86/2.9 650/2.18/2.5 590/5.90/76.8 6 602/2.40/2.6 600/2.50/3.3 563/4.00/85.5 7 582/2.53/1.8 574/6.20/10.6 552/15.6/80.6 8 533/2.30/1.5 541/5.90/41.5 528/12.3/90.1 9 565/2.37/2.3 582/2.80/16.8 548/4.20/80.2 10 541/3.11/0.1 590/3.46/0.1 522/4.58/0.8 11 513/2.61/0.1 530/2.99/0.1 472/2.34/0.1 12 550/2.11/0.1 570/2.69/0.1 542/4.41/0.6 13 562/2.39/0.1 590/2.56/0.1 533/5.43/2.1 14 653/1.92/0.1 687/2.32/0.1 616/5.39/3.0 .sup.[a] The doping film contains 48.5% of mCP, 48.5% of OXD-7 and 3% of PtM.sub.3 complex by weight.

(20) As can be seen from the results in Table 1, PtAu.sub.3 Complexes 1-9 exhibit moderate photoluminescence in a dichloromethane solution and solid state, but very strong phosphorescence in the doping film containing 48.5% of mCP, 48.5% of OXD-7 and 3% of PtM.sub.3 Complex. The luminescence quantum yields up to 76.8% to 90.5% in doping film suggest that they are ideal light-emitting materials for organic light-emitting diodes. The PtAg.sub.3 Complexes 10-14 have photoluminescence properties and can also be used in organic light-emitting diodes.

Example 16: Preparation of Organic Light-Emitting Diode and Measurement of Electroluminescent performance

(21) The phosphorescent complexes 3, 4, 5, 8 and 9 prepared in Examples 3, 4, 5, 8, and 9 respectively were used as the luminescent material and doped at a weight percentage of 3% in the mCP (48.5%): OXD-7 (48.5%) mixed host material as the light-emitting layer to prepare the organic light-emitting diode. The device has the following structure: ITO/PEDOT: PSS (50 nm)/48.5% of mCP: 48.5% of OXD-7:3% of the complex 3, 4, 5, 8 or 9 (50 nm)/BmPyPb (50 nm)/LiF (1 nm)/A1 (100 nm).

(22) Firstly, the ITO substrate was washed with deionized water, acetone, and isopropanol and then treated with UV-ozone for 15 minutes. The ITO substrate was spin-coated with a filtered PEDOT: PSS aqueous solution by using a spin coater at a speed of 4800 revolutions/minute, and then was dried at 140? C. for 20 minutes to obtain a hole injection layer with a thickness of 50 nm. Secondly, on the thin film of PEDOT: PSS, a filtered dichloromethane solution of 48.5% of mCP: 48.5% of OXD-7:3% of the complex 3, 4, 5, 8 or 9 (weight percentage) of the present invention at a concentration of 5.5 mg/mL was spin-coated by using a spin coater at a speed of 2100 revolutions/min to form a light-emitting layer with a thickness of 50 nm. Subsequently, the ITO substrate was placed in a vacuum chamber with a vacuum degree of not less than 4?10.sup.?4 Pa to thermally evaporate in sequence with Bmpypb with 50 nm thickness as electron transport layer, LiF with 1 nm thickness as electron-injection layer, and A1 with 100 nm thickness as the cathode of the device.

(23) The electroluminescence performance of the light-emitting diode device was measured in a dry air environment (humidity<30%) at room temperature. Electroluminescence performance parameters include electroluminescence wavelength (?.sub.EL), turn-on voltage (V.sub.on), maximum brightness (L.sub.max), maximum current efficiency (CE.sub.max), maximum power efficiency (PE.sub.max) and maximum external quantum efficiency (EQE.sub.max). The relevant electroluminescent data are listed in Table 2.

(24) TABLE-US-00002 TABLE 2 Electroluminescence performance data of organic light-emitting diodes based on phosphorescent complexes 3, 4, 5, 8 or 9 L.sub.max CE.sub.max PE.sub.max Com- ?.sub.EL V.sub.on (cd/ (cd/ (lm/ EQE.sub.max plex (nm) (V).sup.[a] m.sup.2).sup.[b] A).sup.[c] W).sup.[d] (%).sup.[e] CIE.sup.[f] 3 541 5.2 10911 58.3 26.1 14.9 0.33, 0.61 4 556 5.5 12711 62.8 25.1 17.7 0.24, 0.51 5 588 4.9 19308 45.2 20.3 18.1 0.47, 0.52 8 527 3.0 10415 38.7 22.9 10.3 0.30, 0.61 9 537 3.4 17079 55.6 35.0 14.8 0.33, 0.61 .sup.[a]Turn-on voltage at a brightness of 1 cd/m.sup.2. .sup.[b]Maximum brightness. .sup.[c]Maximum current efficiency. .sup.[d]Maximum power efficiency. .sup.[e]Maximum external quantum efficiency. .sup.[f]Chromaticity coordinates.

(25) As can be seen from the results in Table 2, the organic light-emitting diode prepared by the solution spin-coating method with Complex 3, 4, 5, 8 or 9 as the luminescent material has excellent electroluminescence performance, with the maximum luminous brightness exceeding 10000 cd/m.sup.2, the maximum current efficiency being 38.7 to 62.8 cd/A, and the maximum external quantum efficiency (EQE) exceeding 10%.

(26) The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent alternative, improvement, and the like, falling within the spirit and scope of the present invention, are intended to be included within the protection scope of the present invention.