Phosphorescent PtAg2 complex, preparation method therefor and use thereof

Abstract

Provided is an ionic type phosphorescent metal complex with a racemization structure, a preparation method therefor and a use thereof. The structure of the complex is [PtAg.sub.2{rac-(PPh.sub.2CH.sub.2PPhCH.sub.2—).sub.2}(C≡CR).sub.2(PR′.sub.3).sub.2].sup.2+A.sup.n−.sub.2/n or [PtAg.sub.2{meso-(PPh.sub.2CH.sub.2PPhCH.sub.2—).sub.2}(C≡CR).sub.2(PR′.sub.3)(μ-X)].sup.+.sub.mA.sup.m−, wherein R is the same or different and is independently selected from alkyl, aryl, heteroaryl, and heteroaryl aryl; R′ is the same or different and is independently selected from alkyl, aryl, and heteroaryl; the alkyl, aryl, and heteroaryl can be substituted by one or more substituents which are selected from alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, halogenated alkyl, and aryl; X is halogen; A.sup.m− and A.sup.n− are monovalent or bivalent anions; and m or n is 1 or 2. The present invention also relates to an organic light emitting diode, a preparation method therefor and use thereof. The organic light emitting diode prepared by taking the phosphorescent metal complex of the present invention as a luminous layer dopant has high-performance organic electroluminescence and can be applied to panel display.

Claims

1. An ionic-type phosphorescent metal complex having a structure as shown in the following formula (I) or formula (II):
[PtAg.sub.2{rac-(PPh.sub.2CH.sub.2PPhCH.sub.2—).sub.2}(C≡CR).sub.2(PR′.sub.3).sub.2].sup.2+A.sup.n−.sub.2/n;  (I)
or
[PtAg.sub.2{meso-(PPh.sub.2CH.sub.2PPhCH.sub.2—).sub.2}(C≡CR).sub.2(PR′.sub.3)(μ-X)].sup.+.sub.mA.sup.m−  (II), wherein: R is identical or different, independently selected from alkyl, aryl, heteroaryl, and heteroaryl aryl; R′ is identical or different, independently selected from alkyl, aryl, and heteroaryl; the alkyl, the aryl, or the heteroaryl is optionally substituted by one or more substituents selected from an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a halogen, a haloalkyl group, and an aryl group; X is halogen; A.sup.m− is a monovalent or bivalent anion, A.sup.n− is a monovalent or bivalent anion, m is 1 or 2, and n is 1 or 2; and μ stands for bridging.

2. The ionic-type phosphorescent metal complex according to claim 1, wherein a stereostructure of the ionic-type phosphorescent metal complex of formula (I) or formula (II) is represented as follows: ##STR00004##

3. The ionic-type phosphorescent metal complex according to claim 1, wherein R is aryl, carbazolyl, phenothiazinyl or carbazolylaryl; the aryl, the carbazolyl or the phenothiazinyl is optionally substituted by one or more substituents selected from alkyl, alkoxy, amino, halogen, haloalkyl, and aryl; R′ is aryl or a nitrogen-containing heterocyclic; the aryl or the nitrogen-containing heterocyclic is optionally substituted by one or more substituents selected from alkyl, alkoxy, amino, halogen, haloalkyl, and aryl.

4. The ionic-type phosphorescent metal complex according to claim 3, wherein R is phenyl, alkylphenyl, haloalkylphenyl, carbazolylphenyl, carbazolyl, alkylcarbazolyl, phenylcarbazolyl, phenothiazinyl, or alkylphenothiazinyl; and R′ is phenyl, alkylphenyl, carbazolyl, alkylcarbazolyl, or phenylcarbazolyl.

5. The ionic-type phosphorescent metal complex according to claim 1 selected from eleven complexes illustrated in the following: ##STR00005## ##STR00006##

6. A method for preparing the ionic-type phosphorescent metal complex according to claim 1, wherein the preparation method of the phosphorescent metal complex of formula (I) comprises the following steps: 1) reacting rac-(PPh.sub.2CH.sub.2PPhCH.sub.2-).sub.2 with Pt(PPh.sub.3).sub.2(C≡CR).sub.2 in a solvent to obtain an intermediate; 2) reacting the intermediate obtained in step 1) with [Ag(tht)](A.sup.n−) and PR′.sub.3 in a solvent to obtain the phosphorescent complex of formula (I), wherein the tht is tetrahydrothiophene; or, the preparation method of the phosphorescent complex of formula (II) comprises the following steps: A) reacting meso-(PPh.sub.2CH.sub.2PPhCH.sub.2-).sub.2 with Pt(PPh.sub.3).sub.2(C≡CR).sub.2 in a solvent to obtain an intermediate; B) reacting the intermediate obtained in step A) with PR′.sub.3, .sup.nBu.sub.4NX and [Ag(tht)](A.sup.m−) in a solvent to obtain the phosphorescent complex of formula (II), wherein the tht is tetrahydrothiophene.

7. The ionic-type phosphorescent metal according to claim 1, wherein the anion is ClO.sub.4.sup.−, PF.sub.6.sup.−, SbF.sub.6.sup.−, BF.sub.4.sup.−, or SiF.sub.6.sup.2−.

8. An organic light emitting diode, comprising a light-emitting layer, wherein the light-emitting layer comprises the ionic-type phosphorescent complex of formula (I) or formula (II) according to claim 1.

9. The organic light emitting diode according to claim 8, wherein the organic light emitting diode further comprises an anode layer, a hole injection layer, optionally a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode layer.

10. The organic light emitting diode according to claim 9, wherein the anode layer is indium tin oxide, and the hole injection layer is PEDOT:PSS poly(3,4-ethyleneoxythiophene)-poly(styrene sulfonate)); the hole transport layer is CuSCN, CuI, or CuBr; the light-emitting layer comprises the ionic-type phosphorescent complex and a substance having a hole-transport and/or electron-transport property; the electron transport layer is one or more selected from BmPyPB, TPBi, and OXD-7; the electron injection layer is LiF, and the cathode layer is Al, wherein BmPyPB is 3,3″, 5,5″-tetra(pyridin-3-yl)-1,1′:3′,1″-terphenyl, TPBi is 1,3,5-tris(1-phenyl-1H-benzo[d]imidazole-2-yl)phenyl), BCP is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and OXD-7 is 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene.

11. The organic light emitting diode according to claim 9, having a structure of ITO/PEDOT:PSS/CuSCN/70.5% 2,6-DCZPPY:23.5% OXD-7:6 wt % of the complex of formula (I)/BmPyPB/LiF/Al, or ITO/PEDOT:PSS/70.5% mCP:23.5% OXD-7:6 wt % of the complex of formula (I)/BmPyPB/LiF/Al, wherein ITO is an indium tin oxide conductive film, 2,6-DCZPPY is 2,6-bis (3-(9H-carbazol-9-yl)phenyl)pyridine, and mCP is 1,3-bis(9-carbazolyl)benzene.

12. The organic light emitting diode according to claim 9, comprising ITO/PEDOT:PSS/CuSCN/90% 2,6-DCZPPY:10 wt % of the complex of formula (II)/BmPyPB/LiF/Al, or ITO/PEDOT:PSS/90% mCP: 10 wt % of the complex of formula (II)/BmPyPB/LiF/Al, wherein ITO is an indium tin oxide conductive film, 2,6-DCZPPY is 2,6-bis (3-(9H-carbazol-9-yl)phenyl)pyridine, and mCP is 1,3-bis(9-carbazolyl)benzene.

13. The organic light emitting diode of claim 8, wherein, the phosphorescent complex of formula (I) accounts for 3-20% percentage by weight of a total weight of the light emitting layer.

14. The organic light emitting diode of claim 8, wherein the phosphorescent complex of formula (II) accounts for 5-25% percentage by weight of a total weight of the light emitting layer.

Description

DESCRIPTION OF THE DRAWING

(1) FIG. 1 shows the schematic representation of the devices and the chemical structures of organic materials.

EXAMPLES

(2) Hereinafter, the present invention will be further illustrated in more detail below with reference to the accompanying drawings and the examples to make the objects, technical solutions and technical effects clearer. It is to be understood that the examples described in the description are only illustrative of the present invention and are not intended to limit the present invention.

(3) In the following examples, dpmppe stands for (PPh.sub.2CH.sub.2PPhCH.sub.2—).sub.2, carb stands for carbazolyl, PhBu.sup.t-4 stands for 4-tert-butyl-phenyl, 9-Ph-carb-3 stands for 9-phenyl-carbazol-3-yl, 9-Et-carb-3 stands for 9-ethyl-carbazol-3-yl, PhCF.sub.3-4 stands for 4-trifluoromethyl-phenyl, 9-(4-Ph)-carb stands for 9-(4-phenyl)-carbazolyl, 10-Et-PTZ-3 stands for 10-ethyl-phenothiazin-3-yl, and tht is tetrahydrothiophene.

Example 1: Preparation of [PtAg.SUB.2.(rac-dpmppe)(C≡CC.SUB.6.H.SUB.4.Bu.SUP.t.-4).SUB.2.{PhP(9-Ph-carb-3).SUB.2.}.SUB.2.] (ClO.SUB.4.).SUB.2 .(rac-1) Complex

(4) To a dichloromethane solution (20 mL) of Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4Bu.sup.t-4).sub.2 (80.6 mg, 0.078 mmol) was added rac-dpmppe (50 mg, 0.078 mmol). After being stirred for 30 minutes, concentrated and added with 20 mL of hexane, a pale yellow solid was precipitated as an intermediate with a yield of 90% (80.8 mg). To a dichloromethane solution (20 mL) of the above intermediate were added Ag(tht)ClO.sub.4 (41.4 mg, 0.14 mmol) and PhP(9-Ph-carb-3).sub.2 (82.9 mg, 0.14 mmol). After being stirred for 1 hour at room temperature, the reaction solution turned pale green. The product was purified by silica gel column chromatography using CH.sub.2Cl.sub.2:MeCN (8:1) as eluent, and the pale green product was collected. Yield: 70%. Elemental analysis (C.sub.148H.sub.122Ag.sub.2Cl.sub.2N.sub.4O.sub.8P.sub.6Pt), calculated: C, 64.59; H, 4.47; N, 2.04. Found: C, 64.40; H, 4.55; N, 1.96. ESI-MS m/z (%): 1276.2909 (100) [M-2ClO.sub.4].sup.2+. .sup.1H-NMR (CDCl.sub.3, ppm): 8.20-8.14 (dd, 4H, J.sub.1=16 Hz, J.sub.2=12 Hz), 8.08-8.04 (dd, 4H, J.sub.1=12 Hz, J.sub.2=8 Hz), 7.73-7.59 (m, 12H), 7.53-7.35 (m, 36H), 7.27-7.11 (m, 20H), 6.95-6.88 (m, 12H), 6.69-6.67 (d, 4H, J=8 Hz), 6.59-6.57 (d, 4H, J=8 Hz), 4.29 (m, 2H), 3.02-2.93 (3, 2H), 2.63-2.46 (m, 2H), 0.97 (s, 18H), 0.54 (m, 2H). .sup.31P-NMR (CDCl.sub.3, ppm): 46.0 (d, 2P, J.sub.P—P=78 Hz, J.sub.Pt—P=2448 Hz), 13.8 (m, 2P, J.sub.P—Ag=526 Hz), 1.8 (m, 2P, J.sub.P—Ag=526 Hz, J.sub.P—P=52 Hz). IR (KBr, cm.sup.−1): 2081w (C≡C), 1099s (ClO.sub.4.sup.−).

Example 2: Preparation of [PtAg.SUB.2.(rac-dpmppe){(C≡C-4)C.SUB.6.H.SUB.4.-carb-9}.SUB.2.(PPh.SUB.3.).SUB.2.](ClO.SUB.4.).SUB.2 .(rac-2) Complex

(5) The preparation method was basically 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 replaced by Pt(PPh.sub.3).sub.2{(C≡C-4)C.sub.6H.sub.4-carb-9}.sub.2, and PhP(9-Ph-carb-3).sub.2 was replaced by PPh.sub.3. Yield: 71%. Elemental analysis (C.sub.116H.sub.92Ag.sub.2Cl.sub.2N.sub.2O.sub.8P.sub.6Pt), calculated: C, 60.33; H, 4.02; N, 1.21. Found: C, 60.12; H, 4.02; N, 1.15. ESI-MS m/z (%): 1055.1713 (100%, [M-2ClO.sub.4].sup.2+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.21-8.13 (m, 8H), 7.59-7.54 (m, 14H), 7.48-7.14 (m, 18H), 7.34-7.24 (m, 22H), 7.20-7.12 (m, 14H), 7.02-6.98 (m, 4H), 6.86-6.85 (d, 4H, J=7 Hz), 4.59 (m, 2H), 3.15-3.06 (m, 2H), 2.73-2.59 (m, 2H), 0.61 (m, 2H). .sup.31P-NMR (CDCl.sub.3, ppm): 47.0 (d, 2P, J.sub.P—P=76 Hz, J.sub.Pt—P=2375 Hz), 11.8 (m, 2P, J.sub.P—Ag=506 Hz), 3.4 (m, 2P, J.sub.P—Ag=410 Hz, J.sub.P—P=45 Hz). IR (KBr, cm.sup.−1): 2091w (C≡C), 1099s (ClO.sub.4.sup.−).

Example 3: Preparation of [PtAg.SUB.2.(rac-dpmppe){C≡C-(9-Ph-carb-3)}.SUB.2.(PPh.SUB.3.).SUB.2.](ClO.SUB.4.).SUB.2 .(rac-3) Complex

(6) The preparation method was basically 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 replaced by Pt(PPh.sub.3).sub.2(C≡C-(9-Ph-carb-3)).sub.2, and PhP(9-Ph-carb-3).sub.2 was replaced by PPh.sub.3. Yield: 71%. Elemental analysis (C.sub.116H.sub.92Ag.sub.2Cl.sub.2N.sub.2O.sub.8P.sub.6Pt), calculated: C, 60.33; H, 4.02; N, 1.21. Found: C, 60.10; H, 4.05; N, 1.16. ESI-MS m/z (%): 1055.1717 (100%, [M-2ClO.sub.4].sup.2+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.17-8.12 (dd, 4H, J.sub.1=12 Hz, J.sub.2=8 Hz), 7.67-7.63 (t, 4H, J=8 Hz), 7.54-7.46 (m, 22H), 7.43-7.40 (m, 8H), 7.37-7.31 (m, 10H), 7.29-7.18 (m, 10H), 7.13-7.03 (m, 20H), 6.95-6.92 (m, 4H), 6.83-6.81 (d, 2H), 4.45 (m, 2H), 3.18-3.09 (m, 2H), 2.69-2.50 (m, 2H), 0.59 (m, 2H). .sup.31P-NMR (CDCl.sub.3, ppm): 46.3 (d, 2P, J.sub.P—P=75 Hz, J.sub.Pt—P=2384 Hz), 11.9 (m, 2P, J.sub.P—Ag=510 Hz), 2.4 (m, 2P, J.sub.P—Ag=398 Hz, J.sub.P—P=51 Hz). IR (KBr, cm.sup.−1): 2075w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 4: Preparation of [PtAg.SUB.2.(rac-dpmppe)(C≡C-(9-Ph-carb-3)).SUB.2.{P(9-Et-carb-3).SUB.3.}.SUB.2.](ClO.SUB.4.).SUB.2 .(rac-4) Complex

(7) The preparation method was basically 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 replaced by Pt(PPh.sub.3).sub.2{C≡C-(9-Ph-carb-3)}.sub.2, and PhP(9-Ph-carb-3).sub.2 was replaced by P(9-Et-carb-3).sub.3. Yield: 71%. Elemental analysis (C.sub.164H.sub.134Ag.sub.2Cl.sub.2N.sub.8O.sub.8P.sub.6Pt), calculated: C, 65.39; H, 4.48; N, 3.72. Found: C, 65.14; H, 4.53; N, 3.53. ESI-MS m/z (%): 1406.8446 [M-2ClO.sub.4].sup.2+. .sup.1H-NMR (CDCl.sub.3, ppm): 8.27-8.22 (dd, 4H, J.sub.1=12 Hz, J.sub.2=8 Hz), 8.20-8.17 (d, 6H, J=12 Hz), 8.04-7.99 (dd, 6H, J.sub.1=12 Hz, J.sub.2=8 Hz), 7.71 (s, 2H), 7.50-7.40 (m, 16H), 7.37-7.32 (m, 12H), 7.27-7.25 (m, 10H), 7.17-7.14 (m, 6H), 7.07-7.03 (t, 2H, J=7 Hz), 7.0-6.90 (m, 12H), 6.88-6.77 (m, 16H), 6.73-6.66 (m, 4H), 4.4 (m, 2H), 3.88-3.83 (q, 12H, J=7 Hz), 3.27-3.18 (m, 2H), 2.62-2.44 (m, 2H), 1.0-0.97 (d, 18H, J=7 Hz), 0.72 (m, 2H). .sup.31P-NMR (CDCl.sub.3, ppm): 46.5 (d, 2P, J.sub.P—P=78 Hz, J.sub.Pt—P=2380 Hz), 15.3 (m, 2P, J.sub.P—Ag=534 Hz), 0.8 (m, 2P, J.sub.P—Ag=378 Hz, J.sub.P—P=53 Hz). IR (KBr, cm.sup.−1): 2081w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 5: Preparation of [PtAg.SUB.2.(rac-dpmppe){C≡C-(9-Et-carb-3)}.SUB.2.{P(9-Et-carb-3).SUB.3.}.SUB.2.] (ClO.SUB.4.).SUB.2 .(rac-5) Complex

(8) The preparation method was basically 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 replaced by Pt(PPh.sub.3).sub.2{C≡C-(9-Et-carb-3)}.sub.2, and PhP(9-Ph-carb-3).sub.2 was replaced by P(9-Et-carb-3).sub.3. Yield: 72%. Elemental analysis (C.sub.156H.sub.134Ag.sub.2Cl.sub.2N.sub.8O.sub.8P.sub.6Pt), calculated: C, 64.25; H, 4.63; N, 3.84. Found: C, 64.02; H, 4.65; N, 3.58. ESI-MS m/z (%): 1358.3459 (100%) [M-2ClO.sub.4].sup.2+. .sup.1H-NMR (CDCl.sub.3, ppm): 8.25-8.16 (m, 8H), 8.01 (m, 6H), 7.73-7.68 (m, 10H), 7.44-7.27 (m, 28H), 7.18-7.02 (m, 10H), 6.94-6.82 (m, 22H), 6.70-6.64 (m, 4H), 4.33 (m, 2H), 4.05-3.99 (q, 4H, J=7 Hz), 3.85-3.79 (q, 12H, J=7 Hz), 3.26-3.22 (m, 2H), 2.64-2.51 (m, 2H), 1.29-1.15 (t, 6H, J=7 Hz), 1.11-0.97 (t, 18H, J=7 Hz), 0.71 (m, 2H). .sup.31P-NMR (CDCl.sub.3, ppm): 46.2 (d, 2P, J.sub.P—P=78 Hz, J.sub.Pt—P=2376 Hz), 15.3 (m, 2P, J.sub.P—Ag=524 Hz), 0.6 (m, 2P, J.sub.P—Ag=369 Hz, J.sub.P—P=52 Hz). IR (KBr, cm.sup.−1): 2073w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 6: Preparation of [PtAg.SUB.2.(rac-dpmppe){C≡C-(10-Et-PTZ-3)}.SUB.2.{P(9-Et-carb-3).SUB.3.}.SUB.2.] (ClO.SUB.4.).SUB.2 .(rac-6) Complex

(9) The preparation method was basically 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 replaced by Pt(PPh.sub.3).sub.2{C≡C-(10-Et-PTZ-3)}.sub.2, and PhP(9-Ph-carb-3).sub.2 was replaced by P(9-Et-carb-3).sub.3. Yield: 73%. Elemental analysis (C.sub.156H.sub.134Ag.sub.2Cl.sub.2N.sub.8O.sub.8P.sub.6PtS.sub.2), calculated: C, 62.86; H, 4.53; N, 3.76. Found: C, 62.62; H, 4.57; N, 3.59. ESI-MS m/z (%): 1390.8150 (100%) [M-2ClO.sub.4].sup.2+. .sup.1H-NMR (CDCl.sub.3, ppm): 8.16-8.13 (m, 8H), 8.01-7.96 (dd, 6H, J=8 Hz), 7.58-7.55 (m, 6H), 7.42-7.38 (m, 12H), 7.34-7.30 (m, 8H), 7.15-6.99 (m, 22H), 6.90-6.86 (m, 14H), 6.69-6.67 (d, 2H, J=8 Hz), 6.54-6.52 (d, 2H, J=8 Hz), 6.35-6.32 (m, 4H), 5.92-5.90 (d, 2H, J=8 Hz), 4.23 (m, 2H), 4.05-3.99 (q, 12H, J=7 Hz), 3.45-3.39 (q, 4H, J=7 Hz), 3.06-2.97 (m, 2H), 2.64-2.45 (m, 2H), 1.18-1.14 (t, 18H, J=7 Hz), 1.06-1.02 (t, 6H, J=7 Hz), 0.59 (m, 2H). .sup.31P-NMR (CDCl.sub.3, ppm): 46.5 (d, 2P, J.sub.P—P=78 Hz, J.sub.Pt—P=2376 Hz), 15.2 (m, 2P, J.sub.P—Ag=536 Hz), 1.5 (m, 2P, J.sub.P—Ag=381 Hz, J.sub.P—P=54 Hz). IR (KBr, cm.sup.−1): 2081w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 7: Preparation of [PtAg.SUB.2.(meso-dpmppe)(C≡CC.SUB.6.H.SUB.4.CF.SUB.3.-4).SUB.2.(PPh.SUB.3.)Cl](ClO.SUB.4.) (meso-7) Complex

(10) To a dichloromethane solution (20 mL) of Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4CF.sub.3-4).sub.2 (82.5 mg, 0.078 mmol) was added meso-dpmppe (50 mg, 0.078 mmol). After being stirred for 30 minutes, concentrated and added with 20 mL of hexane, a pale yellow solid was precipitated as an intermediate with a yield of 90% (82.4 mg). PPh.sub.3 (18.3 mg, 0.07 mmol) and .sup.nBu.sub.4NCl (19.5 mg, 0.07 mmol) were firstly mixed. To a dichloromethane solution (20 mL) of the above intermediate were added the mixed solution and Ag(tht)ClO.sub.4 (41.4 mg, 0.14 mmol). After being stirred for 1 hour at room temperature, the reaction solution turned pale blue. The product was purified by silica gel column chromatography using CH.sub.2Cl.sub.2:MeCN (15:1) as eluent, and the pale yellow product was collected. Yield: 75%. Elemental analysis (C.sub.76H.sub.61Ag.sub.2Cl.sub.2F.sub.6O.sub.4P.sub.5Pt), calculated: C, 51.03; H, 3.44. Found: C, 51.21; H, 3.60. ESI-MS m/z (%): 1688.0808 (100%, [M-ClO.sub.4].sup.+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.03-7.96 (m, 8H), 7.59-7.36 (m, 22H), 7.33-7.29 (t, 4H, J=7 Hz), 7.25-7.17 (m, 11H), 6.92-6.89 (m, 4H), 6.65-6.62 (m, 4H), 3.86 (m, 2H), 3.37 (m, 2H), 2.28-2.11 (m, 4H). .sup.31P-NMR (CDCl.sub.3, ppm): 47.6 (dd, 2P, J.sub.P—P=30 Hz, J.sub.Pt—P=2412 Hz), 7.6 (m, 1P, J.sub.P—Ag=579 Hz), −8.9 (m, 2P, J.sub.P—Ag=422 Hz, J.sub.P—P=59 Hz). IR (KBr, cm.sup.−1): 2092w (C≡C), 1104s (ClO.sub.4.sup.−).

Example 8: Preparation of [PtAg.SUB.2.(meso-dpmppe)(C≡CC.SUB.6.H.SUB.4.Bu.SUP.t.-4).SUB.2.(PPh.SUB.3.)Cl](ClO.SUB.4.) (meso-8) Complex

(11) The preparation method was basically the same as that in Example 7, except that Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4CF.sub.3-4).sub.2 was replaced by Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4Bu.sup.t-4).sub.2. Yield: 74%. Elemental analysis (C.sub.82H.sub.79Ag.sub.2Cl.sub.2O.sub.4P.sub.5Pt), calculated: C, 55.80; H, 4.51. Found: C, 56.02; H, 4.74. ESI-MS m/z (%): 1665.2304 (100%, [M-ClO.sub.4].sup.+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.03-7.97 (m, 8H), 7.53-7.50 (m, 7H), 7.41-7.31 (m, 20H), 7.24-7.16 (m, 12H), 6.71-6.59 (m, 8H), 3.81 (m, 2H), 3.46 (m, 2H), 2.18-2.01 (m, 4H), 1.45 (s, 18H). .sup.31P-NMR (CDCl.sub.3, ppm): 47.1 (q, 2P, J.sub.P—P=30 Hz, J.sub.Pt—P=2409 Hz), 7.2 (m, 1P, J.sub.P—Ag=565 Hz), −9.5 (m, 2P, J.sub.P—Ag=417 Hz, J.sub.P—P=58 Hz). IR (KBr, cm.sup.−1): 2092w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 9: Preparation of [PtAg.SUB.2.(meso-dpmppe)(C≡CC.SUB.6.H.SUB.4.Bu.SUP.t.-4).SUB.2.{P(9-Et-carb-3).SUB.3.}Cl] (ClO.SUB.4.) (meso-9) Complex

(12) The preparation method was basically the same as that in Example 7, except that Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4CF.sub.3-4).sub.2 was replaced by Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4Bu.sup.t-4).sub.2, and PPh.sub.3 was replaced by P(9-Et-carb-3).sub.3. Yield: 74%. Elemental analysis (C.sub.106H.sub.100Ag.sub.2Cl.sub.2N.sub.3O.sub.4P.sub.5Pt), calculated: C, 60.15; H, 4.76; N, 1.99. Found: C, 60.32; H, 4.73; N, 1.88. ESI-MS m/z (%): 2016.4011 (100%, [M-ClO.sub.4].sup.+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.48-8.45 (d, 2H, J=12 Hz), 8.08-8.04 (dd, 4H, J.sub.1=12 Hz, J.sub.2=8 Hz), 7.94-7.92 (d, 2H, J=8 Hz), 7.89 (m, 4H), 7.53-7.41 (m, 26H), 7.25-7.15 (m, 13H), 6.61-6.59 (m, 4H), 6.40-6.38 (m, 4H), 4.41-4.37 (q, 6H, J=7 Hz), 3.76 (m, 2H), 3.49 (m, 2H), 2.24-2.05 (m, 4H), 1.49-1.47 (t, 9H, J=7 Hz), 0.76 (s, 18H). .sup.31P-NMR (CDCl.sub.3, ppm): 47.5 (q, 2P, J.sub.P—P=29 Hz, J.sub.Pt—P=2394 Hz), 10.4 (m, 1P, J.sub.P—Ag=601 Hz), −9.3 (m, 2P, J.sub.P—Ag=417 Hz, J.sub.P—P=56 Hz). IR (KBr, cm.sup.−1): 2110w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 10: Preparation of [PtAg.SUB.2.(meso-dpmppe)(C≡CC.SUB.6.H.SUB.4.Bu.SUP.t.-4).SUB.2.{P(9-Et-carb-3).SUB.3.}I] (ClO.SUB.4.) (meso-10) Complex

(13) The preparation method was basically the same as that in Example 7, except that Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4CF.sub.3-4).sub.2 was replaced by Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4Bu.sup.t-4).sub.2, PPh.sub.3 was replaced by P(9-Et-carb-3).sub.3, and .sup.nBu.sub.4NCl was replaced by .sup.nBu.sub.4NI. Yield: 72%. Elemental analysis (C.sub.106H.sub.100Ag.sub.2ClIN.sub.3O.sub.4P.sub.5Pt), calculated: C, 57.66; H, 4.56; N, 1.90. Found: C, 57.57; H, 4.60; N, 1.83. ESI-MS m/z (%): 2108.3387 (100%, [M-ClO.sub.4].sup.+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.51-8.48 (d, 2H, J=12 Hz), 8.11-8.07 (dd, 4H, J.sub.1=12 Hz, J.sub.2=8 Hz), 7.98-7.96 (d, 2H, J=8 Hz), 7.82 (m, 4H), 7.54-7.40 (m, 26H), 7.29-7.16 (m, 13H), 6.54-6.52 (m, 4H), 6.37-6.35 (m, 4H), 4.39-4.35 (q, 6H, J=7 Hz), 3.71 (m, 2H), 3.52 (m, 2H), 2.25-2.05 (m, 4H), 1.49-1.47 (t, 9H, J=7 Hz), 0.72 (s, 18H). .sup.31P-NMR (CDCl.sub.3, ppm): 48.5 (q, 2P, J.sub.P—P=30 Hz, J.sub.Pt—P=2391 Hz), 9.0 (m, 1P, J.sub.P—Ag=547 Hz), −11.7 (m, 2P, J.sub.P—Ag=386 Hz, J.sub.P—P=59 Hz). IR (KBr, cm.sup.−1): 2104w (C≡C), 1093s (ClO.sub.4.sup.−).

Example 11: Preparation of [PtAg.SUB.2.(meso-dpmppe)(C≡C-(10-Et-PTZ-3)).SUB.2 .{P(9-Et-carb-3).SUB.3.}(μ-I)](ClO.SUB.4.) (meso-11) Complex

(14) The preparation method was basically the same as that in Example 7, except that Pt(PPh.sub.3).sub.2(C≡CC.sub.6H.sub.4CF.sub.3-4).sub.2 was replaced by Pt(PPh.sub.3).sub.2{C≡C-(10-Et-PTZ-3)}.sub.2, PPh.sub.3 was replaced by P(9-Et-carb-3).sub.3, and .sup.nBu.sub.4NCl was replaced by .sup.nBu.sub.4NI. Yield: 75%. Elemental analysis (C.sub.114H.sub.98Ag.sub.2ClIN.sub.5O.sub.4P.sub.5PtS.sub.2), calculated: C, 57.19; H, 4.13; N, 2.93. Found: C, 57.42; H, 4.33; N, 2.84. ESI-MS m/z (%): 2294.2671 (100%, [M-ClO.sub.4].sup.+). .sup.1H-NMR (CDCl.sub.3, ppm): 8.54-8.51 (d, 2H, J=12 Hz), 8.09-8.04 (dd, 4H, J.sub.1=12 Hz, J.sub.2=8 Hz), 7.95-7.93 (d, 2H, J=8 Hz), 7.80 (m, 4H), 7.59-7.29 (m, 29H), 7.18-7.01 (m, 12H), 6.75 (m, 4H), 6.51-6.49 (d, 2H, J=8 Hz), 6.41-6.39 (d, 2H, J=8 Hz), 6.22 (s, 2H), 5.63-5.61 (d, 2H, J=8 Hz), 4.45-4.27 (q, 6H, J=7 Hz), 3.71 (m, 2H), 3.46 (m, 2H), 3.14-3.08 (q, 4H, J=6 Hz), 2.28-2.03 (m, 4H), 1.44-1.40 (t, 9H, J=7 Hz), 0.86-0.81 (t, 6H, J=6 Hz). .sup.31P-NMR (CDCl.sub.3, ppm): 48.6 (q, 2P, J.sub.P—P=29 Hz, J.sub.Pt—P=2391 Hz), 9.1 (m, 1P, J.sub.P—Ag=548 Hz), −11.4 (m, 2P, J.sub.P—Ag=384 Hz, J.sub.P—P=60 Hz). IR (KBr, cm.sup.−1): 2101w (C≡C), 1094s (ClO.sub.4.sup.−).

Example 12: Photoluminescence Performance Measurement

(15) The excitation spectra, emission spectra, luminescence lifetimes and luminescence quantum yields of the complex rac-1, rac-4, rac-5, rac-6 prepared in Examples 1, 4, 5 and 6 in solid powder and in the thin film of 70.5% 2,6-DCZPPY:23.5% OXD-7:6% of the complex rac-1, rac-4, rac-5 and rac-6 of the present invention (by weight), and the complex meso-11 prepared in Example 11 in solid powder and in the thin film of 90% 2,6-DCZPPY:10% of the complex meso-11 of the present invention (by weight) were measured on Edinburgh FLS920 fluorescence spectrometer, respectively. The luminescence quantum yields of the solid powder samples were determined by using a 142-mm-diameter integrating sphere.

(16) The emission wavelengths and quantum yields of the complexes rac-1, rac-4, rac-5, rac-6 and meso-11 in solid state were 500 nm and 15.1% (rac-1), 566 nm and 37.1% (rac-4), 580 nm and 30.4% (rac-5), 662 nm and 1.7% (rac-6) and 600 nm and 8.1% (meso-11), respectively;

(17) The emission wavelengths and quantum yields of the complexes rac-1, rac-4, rac-5 and rac-6 in the thin film of 70.5% 2,6-DCZPPY:23.5% OXD-7:6% of the complexes rac-1, rac-4, rac-5 and rac-6 of the present invention (by weight) were 487 nm and 52.2% (rac-1), 527 nm and 90.5% (rac-4), 535 nm and 77.0% (rac-5), 616 nm and 56.8% (rac-6), respectively; the emission wavelength and quantum yield of the complex meso-11 in the thin film of 90% 2,6-DCZPPY: 10% of the complex meso-11 of the present invention (by weight) were 570 nm and 52.2% (meso-11).

Example 13: Fabrication of Organic Light Emitting Diodes and Electroluminescence Performance Measurement

(18) The organic light emitting diode was prepared with a light-emitting layer by doping the blended host materials of 2,6-DCZPPY (70.5%):OXD-7 (23.5%) with 6 wt % of the phosporescent complex rac-1, rac-4, rac-5, or rac-6 prepared in Example 1, 4, 5, or 6 as a luminescent material, respectively. The device structure was ITO/PEDOT:PSS (50 nm)/CuSCN (30 nm)/70.5% 2,6-DCZPPY:23.5% OXD-7:6 wt % of the complex rac-1, rac-4, rac-5, or rac-6 of the invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm); the organic light emitting diode was prepared with a light-emitting layer by doping the host materials of 2,6-DCZPPY (90%) with 10 wt % of the phosporescent complex meso-11 prepared in Example 11 as a luminescent material. The device structure was ITO/PEDOT:PSS (50 nm)/CuSCN (30 nm)/90% 2,6-DCZPPY:10 wt % of the complex meso-11 of the present invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm).

(19) Firstly, an ITO substrate was cleaned with deionized water, acetone and isopropanol, respectively, followed by UV-ozone treatment for 15 minutes. The filtered aqueous solution of PEDOT:PSS was spin coated onto the ITO substrate at 4800 rpm, dried at 140° C. for 20 minutes to afford a 50-nm-thick hole injection layer. And then a solution of CuSCN in diethyl sulfide (10 mg/mL) was spin coated at 4800 rpm onto the PEDOT:PSS hole injection layer, dried at 120° C. for 30 minutes to afford a 30-nm-thick hole transport layer. Secondly, the filtered solution of 70.5% 2,6-DCZPPY:23.5% OXD-7:6% the complex rac-1, rac-4, rac-5, or rac-6 of the present invention (percentage by weight) in diethyl sulfide (5.5 mg/mL), or a solution of 90% 2,6-DCZPPY:10% the complex meso-11 of the present invention (percentage by weight) in diethyl sulfide (5.5 mg/mL) was spin coated at 2100 rpm onto the PEDOT:PSS thin film to form a 50-nm-thick light-emitting layer. After that, the ITO substrate was loaded into a vacuum deposition chamber with a pressure of less than 4×10.sup.−4 Pa, and subsequently thermally deposited with a 50-nm-thick BmPyPB layer, a 1-nm-thick LiF electron injection layer, and 100-nm-thick Al as a cathode of the device.

(20) The LED device performance was determined at room temperature in dry ambient air. The parameters of the electroluminescence performance, including electroluminescence emission wavelength (λ.sub.EL), turn-on voltage (V.sub.on), maximum luminance (L.sub.max), maximum current efficiency (CE.sub.max), maximum power efficiency (PE.sub.max), and maximum external quantum efficiency (EQE.sub.max), are listed in Table 1.

(21) TABLE-US-00001 TABLE 1 Electroluminescence performance data of the phosphorescent complex rac-1, rac-4, rac-5, rac-6 or meso-11 of the invention L.sub.max Com- λ.sub.EL V.sub.on [cd/ CE.sub.max PE.sub.max EQE.sub.max plex [nm] [V].sup.a) m.sup.2].sup.b) [cd/A].sup.c) [lm/W].sup.d) [%].sup.e) CIE.sup.f) rac-1 486 4.8 1703 27.20 13.25 11.1 0.19, 0.24 rac-4 527 4.8 7764 60.96 30.89 18.1 0.24, 0.48 rac-5 537 4.7 6652 57.00 28.70 16.6 0.28, 0.53 rac-6 616 4.6 1898 19.84 9.89 12.4 0.53, 0.46 meso- 572 3.9 2336 30.65 18.68 10.4 0.41, 0.54 11 .sup.a)turn-on voltage at luminance of 1 cd/m.sup.2, .sup.b)maximum luminance, .sup.c)maximum current efficiency, .sup.d)maximum power efficiency, .sup.e)maximum external quantum efficiency, .sup.f)chromaticity coordinates.