(en)A metal coordination compound having a basic structure represented by formula: ML m L′ n (1), wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3; wherein at least one bidentate ligand has a partial structure formed by condensation via an alkylene group having 2–10 carbon atoms, is provided. In an electroluminescence device composed of one or a plurality of organic films disposed between a cathode and an anode, at least one layer is a luminescence layer which is formed by incorporating luminescence molecules constituting the metal coordination compound having a structure of the formula (1) described above as a guest material in a host material thereby to provide an electroluminescence device producing luminescence at high efficiency and stably keeping a high luminance for a long period.

1.ApplicationNumber: US-94286104-A
1.PublishNumber: US-7078115-B2
2.Date Publish: 20060718
3.Inventor: TAKIGUCHI TAKAO
TSUBOYAMA AKIRA
OKADA SHINJIRO
KAMATANI JUN
MIURA SEISHI
MORIYAMA TAKASHI
IGAWA SATOSHI
FURUGORI MANABU
MIZUTANI HIDEMASA

4.Inventor Harmonized: TAKIGUCHI TAKAO(JP)
TSUBOYAMA AKIRA(JP)
OKADA SHINJIRO(JP)
KAMATANI JUN(JP)
MIURA SEISHI(JP)
MORIYAMA TAKASHI(JP)
IGAWA SATOSHI(JP)
FURUGORI MANABU(JP)
MIZUTANI HIDEMASA(JP)

5.Country: US
6.Claims:
(en)A metal coordination compound having a basic structure represented by formula: ML m L′ n (1), wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3; wherein at least one bidentate ligand has a partial structure formed by condensation via an alkylene group having 2–10 carbon atoms, is provided. In an electroluminescence device composed of one or a plurality of organic films disposed between a cathode and an anode, at least one layer is a luminescence layer which is formed by incorporating luminescence molecules constituting the metal coordination compound having a structure of the formula (1) described above as a guest material in a host material thereby to provide an electroluminescence device producing luminescence at high efficiency and stably keeping a high luminance for a long period.

7.Description:
(en)CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a division of application Ser. No. 10/181,342, filed on Jul. 17, 2002, now U.S. Pat. No. 6,824,894 B2, which is a national stage submission filed under 35 U.S.C. 371 of International Application No. PCT/JP02/06001 filed Jun. 17, 2002.


TECHNICAL FIELD
The present invention relates to an electroluminescence device using an organic compound, more particularly to an organic electroluminescence device (hereinafter, referred to as an “organic EL device”) using a metal coordination compound as a luminescent material.
BACKGROUND ART
An applied study on an organic EL device as a luminescence device of a high-speed responsiveness and a high efficiency has been energetically conducted. Basic structures thereof are shown in FIGS. 1( a ) and ( b ) (e.g., Macromol. Symp. 125, 1–48 (1997)).
As shown in FIG. 1 , an organic EL device generally has a structure comprising a transparent electrode 14 , a metal electrode 11 , and a plurality of organic film layers therebetween on a transparent substrate 15 .
In the device of FIG. 1( a ), the organic layers comprise a luminescence layer 12 and a hole-transporting layer 13 . For the transparent electrode 14 , ITO, etc., having a large work function are used, for providing a good hole-injection characteristic from the transparent electrode 14 to the hole-transporting layer 13 . For the metal electrode 11 , a metal, such as aluminum, magnesium or an alloy of these, having a small work function is used for providing a good electron-injection characteristic to the organic layers. These electrodes have a thickness of 50–200 nm.
For the luminescence layer 12 , aluminum quinolinol complexes (a representative example thereof is Alq3 shown hereinafter), etc., having an electron-transporting characteristic and luminescence characteristic are used. For the hole-transporting layer 13 , biphenyldiamine derivatives (a representative example thereof is α-NPD shown hereinafter), etc., having an electron-donative characteristic are used.
The above-structured device has a rectifying characteristic, and when an electric field is applied between the metal electrode 11 as a cathode and the transparent electrode 14 as an anode, electrons are injected from the metal electrode 11 into the luminescence layer 12 and holes are injected from the transparent electrode 15 . The injected holes and electrons are recombined within the luminescence layer 12 to form excitons and cause luminescence. At this time, the hole-transporting layer 13 functions as an electron-blocking layer to increase the recombination efficiency at a boundary between the luminescence layer 12 and hole-transporting layer 13 , thereby increasing the luminescence efficiency.
Further, in the structure of FIG. 1( b ), an electron-transporting layer 16 is disposed between the metal electrode 11 and the luminescence layer 12 . By separating the luminescence and the electron and hole-transportation to provide a more effective carrier blocking structure, efficient luminescence can be performed. For the electron-transporting layer 16 , an electron-transporting material, such as an oxadiazole derivative, can be used.
Luminescence used heretofore in organic EL devices generally includes two types including fluorescence and phosphorescence. In a fluorescence device, fluorescence at the time of transition of luminescence material molecule from a singlet exciton state to the ground state is produced. On the other hand, in a phosphorescence device, luminescence via a triplet exciton state is utilized.
In recent years, the phosphorescence device providing a higher luminescence yield than the fluorescence device has been studied.
Representative published literature may include:
Article 1: Improved energy transfer in electrophosphorescent device (D. F. O'Brien, et al., Applied Physics Letters, Vol. 74, No. 3, p. 422 (1999)); and Article 2: Very high-efficiency green organic light-emitting devices based on electrophosphorescence (M. A. Baldo, et al., Applied Physics Letters, Vol. 75, No. 1, p. 4 (1999)).

In these articles, a structure including 4 organic layers as shown in FIG. 1( c ) has been principally used, including, from the anode side, a hole-transporting layer 13 , a luminescence layer 12 , an exciton diffusion-prevention layer 17 and an electron-transporting layer 16 . Materials used therein include carrier-transporting materials and phosphorescent materials. Abbreviations of the respective materials are as follows.
Alq3: aluminum quinolinol complex α-NPD: N4,N4′-di-naphthalene-1-yl-N4,N4′-diphenyl-biphenyl-4,4′-diamine CBP: 4,4′-N,N′-dicarbazole-biphenyl BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline PtOEP: platinum-octaethylporphyrin complex Ir(ppy) 3 : iridium-phenylpyridine complex










However, the organic EL device utilizing phosphorescence described above is accompanied with a problem regarding a deterioration in luminescence particularly in an energization state. The reason of the deterioration has not been clarified, but is conceived as follows. Generally, a life of the triplet excitons is longer by three or more digits than the life of a singlet exciton, so that excited molecules are held in a high-energy state for a longer period. As a result, it may be considered that reaction with surrounding materials such as polymer formation among the excitons, a change in minute molecular structure and a change in structure of the surrounding material are caused.
Anyway, the phosphorescence device is expected to have a high luminescence efficiency but on the other hand, the device is problematic in terms of deterioration in energized state. As a result, the luminescent material used in the phosphorescence device is desired to be a compound providing a high-efficiency luminescence and a high stability.
DISCLOSURE OF INVENTION
Accordingly, an object of the present invention is to provide a luminescence device allowing high-efficiency luminescence, retaining a high luminance or brightness for a long period and exhibiting a stability. The present invention provides a particular metal coordination compound as a novel luminescent material therefor.
A metal coordination compound according to the present invention is represented by the following formula (1):

ML m L′ n (1),

wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3; n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial structure ML m is represented by formula (2) shown below and a partial structure ML′ n is represented by formula (3), (4) or (5) shown below:


wherein N and C are nitrogen and carbon atoms, respectively; A, A′ and A″ are respectively a cyclic group capable of having a substituent and connected to the metal atom M via the nitrogen atom; B, B′ and B″ are respectively a cyclic group capable of having a substituent and connected to the metal atom M via the carbon atom;

{wherein the substituent denotes a halogen atom, a cyano group, a nitro group, a trialkylsilyl group (of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms), a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom), or an aromatic cyclic group capable of having a substituent (of which the substituent denotes a halogen atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms, (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom)};
A and B, A′ and B′, and A″ and B″, are respectively bonded to each other via a covalent bond; and
A and B, and A′ and B′ are bonded to each other via X and X′, respectively, in which X and X′ are respectively a linear or branched alkylene group having 2–10 carbon atoms (of which the alkylene group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkylene group can include a hydrogen atom that can be replaced with a fluorine atom); and
E and G are independently a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom), or an aromatic cyclic group capable of having a substituent {of which the substituent denotes a halogen atom, a cyano group, a nitro group, a trialkylsilyl group (of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms), or a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO_, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom)}.
In the metal coordination compound according to the present invention; n in the formula (1) may preferably be 0, the partial structure ML′ n in the formula (1) may preferably be represented by the formula (3), the partial structure ML′ n in the formula (1) may preferably be represented by the formula (4), and the partial structure ML′ n in the formula (1) may preferably be represented by the formula (5).
Further, X in the formula (1) may preferably be a linear or branched alkylene group having 2–6 carbon atoms (of which the alkylene group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkylene group can include a hydrogen atom that can be replaced with a fluorine atom).
Further, M in the formula (1) may preferably be Ir.
Further, the present invention provides an electro-luminescence device, wherein a layer comprising the above-mentioned metal coordination compound is sandwiched between opposing two electrodes between which a voltage is applied thereby to provide luminescence.
Particularly, an electroluminescence device causing phosphorescence by application of an electric field is preferred.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates embodiments of the luminescence device according to the present invention, wherein (a) is a device structure comprising 2 organic layers, (b) is a device structure comprising 3 organic layers, and (c) is a device structure comprising 4 organic layers.
FIG. 2 schematically illustrates an example of a panel structure including an organic EL device and drive means.
FIG. 3 illustrates an example of pixel circuit using TFTs (thin film transistors).



BEST MODE FOR PRACTICING THE INVENTION
Needless to say, in the case of constituting a luminescence layer with a carrier-transporting host material and a luminescent guest, the luminescent material per se requires a high quantum yield but it is important to efficiently effect energy transfer between host materials or between host and guest materials, in order to enhance a luminescence efficiency of an organic EL device. Further, the reason of a deterioration in luminescence by current application (energization) has not been clarified as yet but may be considered to be associated with at least an environmental change of the luminescent material due to the luminescence material by itself or its surrounding materials.
The present inventors have conducted various studies and have found the above-mentioned metal coordination compound of the formula (1) and also that an organic EL device using the luminescent material allows high-efficiency luminescence, keeps a high luminance (brightness) for a long period, and causes less deterioration under current application.
In the metal coordination compound represented by the above-mentioned formula (1), n may preferably be 0 or 1, more preferably 0. Further, the partial structure ML′ n may preferably be represented by the above-mentioned formula (3). Further, in the formula (1) described above, X may preferably be a linear or branched alkylene group having 2–6 carbon atoms (of which the alkylene group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkylene group can include a hydrogen atom that can be replaced with a fluorine atom). Further, M in the formula may preferably be Ir or Rh, more preferably Ir.
The metal coordination compound used in the present invention emits phosphorescence, and its lowest excited state is believed to be an MLCT* (metal-to-ligand charge transfer) excited state or π-π* excited state in a triplet state. Phosphorescence is caused at the time of transition from such a state to the ground state.
By utilizing phosphorescence by photo-excitation, it is possible to determine a phosphorescence yield and a life of phosphorescence.
<Measuring Methods of Physical Properties>
Hereinbelow, measuring methods of physical properties in the present invention will be described.
(1) Discrimination Method Between Phosphorescence and Fluorescence
Discrimination of phosphorescence was effected whether a sample compound caused oxygen deactivation or not. The compound is dissolved in chloroform and divided into a solution aerated with oxygen and a solution aerated with nitrogen, followed by irradiation with light to compare their photoluminescence. As a result, luminescence resulting from the compound is little observed with respect to the oxygen-aerated solution, whereas photoluminescence can be confirmed with respect to the nitrogen-aerated solution, thus discriminating these luminescence. Hereinafter, with respect to all the compounds according to the present invention, photoluminescence is confirmed by this method unless otherwise noted specifically.
(2) A Phosphorescence Yield Used in the Present Invention may be Determined According to the Following Formula:

Φ( sample )/Φ(st)=[ Sem ( sample )/ I abs( sample )]/[ Sem (st)/ I abs(st)],

wherein Iabs(st) denotes an absorption coefficient at an excitation wavelength of the standard sample; Sem(st), a luminescence spectral areal intensity when excited at the same wavelength: Iabs(sample), an absorption coefficient at an excitation wavelength of an objective compound; and Sem(sample), a luminescence spectral areal intensity when excited at the same wavelength.

Phosphorescence quantum yield values described herein are relative quantum yield with respect to a quantum yield Φ=1 of Ir(ppy) 3 as a standard sample.
(3) Method of Measurement of Phosphorescence Life
A compound is dissolved in chloroform and spin-coated onto a quartz substrate in a thickness of ca. 0.1 μm and used as a sample for measurement. This sample is exposed to pulsative nitrogen laser light at an excitation wavelength of 337 nm at room temperature by using a luminescence life meter (made by Hamamatsu Photonics K.K.). After completion of the excitation pulses, the decay time of luminescence intensity is measured.
When an initial luminescence intensity is denoted by I 0 , a luminescence intensity after t(sec) is defined according to the following formula with reference to a luminescence life τ(sec):

I=I 0 ·exp(− t/τ ).

A phosphorescence yield of the metal coordination compound of the present invention is a high value of 0.11–0.8, and a phosphorescence life is a short one of 1–40 μsec.
If the phosphorescence life is long, the number of molecules in a triplet excited state waiting for the luminescence when used in an organic EL device is increased, thus leading to a problem of a lowering in luminescence efficiency particularly at a high current density. Accordingly, in order to enhance the luminescence efficiency, it is effective to shorten the above-mentioned phosphorescence life. The metal coordination compound of the present invention is a suitable luminescence material for an organic EL, device because of a high phosphorescence yield and a short phosphorescence life.
Further, because rotational vibration in a dihedral angle direction between the cyclic groups A and B within a molecule is suppressed by the alkylene group represented by X in the formula (2) characterizing the present invention (and further that between the cyclic groups A′ and B′ in a molecule is suppressed by the alkylene group shown by X′ in the case where the partial structure ML′n is represented by the formula (3)), it may be considered that the metal coordination compound of the present invention is decreased in intermolecular energy deactivation pass to accomplish a high efficiency luminescence.
Further, by appropriately selecting the length of the above-mentioned alkylene groups, it becomes possible to change dihedral angles between the cyclic groups A and B and between the cyclic groups A and B and between the cyclic groups A′ and B′ within molecule to allow control of emission wavelength, particularly shift to shorter wavelength.
Also from the above-described viewpoint, the metal coordination compound of the present invention is suitable as a luminescent material for the organic EL device.
Further, as shown in Examples described hereinafter, it has been clarified that the metal coordination compound of the present invention exhibited an excellent performance for stability in a current conduction durability test. By a state change in intermolecular interaction due to introduction of the above-mentioned alkylene group(s) as a characteristic feature of the present invention, it is possible to control intermolecular interaction with a host material etc., thus suppressing formation of excited association product causing thermal deactivation. As a result, it may be considered that the device characteristic is improved.
<Synthesis of Iridium Coordination Compound>
Synthesis schemes of the metal coordination compound represented by the above-mentioned formula (1) used in the present invention will be shown by taking an iridium coordination compound as an example.
Synthesis of iridium coordination compound









Hereinbelow, specific structural formulas of the metal coordination compound used in the present invention are shown in Tables 1 — 1 to 1 — 14 , which are however only representative examples and the present invention is not restricted to these examples.
L 1 –L 11 ′ used in Tables 1 — 1 to 1—14 have structures shown below.





































B–M′ used for X and X′ in Tables 1 — 1 to 1 — 14 have structures shown below.









Pi–Qn2 used for A″ and B″ in Tables 1-10 and 1-11 have structures shown below.























Further, L and L′, aromatic groups present as substituents for the cyclic structures A″ and B″, and Ph2 to Ph3 used for E and G in Tables 1 — 1 to 1—14 have structures shown below.




































TABLE 1-1



No
M
m
n
L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10






















1
Ir
3
0
L1
B
H
H
H
H
H
H
—
—
—
—

2
Ir
3
0
L1
B
H
H
F
H
H
H
—
—
—
—

3
Ir
3
0
L1
B
H
H
H
F
H
H
—
—
—
—

4
Ir
3
0
L1
B
H
H
F
F
H
H
—
—
—
—

5
Ir
3
0
L1
B
H
H
CF3
H
H
H
—
—
—
—

6
Ir
3
0
L1
B
H
H
H
CF3
H
H
—
—
—
—

7
Ir
3
0
L1
B
H
H
F
CF3
H
H
—
—
—
—

8
Ir
3
0
L1
B
H
H
CF3
F
H
H
—
—
—
—

9
Ir
3
0
L1
B
H
H
Cl
CF3
H
H
—
—
—
—

10
Ir
3
0
L1
B
H
H
CH3
H
H
H
—
—
—
—

11
Ir
3
0
L1
B
H
H
H
CH3
H
H
—
—
—
—

12
Ir
3
0
L1
B
H
H
OCH3
H
H
H
—
—
—
—

13
Ir
3
0
L1
B
H
H
H
OCH3
H
H
—
—
—
—

14
Ir
3
0
L1
B
H
H
OCF3
H
H
H
—
—
—
—

15
Ir
3
0
L1
B
H
H
H
OCF3
H
H
—
—
—
—

16
Ir
3
0
L1
B
H
H
Cl
H
H
H
—
—
—
—

17
Ir
3
0
L1
B
H
H
H
Cl
H
H
—
—
—
—

18
Ir
3
0
L1
B
H
H
Br
H
H
H
—
—
—
—

19
Ir
3
0
L1
B
H
H
H
Br
H
H
—
—
—
—

20
Ir
3
0
L1
B
H
H
H
OC4H9
H
H
—
—
—
—

21
Ir
3
0
L1
B
H
H
OC4H9
H
H
H
—
—
—
—

22
Ir
3
0
L1
B
H
H
H
OCH(CH3)2
H
H
—
—
—
—

23
Ir
3
0
L1
B
H
H
Br
H
H
H
—
—
—
—

24
Ir
3
0
L1
B
H
H
H
H
Cl
H
—
—
—
—

25
Ir
3
0
L1
B
H
H
H
H
H
Cl
—
—
—
—

26
Ir
3
0
L1
B
H
H
H
H
CF3
H
—
—
—
—

27
Ir
3
0
L1
B
H
H
H
H
H
CF3
—
—
—
—

28
Ir
3
0
L1
B
H
H
Ph3
H
H
H
—
—
—
—

29
Ir
3
0
L1
B
H
H
Ph3
H
H
CF3
—
—
—
—

30
Ir
3
0
L1
B
H
H
Ph2
H
H
H
H
F
H
H

31
Ir
3
0
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H

32
Ir
3
0
L1
B
H
H
Tn5
H
H
H
H
H
—
—

33
Ir
3
0
L1
B
H
H
Np3
H
H
H
H
H
—
—

34
Ir
3
0
L1
B
H
H
H
Tn5
H
H
H
H
—
—

35
Ir
3
0
L1
B
H
H
Tn7
H
H
H
H
H
—
—

36
Ir
3
0
L1
B
H
H
Pe2
H
H
H
H
—
—
—

37
Ir
3
0
L1
B
H
H
Tn8
H
H
H
H
H
—
—

38
Ir
3
0
L1
B
H
H
Np4
H
H
H
H
—
—
—

39
Ir
3
0
L1
B
H
H
Tn6
H
H
H
H
H
—
—

40
Ir
3
0
L1
B
CH3
H
H
H
H
H
—
—
—
—

41
Ir
3
0
L1
B
CH3
H
F
H
H
H
—
—
—
—

42
Ir
3
0
L1
B
CH3
H
CF3
H
H
H
—
—
—
—

43
Ir
3
0
L1
B
CH3
H
H
CF3
H
H
—
—
—
—

44
Ir
3
0
L1
B
CH3
H
F
CF3
H
H
—
—
—
—

45
Ir
3
0
L1
B
H
CH3
CF3
F
H
H
—
—
—
—

46
Ir
3
0
L1
B
H
CH3
Cl
CF3
H
H
—
—
—
—

47
Ir
3
0
L1
B
H
CH3
OC4H9
H
H
H
—
—
—
—

48
Ir
3
0
L1
B
H
CH3
H
OCH(CH3)2
H
H
—
—
—
—

49
Ir
3
0
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H

50
Ir
3
0
L1
B
H
CH3
Np3
H
H
H
H
H
—
—


























































































TABLE 1-2



No
M
m
n
L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10






















51
Ir
3
0
L1
B
H
CH3
Tn6
H
H
H
H
H
—
—

52
Ir
3
0
L1
B
CH3
CH3
H
H
H
H
—
—
—
—

53
Ir
3
0
L1
C
H
—
H
H
H
H
—
—
—
—

54
Ir
3
0
L1
C
H
—
F
H
H
H
—
—
—
—

55
Ir
3
0
L1
C
H
—
H
F
H
H
—
—
—
—

56
Ir
3
0
L1
C
H
—
F
F
H
H
—
—
—
—

57
Ir
3
0
L1
C
H
—
CF3
H
H
H
—
—
—
—

58
Ir
3
0
L1
C
H
—
H
CF3
H
H
—
—
—
—

59
Ir
3
0
L1
C
H
—
F
CF3
H
H
—
—
—
—

60
Ir
3
0
L1
C
H
—
CF3
F
H
H
—
—
—
—

61
Ir
3
0
L1
C
H
—
Cl
CF3
H
H
—
—
—
—

62
Ir
3
0
L1
C
H
—
CH3
H
H
H
—
—
—
—

63
Ir
3
0
L1
C
H
—
H
CH3
H
H
—
—
—
—

64
Ir
3
0
L1
C
H
—
OCH3
H
H
H
—
—
—
—

65
Ir
3
0
L1
C
H
—
H
OCH3
H
H
—
—
—
—

66
Ir
3
0
L1
C
H
—
OCF3
H
H
H
—
—
—
—

67
Ir
3
0
L1
C
H
—
H
OCF3
H
H
—
—
—
—

68
Ir
3
0
L1
C
H
—
Cl
H
H
H
—
—
—
—

69
Ir
3
0
L1
C
H
—
H
Cl
H
H
—
—
—
—

70
Ir
3
0
L1
C
H
—
Br
H
H
H
—
—
—
—

71
Ir
3
0
L1
C
H
—
H
Br
H
H
—
—
—
—

72
Ir
3
0
L1
C
H
—
H
OC4H9
H
H
—
—
—
—

73
Ir
3
0
L1
C
H
—
OC4H9
H
H
H
—
—
—
—

74
Ir
3
0
L1
C
H
—
H
OCH(CH3)2
H
H
—
—
—
—

75
Ir
3
0
L1
C
H
—
Br
H
H
H
—
—
—
—

76
Ir
3
0
L1
C
H
—
H
H
Cl
H
—
—
—
—

77
Ir
3
0
L1
C
H
—
H
H
H
Cl
—
—
—
—

78
Ir
3
0
L1
C
H
—
H
H
CF3
H
—
—
—
—

79
Ir
3
0
L1
C
H
—
H
H
H
CF3
—
—
—
—

80
Ir
3
0
L1
C
H
—
Ph3
H
H
H
—
—
—
—

81
Ir
3
0
L1
C
H
—
Ph3
H
H
CF3
—
—
—
—

82
Ir
3
0
L1
C
H
—
Ph2
H
H
H
H
F
H
H

83
Ir
3
0
L1
C
H
—
Ph2
H
H
H
H
H
CF3
H

84
Ir
3
0
L1
C
H
—
Tn5
H
H
H
H
H
—
—

85
Ir
3
0
L1
C
H
—
Np3
H
H
H
H
H
—
—

86
Ir
3
0
L1
C
H
—
H
Tn5
H
H
H
H
—
—

87
Ir
3
0
L1
C
H
—
Tn7
H
H
H
H
H
—
—

88
Ir
3
0
L1
C
H
—
Pe2
H
H
H
H
—
—
—

89
Ir
3
0
L1
C
H
—
Tn8
H
H
H
H
H
—
—

90
Ir
3
0
L1
C
H
—
Np4
H
H
H
H
—
—
—

91
Ir
3
0
L1
C
H
—
Tn6
H
H
H
H
H
—
—

92
Ir
3
0
L1
C
CH3
—
H
H
H
H
—
—
—
—

93
Ir
3
0
L1
C
CH3
—
F
H
H
H
—
—
—
—

94
Ir
3
0
L1
C
CH3
—
CF3
H
H
H
—
—
—
—

95
Ir
3
0
L1
C
CH3
—
H
CF3
H
H
—
—
—
—

96
Ir
3
0
L1
C
CH3
—
F
CF3
H
H
—
—
—
—

97
Ir
3
0
L1
C
CH3
—
CF3
F
H
H
—
—
—
—

98
Ir
3
0
L1
C
CH3
—
Cl
CF3
H
H
—
—
—
—

99
Ir
3
0
L1
C
CH3
—
OC4H9
H
H
H
—
—
—
—

100
Ir
3
0
L1
C
CH3
—
H
OCH(CH3)2
H
H
—
—
—
—


























































































TABLE 1-3



No
M
m
n
L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10



101
Rh
3
0
L1
B
H
H
H
H
H
H
—
—
—
—

102
Rh
3
0
L1
B
H
H
F
H
H
H
—
—
—
—

103
Rh
3
0
L1
B
H
H
H
F
H
H
—
—
—
—

104
Rh
3
0
L1
B
H
H
F
F
H
H
—
—
—
—

105
Rh
3
0
L1
B
H
H
CF3
H
H
H
—
—
—
—

106
Rh
3
0
L1
B
H
H
H
CF3
H
H
—
—
—
—

107
Rh
3
0
L1
B
H
H
F
CF3
H
H
—
—
—
—

108
Rh
3
0
L1
B
H
H
CF3
F
H
H
—
—
—
—

109
Rh
3
0
L1
B
H
H
Cl
CF3
H
H
—
—
—
—

110
Rh
3
0
L1
B
H
H
CH3
H
H
H
—
—
—
—

111
Rh
3
0
L1
B
H
H
H
CH3
H
H
—
—
—
—

112
Rh
3
0
L1
B
H
H
OCH3
H
H
H
—
—
—
—

113
Rh
3
0
L1
B
H
H
H
OCH3
H
H
—
—
—
—

114
Rh
3
0
L1
B
H
H
OCF3
H
H
H
—
—
—
—

115
Rh
3
0
L1
B
H
H
H
OCF3
H
H
—
—
—
—

116
Rh
3
0
L1
B
H
H
Cl
H
H
H
—
—
—
—

117
Rh
3
0
L1
B
H
H
H
Cl
H
H
—
—
—
—

118
Rh
3
0
L1
B
H
H
Br
H
H
H
—
—
—
—

119
Rh
3
0
L1
B
H
H
H
Br
H
H
—
—
—
—

120
Rh
3
0
L1
B
H
H
H
OC4H9
H
H
—
—
—
—

121
Rh
3
0
L1
B
H
H
OC4H9
H
H
H
—
—
—
—

122
Rh
3
0
L1
B
H
H
H
OCH(CH3)2
H
H
—
—
—
—

123
Rh
3
0
L1
B
H
H
Br
H
H
H
—
—
—
—

124
Rh
3
0
L1
B
H
H
H
H
Cl
H
—
—
—
—

125
Rh
3
0
L1
B
H
H
H
H
H
Cl
—
—
—
—

126
Pt
2
0
L1
B
H
H
H
H
CF3
H
—
—
—
—

127
Pt
2
0
L1
B
H
H
H
H
H
CF3
—
—
—
—

128
Pt
2
0
L1
B
H
H
Ph3
H
H
H
—
—
—
—

129
Pt
2
0
L1
B
H
H
Ph3
H
H
CF3
—
—
—
—

130
Pt
2
0
L1
B
H
H
Ph2
H
H
H
H
F
H
H

131
Pt
2
0
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H

132
Pt
2
0
L1
B
H
H
Tn5
H
H
H
H
H
—
—

133
Pt
2
0
L1
B
H
H
Np3
H
H
H
H
H
—
—

134
Pt
2
0
L1
B
H
H
H
Tn5
H
H
H
H
—
—

135
Pt
2
0
L1
B
H
H
Tn7
H
H
H
H
H
—
—

136
Pt
2
0
L1
B
CH3
H
F
H
H
H
—
—
—
—

137
Pt
2
0
L1
B
CH3
H
CF3
H
H
H
—
—
—
—

138
Pt
2
0
L1
B
CH3
H
H
CF3
H
H
—
—
—
—

139
Pt
2
0
L1
B
CH3
H
F
CF3
H
H
—
—
—
—

140
Pt
2
0
L1
B
CH3
H
H
H
H
H
—
—
—
—

141
Pd
2
0
L1
B
CH3
H
F
H
H
H
—
—
—
—

142
Pd
2
0
L1
B
CH3
H
CF3
H
H
H
—
—
—
—

143
Pd
2
0
L1
B
CH3
H
H
CF3
H
H
—
—
—
—

144
Pd
2
0
L1
B
CH3
H
F
CF3
H
H
—
—
—
—

145
Pd
2
0
L1
B
H
CH3
CF3
F
H
H
—
—
—
—

146
Pd
2
0
L1
B
H
CH3
Cl
CF3
H
H
—
—
—
—

147
Pd
2
0
L1
B
H
CH3
OC4H9
H
H
H
—
—
—
—

148
Pd
2
0
L1
B
H
CH3
H
OCH(CH3)2
H
H
—
—
—
—

149
Pd
2
0
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H

150
Pd
2
0
L1
B
H
CH3
Np3
H
H
H
H
H
—
—






















































































TABLE 1-4



No
M
m
n
L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10



151
Ir
3
0
L1
D
H
H
H
H
H
H
—
—
—
—

152
Ir
3
0
L1
D
H
H
F
H
H
H
—
—
—
—

153
Ir
3
0
L1
D
H
H
H
F
H
H
—
—
—
—

154
Ir
3
0
L1
D
H
H
F
F
H
H
—
—
—
—

155
Ir
3
0
L1
D
H
H
CF3
H
H
H
—
—
—
—

156
Ir
3
0
L1
D
H
H
H
CF3
H
H
—
—
—
—

157
Ir
3
0
L1
D
H
H
F
CF3
H
H
—
—
—
—

158
Ir
3
0
L1
D
H
H
CF3
F
H
H
—
—
—
—

159
Ir
3
0
L1
D
H
H
Cl
CF3
H
H
—
—
—
—

160
Ir
3
0
L1
D
H
H
CH3
H
H
H
—
—
—
—

161
Ir
3
0
L1
D
H
H
H
CH3
H
H
—
—
—
—

162
Ir
3
0
L1
D
CH3
H
OCH3
H
H
H
—
—
—
—

163
Ir
3
0
L1
D
H
CH3
H
OCH3
H
H
—
—
—
—

164
Ir
3
0
L1
D
CH3
CH3
OCF3
H
H
H
—
—
—
—

165
Ir
3
0
L1
D
H
H
H
OCF3
H
H
—
—
—
—

166
Ir
3
0
L1
E
—
—
H
H
H
H
—
—
—
—

167
Ir
3
0
L1
E
—
—
H
Cl
H
H
—
—
—
—

168
Ir
3
0
L1
E
—
—
Br
H
H
H
—
—
—
—

169
Ir
3
0
L1
E
—
—
H
Br
H
H
—
—
—
—

170
Ir
3
0
L1
E
—
—
H
OC4H9
H
H
—
—
—
—

171
Ir
3
0
L1
F
H
—
H
H
H
H
—
—
—
—

172
Ir
3
0
L1
F
H
—
H
OCH(CH3)2
H
H
—
—
—
—

173
Ir
3
0
L1
F
H
—
Br
H
H
H
—
—
—
—

174
Ir
3
0
L1
F
H
—
H
H
Cl
H
—
—
—
—

175
Ir
3
0
L1
F
C2H5
—
H
H
H
Cl
—
—
—
—

176
Ir
3
0
L1
G
H
—
H
H
CF3
H
—
—
—
—

177
Ir
3
0
L1
G
H
—
H
H
H
H
—
—
—
—

178
Ir
3
0
L1
G
H
—
Ph3
H
H
H
—
—
—
—

179
Ir
3
0
L1
G
H
—
Ph3
H
H
CF3
—
—
—
—

180
Ir
3
0
L1
G
H
—
H
H
H
H
—
—
—
—

181
Ir
3
0
L1
H
H
—
Ph2
H
H
H
H
H
CF3
H

182
Ir
3
0
L1
H
H
—
Tn5
H
H
H
H
H
—
—

183
Ir
3
0
L1
H
H
—
Np3
H
H
H
H
H
—
—

184
Ir
3
0
L1
H
CH3
—
H
Tn5
H
H
H
H
—
—

185
Ir
3
0
L1
H
H
—
Tn7
H
H
H
H
H
—
—

186
Ir
3
0
L1
I
H
H
H
H
H
H
—
—
—
—

187
Ir
3
0
L1
I
H
H
Tn8
H
H
H
H
H
—
—

188
Ir
3
0
L1
I
H
H
Np4
H
H
H
H
—
—
—

189
Ir
3
0
L1
I
H
H
Tn6
H
H
H
H
H
—
—

190
Ir
3
0
L1
I
CH3
H
H
H
H
H
—
—
—
—

191
Ir
3
0
L1
J
H
H
F
H
H
H
—
—
—
—

192
Ir
3
0
L1
J
H
H
CF3
H
H
H
—
—
—
—

193
Ir
3
0
L1
J
H
H
H
CF3
H
H
—
—
—
—

194
Ir
3
0
L1
J
CH3
H
F
CF3
H
H
—
—
—
—

195
Ir
3
0
L1
J
H
CH3
CF3
F
H
H
—
—
—
—

196
Ir
3
0
L1
K
—
H
Cl
CF3
H
H
—
—
—
—

197
Ir
3
0
L1
K
—
H
OC4H9
H
H
H
—
—
—
—

198
Ir
3
0
L1
K
—
H
H
OCH(CH3)2
H
H
—
—
—
—

199
Ir
3
0
L1
K
—
H
Ph2
H
H
H
H
F
H
H

200
Ir
3
0
L1
K
—
CH3
Np3
H
H
H
H
H
—
—






















































































TABLE 1-5



No
M
m
n
L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10



201
Ir
3
0
L1
M
H
—
H
H
H
H
—
—
—
—

202
Ir
3
0
L1
M
H
—
F
H
H
H
—
—
—
—

203
Ir
3
0
L1
M
H
—
H
F
H
H
—
—
—
—

204
Ir
3
0
L1
N
H
H
H
H
H
H
—
—
—
—

205
Ir
3
0
L1
N
H
H
CF3
H
H
H
—
—
—
—

206
Ir
3
0
L1
N
CH3
H
H
CF3
H
H
—
—
—
—

207
Ir
3
0
L1
O
H
H
F
CF3
H
H
—
—
—
—

208
Ir
3
0
L1
O
H
H
CF3
F
H
H
—
—
—
—

209
Ir
3
0
L1
O
H
H
Cl
CF3
H
H
—
—
—
—

210
Ir
3
0
L1
P
—
H
H
H
H
H
—
—
—
—

211
Ir
3
0
L1
P
—
H
H
CH3
H
H
—
—
—
—

212
Ir
3
0
L1
P
—
H
OCH3
H
H
H
—
—
—
—

213
Ir
3
0
L1
Q
H
—
H
H
H
H
—
—
—
—

214
Ir
3
0
L1
Q
H
—
OCF3
H
H
H
—
—
—
—

215
Ir
3
0
L1
Q
H
—
H
OCF3
H
H
—
—
—
—

216
Ir
3
0
L1
R
H
—
H
H
H
H
—
—
—
—

217
Ir
3
0
L1
R
H
—
H
Cl
H
H
—
—
—
—

218
Ir
3
0
L1
R
H
—
H
H
H
H
—
—
—
—

219
Ir
3
0
L1
S
H
—
H
Br
H
H
—
—
—
—

220
Ir
3
0
L1
S
H
—
H
OC4H9
H
H
—
—
—
—

221
Ir
3
0
L1
S
H
—
OC4H9
H
H
H
—
—
—
—

222
Ir
3
0
L1
T
—
—
H
H
H
H
—
—
—
—

223
Ir
3
0
L1
T
—
—
Br
H
H
H
—
—
—
—

224
Ir
3
0
L1
T
—
—
H
H
H
H
—
—
—
—

225
Ir
3
0
L1
U
—
—
H
H
H
Cl
—
—
—
—

226
Ir
3
0
L1
U
—
—
H
H
CF3
H
—
—
—
—

227
Ir
3
0
L1
U
—
—
H
H
H
CF3
—
—
—
—

228
Ir
3
0
L1
V
H
—
H
H
H
H
—
—
—
—

229
Ir
3
0
L1
V
H
—
Ph3
H
H
H
—
—
—
—

230
Ir
3
0
L1
V
H
—
Ph2
H
H
H
H
F
H
H

231
Ir
3
0
L1
W
—
—
H
H
H
H
—
—
—
—

232
Ir
3
0
L1
W
—
—
Tn5
H
H
H
H
H
—
—

233
Ir
3
0
L1
W
—
—
Np3
H
H
H
H
H
—
—

234
Ir
3
0
L1
Y
H
—
H
H
H
H
—
—
—
—

235
Ir
3
0
L1
Y
H
—
Tn7
H
H
H
H
H
—
—

236
Ir
3
0
L1
Y
H
—
Pe2
H
H
H
H
—
—
—

237
Ir
3
0
L1
Z
—
—
H
H
H
H
—
—
—
—

238
Ir
3
0
L1
Z
—
—
Np4
H
H
H
H
—
—
—

239
Ir
3
0
L1
Z
—
—
Tn6
H
H
H
H
H
—
—

240
Ir
3
0
L1
A′
H
—
H
H
H
H
—
—
—
—

241
Ir
3
0
L1
A′
H
—
F
H
H
H
—
—
—
—

242
Ir
3
0
L1
A′
CH3
—
CF3
H
H
H
—
—
—
—

243
Ir
3
0
L1
B′
—
H
H
H
H
H
—
—
—
—

244
Ir
3
0
L1
B′
—
H
F
CF3
H
H
—
—
—
—

245
Ir
3
0
L1
B′
—
CH3
CF3
F
H
H
—
—
—
—

246
Ir
3
0
L1
C′
H
H
Cl
CF3
H
H
—
—
—
—

247
Ir
3
0
L1
C′
H
H
OC4H9
H
H
H
—
—
—
—

248
Ir
3
0
L1
C′
H
CH3
H
H
H
H
—
—
—
—

249
Ir
3
0
L1
D′
H
—
Ph2
H
H
H
H
F
H
H

250
Ir
3
0
L1
D′
CH3
—
Np3
H
H
H
H
H
—
—






















































































TABLE 1-6



No
M
m
n
L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10



251
Ir
3
0
L1
D′
H
H
H
H
H
H
—
—
—
—

252
Ir
3
0
L1
E′
H
H
H
H
H
H
—
—
—
—

253
Ir
3
0
L1
E′
H
H
H
F
H
H
—
—
—
—

254
Ir
3
0
L1
E′
H
CH3
F
F
H
H
—
—
—
—

255
Ir
3
0
L1
F′
—
—
CF3
H
H
H
—
—
—
—

256
Ir
3
0
L1
F′
—
—
H
H
H
H
—
—
—
—

257
Ir
3
0
L1
F′
—
—
F
CF3
H
H
—
—
—
—

258
Ir
3
0
L1
F′
—
—
CF3
F
H
H
—
—
—
—

259
Ir
3
0
L1
F′
—
—
Cl
CF3
H
H
—
—
—
—

260
Ir
3
0
L1
G′
—
—
H
H
H
H
—
—
—
—

261
Ir
3
0
L1
G′
—
—
H
CH3
H
H
—
—
—
—

262
Ir
3
0
L1
G′
—
—
OCH3
H
H
H
—
—
—
—

263
Ir
3
0
L1
G′
—
—
H
OCH3
H
H
—
—
—
—

264
Ir
3
0
L1
G′
—
—
OCF3
H
H
H
—
—
—
—

265
Ir
3
0
L1
G′
—
—
H
OCF3
H
H
—
—
—
—

266
Ir
3
0
L1
H′
—
—
H
H
H
H
—
—
—
—

267
Ir
3
0
L1
H′
—
—
H
Cl
H
H
—
—
—
—

268
Ir
3
0
L1
H′
—
—
Br
H
H
H
—
—
—
—

269
Ir
3
0
L1
H′
—
—
H
Br
H
H
—
—
—
—

270
Ir
3
0
L1
H′
—
—
H
OC4H9
H
H
—
—
—
—

271
Ir
3
0
L1
I′
—
—
H
H
H
H
—
—
—
—

272
Ir
3
0
L1
I′
—
—
H
OCH(CH3)2
H
H
—
—
—
—

273
Ir
3
0
L1
I′
—
—
Br
H
H
H
—
—
—
—

274
Ir
3
0
L1
I′
—
—
H
H
Cl
H
—
—
—
—

275
Ir
3
0
L1
I′
—
—
H
H
H
Cl
—
—
—
—

276
Ir
3
0
L1
J′
—
—
H
H
H
H
—
—
—
—

277
Ir
3
0
L1
J′
—
—
H
H
H
CF3
—
—
—
—

278
Ir
3
0
L1
J′
—
—
Ph3
H
H
H
—
—
—
—

279
Ir
3
0
L1
J′
—
—
Ph3
H
H
CF3
—
—
—
—

280
Ir
3
0
L1
J′
—
—
Ph2
H
H
H
H
F
H
H

281
Ir
3
0
L1
K′
—
—
Ph2
H
H
H
H
H
CF3
H

282
Ir
3
0
L1
K′
—
—
H
H
H
H
—
—
—
—

283
Ir
3
0
L1
K′
—
—
Np3
H
H
H
H
H
—
—

284
Ir
3
0
L1
K′
—
—
H
Tn5
H
H
H
H
—
—

285
Ir
3
0
L1
K′
—
—
Tn7
H
H
H
H
H
—
—

286
Rh
3
0
L1
C
H
—
Pe2
H
H
H
H
—
—
—

287
Rh
3
0
L1
C
H
—
Tn8
H
H
H
H
H
—
—

288
Rh
3
0
L1
C
H
—
Np4
H
H
H
H
—
—
—

289
Rh
3
0
L1
I
H
H
Tn6
H
H
H
H
H
—
—

290
Rh
3
0
L1
D′
CH3
—
H
H
H
H
—
—
—
—

291
Rh
3
0
L1
F′
—
—
F
H
H
H
—
—
—
—

292
Pt
2
0
L1
C
H
—
CF3
H
H
H
—
—
—
—

293
Pt
2
0
L1
O
H
H
H
CF3
H
H
—
—
—
—

294
Pt
2
0
L1
Z
—
—
F
CF3
H
H
—
—
—
—

295
Pt
2
0
L1
D′
H
—
CF3
F
H
H
—
—
—
—

296
Pt
2
0
L1
F′
—
—
Cl
CF3
H
H
—
—
—
—

297
Pt
2
0
L1
H′
—
—
OC4H9
H
H
H
—
—
—
—

298
Pd
2
0
L1
I′
—
—
H
OCH(CH3)2
H
H
—
—
—
—

299
Pd
2
0
L1
G
H
—
Ph2
H
H
H
H
F
H
H

300
Pd
2
0
L1
C
H
—
Np3
H
H
H
H
H
—
—






















































































TABLE 1-7







L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10

No
M
m
n
L′
X′
R1
R2
X1′
X2′
X3′
X4′
R7
R8
R9
R10



301
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
F
H
H
H
—
—
—
—

302
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
H
F
H
H
—
—
—
—

303
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
F
F
H
H
—
—
—
—

304
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
CF3
H
H
H
—
—
—
—

305
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
H
CF3
H
H
—
—
—
—

306
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
F
CF3
H
H
—
—
—
—

307
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
Cl
CF3
H
H
—
—
—
—

308
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
CH3
H
H
H
—
—
—
—

309
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
OCF3
H
H
H
—
—
—
—

310
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
H
OC4H9
H
H
—
—
—
—

311
Ir
2
1
L1
B
H
H
OC4H9
H
H
H
—
—
—
—





L1′
B
H
H
H
OCH(CH3)2
H
H
—
—
—
—

312
Ir
2
1
L1
B
H
H
Br
H
H
H
—
—
—
—





L1′
B
H
H
H
H
Cl
H
—
—
—
—

313
Ir
2
1
L1
B
H
H
H
H
H
Cl
—
—
—
—





L1′
B
H
H
H
H
CF3
H
—
—
—
—

314
Ir
2
1
L1
B
H
H
H
H
H
CF3
—
—
—
—





L1′
B
H
H
Ph3
H
H
H
—
—
—
—

315
Ir
2
1
L1
B
H
H
Ph3
H
H
CF3
—
—
—
—





L1′
B
H
H
Ph2
H
H
H
H
F
H
H

316
Ir
2
1
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H





L1′
B
H
H
Tn5
H
H
H
H
H
—
—

317
Ir
2
1
L1
B
H
H
Np3
H
H
H
H
H
—
—





L1′
B
H
H
H
Tn5
H
H
H
H
—
—

318
Ir
2
1
L1
B
H
H
Tn7
H
H
H
H
H
—
—





L1′
B
H
H
Pe2
H
H
H
H
—
—
—

319
Ir
2
1
L1
B
H
H
Tn8
H
H
H
H
H
—
—





L1′
B
H
H
Np4
H
H
H
H
—
—
—

320
Ir
2
1
L1
B
H
H
Tn6
H
H
H
H
H
—
—





L1′
B
CH3
H
H
H
H
H
—
—
—
—

321
Ir
2
1
L1
B
CH3
H
F
H
H
H
—
—
—
—





L1′
B
CH3
H
CF3
H
H
H
—
—
—
—

322
Ir
2
1
L1
B
CH3
H
H
CF3
H
H
—
—
—
—





L1′
B
CH3
H
F
CF3
H
H
—
—
—
—

323
Ir
2
1
L1
B
H
CH3
CF3
F
H
H
—
—
—
—





L1′
B
H
CH3
Cl
CF3
H
H
—
—
—
—

324
Ir
2
1
L1
B
H
CH3
OC4H9
H
H
H
—
—
—
—





L1′
B
H
CH3
H
OCH(CH3)2
H
H
—
—
—
—

325
Ir
2
1
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H





L1′
B
H
CH3
Np3
H
H
H
H
H
—
—























































































TABLE 1-8







L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10

No
M
m
n
L′
X′
R1
R2
X1′
X2′
X3′
X4′
R7
R8
R9
R10



326
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
C
H
—
H
H
H
H
—
—
—
—

327
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
C
H
—
F
H
H
H
—
—
—
—

328
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
C
H
—
F
F
H
H
—
—
—
—

329
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
C
H
—
F
CF3
H
H
—
—
—
—

330
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
C
H
—
Cl
CF3
H
H
—
—
—
—

331
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
D
CH3
H
OCH3
H
H
H
—
—
—
—

332
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
E
—
—
H
OC4H9
H
H
—
—
—
—

333
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
F
C2H5
—
H
H
H
Cl
—
—
—
—

334
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
G
H
—
Ph3
H
H
CF3
—
—
—
—

335
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
H
H
—
Ph2
H
H
H
H
H
CF3
H

336
Ir
2
1
L1
B
H
H
OC4H9
H
H
H
—
—
—
—





L1′
I
H
H
H
H
H
H
—
—
—
—

337
Ir
2
1
L1
B
H
H
Br
H
H
H
—
—
—
—





L1′
J
H
H
CF3
H
H
H
—
—
—
—

338
Ir
2
1
L1
B
H
H
H
H
H
Cl
—
—
—
—





L1′
K
—
CH3
Np3
H
H
H
H
H
—
—

339
Ir
2
1
L1
B
H
H
H
H
H
CF3
—
—
—
—





L1′
M
H
—
H
F
H
H
—
—
—
—

340
Ir
2
1
L1
B
H
H
Ph3
H
H
CF3
—
—
—
—





L1′
N
CH3
H
H
CF3
H
H
—
—
—
—

341
Ir
2
1
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H





L1′
O
H
H
Cl
CF3
H
H
—
—
—
—

342
Ir
2
1
L1
B
H
H
Np3
H
H
H
H
H
—
—





L1′
P
—
H
OCH3
H
H
H
—
—
—
—

343
Ir
2
1
L1
B
H
H
Tn7
H
H
H
H
H
—
—





L1′
Q
H
—
H
H
H
H
—
—
—
—

344
Ir
2
1
L1
B
H
H
Tn8
H
H
H
H
H
—
—





L1′
R
H
—
H
Cl
H
H
—
—
—
—

345
Ir
2
1
L1
B
H
H
Tn6
H
H
H
H
H
—
—





L1′
S
H
—
H
OC4H9
H
H
—
—
—
—

346
Ir
2
1
L1
B
CH3
H
F
H
H
H
—
—
—
—





L1′
V
H
—
Ph2
H
H
H
H
F
H
H

347
Ir
2
1
L1
B
CH3
H
H
CF3
H
H
—
—
—
—





L1′
Y
H
—
Pe2
H
H
H
H
—
—
—

348
Ir
2
1
L1
B
H
CH3
CF3
F
H
H
—
—
—
—





L1′
A′
CH3
—
CF3
H
H
H
—
—
—
—

349
Ir
2
1
L1
B
H
CH3
OC4H9
H
H
H
—
—
—
—





L1′
C′
H
H
Cl
CF3
H
H
—
—
—
—

350
Ir
2
1
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H





L1′
D′
CH3
—
Np3
H
H
H
H
H
—
—























































































TABLE 1-9







L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10

No
M
m
n
L′
X′
R1
R2
X1′
X2′
X3′
X4′
R7
R8
R9
R10



351
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
F
H
H
H
—
—
—
—

352
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
H
F
H
H
—
—
—
—

353
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
F
F
H
H
—
—
—
—

354
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
CF3
H
H
H
—
—
—
—

355
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
H
CF3
H
H
—
—
—
—

356
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
F
CF3
H
H
—
—
—
—

357
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
Cl
CF3
H
H
—
—
—
—

358
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
CH3
H
H
H
—
—
—
—

359
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
OCF3
H
H
H
—
—
—
—

360
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
B
H
H
H
OC4H9
H
H
—
—
—
—

361
Pt
1
1
L1
B
H
H
OC4H9
H
H
H
—
—
—
—





L1′
B
H
H
H
OCH(CH3)2
H
H
—
—
—
—

362
Pt
1
1
L1
B
H
H
Br
H
H
H
—
—
—
—





L1′
B
H
H
H
H
Cl
H
—
—
—
—

363
Pt
1
1
L1
B
H
H
H
H
H
Cl
—
—
—
—





L1′
B
H
H
H
H
CF3
H
—
—
—
—

364
Pt
1
1
L1
B
H
H
H
H
H
CF3
—
—
—
—





L1′
B
H
H
Ph3
H
H
H
—
—
—
—

365
Pt
1
1
L1
B
H
H
Ph3
H
H
CF3
—
—
—
—





L1′
B
H
H
Ph2
H
H
H
H
F
H
H

366
Pd
1
1
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H





L1′
B
H
H
Tn5
H
H
H
H
H
—
—

367
Pd
1
1
L1
B
H
H
Np3
H
H
H
H
H
—
—





L1′
B
H
H
H
Tn5
H
H
H
H
—
—

368
Pd
1
1
L1
B
H
H
Tn7
H
H
H
H
H
—
—





L1′
B
H
H
Pe2
H
H
H
H
—
—
—

369
Pd
1
1
L1
B
H
H
Tn8
H
H
H
H
H
—
—





L1′
B
H
H
Np4
H
H
H
H
—
—
—

370
Pd
1
1
L1
B
H
H
Tn6
H
H
H
H
H
—
—





L1′
B
CH3
H
H
H
H
H
—
—
—
—

371
Rh
2
1
L1
B
H
H
H
H
H
H
—
—
—
—





L1′
C
H
—
Cl
CF3
H
H
—
—
—
—

372
Rh
2
1
L1
B
H
H
Ph3
H
H
CF3
—
—
—
—





L1′
N
CH3
H
H
CF3
H
H
—
—
—
—

373
Pt
1
1
L1
B
H
H
Tn6
H
H
H
H
H
—
—





L1′
S
H
—
H
OC4H9
H
H
—
—
—
—

374
Pt
1
1
L1
B
H
CH3
OC4H9
H
H
H
—
—
—
—





L1′
C′
H
H
Cl
CF3
H
H
—
—
—
—

375
Pd
1
1
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H





L1′
D′
CH3
—
Np3
H
H
H
H
H
—
—























































































TABLE 1-10







L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10





A″








R7
R8
R9
R10





B″

















No
M
m
n
L′
A″
B″
R3
R4
R5
R6
R7
R8
R9
R10




















376
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















377
Ir
2
1
L1
B
H
H
F
CF3
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















378
Ir
2
1
L1
B
H
H
Cl
CF3
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















379
Ir
2
1
L1
B
H
H
H
OCF3
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















380
Ir
2
1
L1
B
H
H
OC4H9
H
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















381
Ir
2
1
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H















—
Ph1
Pi
Ph2
H
H
H
H
F
H
H








—
—
—
—


















382
Ir
2
1
L1
B
H
H
Tn7
H
H
H
H
H
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















383
Ir
2
1
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H















—
Tn2
Pi
H
CH3
H
H
—
—
—
—








—
—
—
—


















384
Ir
2
1
L1
B
H
CH3
Np3
H
H
H
H
H
—
—















—
Tn3
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















385
Ir
2
1
L1
C
H
—
H
H
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















386
Ir
2
1
L1
D
H
H
CF3
H
H
H
—
—
—
—















—
Np2
Pi
H
H
H
CF3
—
—
—
—








—
—
—
—


















387
Ir
2
1
L1
E
—
—
H
Cl
H
H
—
—
—
—















—
Pe1
Py1
H
—
H
H
—
—
—
—








—
—
—
—


















388
Ir
2
1
L1
F
H
—
H
OCH(CH3)2
H
H
—
—
—
—















—
Tn1
Pr
H
H
Ph3
H
—
—
—
—








—
—
—
—

















































































































































































































TABLE 1-11







L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10





A″








R7
R8
R9
R10





B″

















No
M
m
n
L′
A″
B″
R3
R4
R5
R6
R7
R8
R9
R10




















389
Ir
2
1
L1
H
H
—
Ph2
H
H
H
H
H
CF3
H















—
Ph1
Pi
H
H
H
Tn5
—
—
—
—








H
H
—
—


















390
Ir
2
1
L1
H
CH3
—
H
Tn5
H
H
H
H
—
—















—
Ph1
Pi
H
H
H
Tn8
—
—
—
—








H
H
—
—


















391
Rh
2
1
L1
I
H
H
Tn8
H
H
H
H
H
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















392
Rh
2
1
L1
P
—
H
OCH3
H
H
H
—
—
—
—















—
Ph1
Pi
H
Ph2
H
H
F
F
F
F








—
—
—
—


















393
Rh
2
1
L1
V
H
—
Ph2
H
H
H
H
F
H
H















—
Tn2
Py2
—
H
H
H
—
—
—
—








—
—
—
—


















394
Rh
2
1
L1
D′
H
—
Ph2
H
H
H
H
F
H
H















—
Tn3
Pi
Np3
H
CF3
H
H
H
—
—








—
—
—
—


















395
Pt
1
1
L1
F′
—
—
F
CF3
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















396
Pt
1
1
L1
J′
—
—
Ph3
H
H
CF3
—
—
—
—















—
Tn1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















397
Pt
1
1
L1
C
H
—
Pe2
H
H
H
H
—
—
—















—
Np2
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















398
Pd
1
1
L1
B
H
H
H
H
H
H
—
—
—
—















—
Ph1
Pi
H
H
H
H
—
—
—
—








—
—
—
—


















399
Pd
1
1
L1
B
H
H
H
OCH(CH3)2
H
H
—
—
—
—















—
Tn3
Pi
Ph2
H
H
CH3
H
C3F7
H
H








—
—
—
—


















400
Pd
1
1
L1
C
H
—
H
H
H
H
—
—
—
—















—
Np1
Pr
H
H
An
H
—
—
—
—








H
—
—
—



































































































































































































TABLE 1-12





L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10





E










E

R7
R8
R9
R10





G












No
M
m
n
G

R7
R8
R9
R10




















401
Ir
2
1
L1
B
H
H
H
H
H
H
—
—
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















402
Ir
2
1
L1
B
H
H
F
CF3
H
H
—
—
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















403
Ir
2
1
L1
B
H
H
Cl
CF3
H
H
—
—
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















404
Ir
2
1
L1
B
H
H
H
OCF3
H
H
—
—
—
—










CF3

—
—
—
—


CF3

—
—
—
—


















405
Ir
2
1
L1
B
H
H
OC4H9
H
H
H
—
—
—
—










CF3

—
—
—
—


CF3

—
—
—
—


















406
Ir
2
1
L1
B
H
H
Ph2
H
H
H
H
H
CF3
H










Ph3

—
—
—
—


Ph3

—
—
—
—


















407
Ir
2
1
L1
B
H
H
Tn7
H
H
H
H
H
—
—










Ph2

H
C3H7
H
H


Ph2

H
C3H7
H
H


















408
Ir
2
1
L1
B
H
CH3
Ph2
H
H
H
H
F
H
H










Tn5

H
H
—
—


Tn5

H
H
—
—


















409
Ir
2
1
L1
B
H
CH3
Np3
H
H
H
H
H
—
—










CH3

—
—
—
—


Ph3

—
—
—
—


















410
Ir
2
1
L1
C
H
—
H
H
H
H
—
—
—
—










Tn6

H
H
—
—


Tn6

H
H
—
—


















411
Ir
2
1
L1
D
H
H
CF3
H
H
H
—
—
—
—










Np3

CH3O
H
—
—


Np3

CH3O
H
—
—


















412
Ir
2
1
L1
E
—
—
H
Cl
H
H
—
—
—
—










Np4

F
—
—
—


Np4

F
—
—
—


















413
Ir
2
1
L1
F
H
—
H
OCH(CH3)2
H
H
—
—
—
—










Tn7

CH3
H
—
—


Tn7

CH3
H
—
—








































































































































































TABLE 1-13





L
X
R1
R2
X1
X2
X3
X4
R7
R8
R9
R10





E










E

R7
R8
R9
R10





G












No
M
m
n
G

R7
R8
R9
R10




















414
Ir
2
1
L1
H
H
—
Ph2
H
H
H
H
H
CF3
H










Tn8

H
H
—
—


Tn8

H
H
—
—


















415
Ir
2
1
L1
H
CH3
—
H
Tn5
H
H
H
H
—
—










Pe2

H
—
—
—


Pe2

H
—
—
—


















416
Rh
2
1
L1
I
H
H
Tn8
H
H
H
H
H
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















417
Rh
2
1
L1
P
—
H
OCH3
H
H
H
—
—
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















418
Rh
2
1
L1
V
H
—
Ph2
H
H
H
H
F
H
H










CH3

—
—
—
—


CH3

—
—
—
—


















419
Rh
2
1
L1
D′
H
—
Ph2
H
H
H
H
F
H
H










Ph3

—
—
—
—


Ph3

—
—
—
—


















420
Pt
1
1
L1
F′
—
—
F
CF3
H
H
—
—
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















421
Pt
1
1
L1
J′
—
—
Ph3
H
H
CF3
—
—
—
—










CF3

—
—
—
—


CF3

—
—
—
—


















422
Pt
1
1
L1
C
H
—
Pe2
H
H
H
H
—
—
—










Pi2

H
H
—
—


Pi2

H
H
—
—


















423
Pd
1
1
L1
B
H
H
H
H
H
H
—
—
—
—










CH3

—
—
—
—


CH3

—
—
—
—


















424
Pd
1
1
L1
B
H
H
H
OCH9CH3)2
H
H
—
—
—
—










CF3

—
—
—
—


CF3

—
—
—
—


















425
Pd
1
1
L1
C
H
—
H
H
H
H
—
—
—
—










Qn2

H
H
—
—


Qn2

H
H
—
—































































































































































TABLE 1-14



No
M
m
n
L
X
R1
R2
R3
R4
X1
X2
X3
X4



426
Ir
3
0
L2
B
H
H
—
—
H
H
—
H

427
Ir
3
0
L3
B
H
H
—
—
F
H
H
—

428
Ir
3
0
L4
B
H
H
—
—
H
F
H
H

429
Ir
3
0
L5
B
H
H
—
—
—
F
H
H

430
Ir
3
0
L6
B
H
H
—
—
CF3
—
—
H

431
Ir
3
0
L7
B
H
H
—
—
H
H
H
H

432
Ir
3
0
L8
B
H
H
—
—
F
CF3
H
H

433
Ir
3
0
L9
B
H
H
—
—
H
H
CF3
F

434
Ir
3
0
L10
B
H
H
—
—
H
H
H
H

435
Ir
3
0
L11
B
H
H
—
—
H
H
H
H

436
Ir
3
0
L2′
B
H
H
—
—
H
CH3
—
H

437
Ir
3
0
L3′
B
H
H
—
—
OCH3
H
H
—

438
Ir
3
0
L4′
B
H
H
—
—
H
H
H
H

439
Ir
3
0
L5′
B
H
H
—
—
—
H
H
H

440
Ir
3
0
L6′
B
H
H
—
—
H
—
—
H

441
Ir
3
0
L7′
B
H
H
—
—
H
H
H
H

442
Ir
3
0
L8′
B
H
H
—
—
H
H
H
H

443
Ir
3
0
L9′
B
H
H
—
—
H
H
H
H

444
Ir
3
0
L10′
B
H
H
—
—
H
H
H
H

445
Ir
3
0
L11′
B
H
H
—
—
H
H
H
H

446
Ir
3
0
L1
M′
CH3
CH3
CH3
CH3
H
H
H
H

447
Ir
3
0
L1
M′
C2H5
C2H5
C2H5
C2H5
H
H
H
H

448
Ir
3
0
L1
M′
CH3
CH3
CH3
CH3
F
H
H
H

449
Ir
3
0
L1
M′
CH3
CH3
CH3
CH3
H
F
H
H

450
Ir
3
0
L1
M′
CH3
CH3
CH3
CH3
F
CH3
H
H









































Hereinbelow, the present invention will be described specifically based on Examples.
EXAMPLE 1
Synthesis of Example Compound No. 1









In a 2 L (liter)-three-necked flask, 69.0 g (472 mM) of α-tetralone, 50.0 g (720 mM) of hydroxylamine hydrochloride, 500 ml of ethanol and 360 ml of 2N-sodium hydroxide aqueous solution were placed and stirred for 1 hour at room temperature. The solvent was removed under reduced pressure to provide a dry solid (residue). To the residue, 500 ml of water was added and extracted three times with 150 ml of ethyl acetate. The organic layer was dried with anhydrous magnesium sulfate, followed by removal of the solvent under reduced pressure to obtain 74 g (Yield: 97.2%) of a pale yellow crystal of α-tetralone=oxime.









In a 1 L-three-necked flask, 80 ml of tetrahydrofuran and 23.8 g (595 M) of 60%-oily sodium hydride were placed and stirred for 5 minutes at room temperature, followed by addition thereof dropwise to solution of 74.0 g (459 mM) of α-tetralone=oxime in 500 ml of anhydrous DMF (dimethylformamide) in 15 minutes. Thereafter, the system was stirred for 1 hour at room temperature, followed by addition of 113.5 g (939 mM) of allyl bromide and further stirring for 12 hours at room temperature. After the reaction, the reaction product was subjected to removal of the solvent under reduced pressure to obtain a residue. To the residue, 500 ml of water was added and extracted three times with 200 ml of ethyl acetate. The organic layer was dried with anhydrous magnesium sulfate and subjected to removal of the solvent under reduced pressure to obtain a brown liquid. The liquid was subjected to distilling-off of the solvent under reduced pressure to obtain 79.5 g (Yield: 86.0%) of α-tetralone=oxime=O-allyl=ether having a boiling agent of 75–80° C. (6.7 Pa).









In a 1 L-autoclave, 58.0 g (288 mM) of α-tetralone=oxime=O-allyl=ether was placed and aerated with oxygen gas, followed by hermetic sealing with a cap and vigorous stirring for 5 days at 190° C. The reaction mixture was cooled to room temperature to provide a high-viscous brown liquid, which was dissolved in chloroform and extracted three times with 300 ml of 5%-hydrochloric acid. The aqueous layer was alkalified with 48%-sodium hydroxide and extracted three times with 350 ml of chloroform. The organic layer was dried with anhydrous magnesium sulfate and concentrated under reduced pressure, followed by purification by silica gel column chromatography using chloroform as an eluent and purification by silica gel column chromatography using a mixture solvent of hexane/ethyl acetate=5/1 as an eluent to obtain 7.7 g of a pale brown liquid. The liquid was purified by using a Kugelrohr distillation apparatus (ball-tube oven) to obtain 6.6 g (Yield: 12.6%) of colorless benzo[h]-5,6-dihydroquinoline.









In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heated for 2 hours at 130–140° C. under stirring and bubbling with nitrogen. The glycerol was cooled to 100° C. by standing, and 0.91 g (5.02 mM) of benzo[h]-5,6-dihydroquinoline and 0.50 g (1.02 mM) of iridium (III) acetylacetonate were added thereto, followed by stirring for 5 hours at 190–215° C. under heating and nitrogen stream. The reaction product was cooled to room temperature and poured into 300 ml of 1N-hydrochloric acid to obtain a precipitate, which was recovered by filtration and washed with water, followed by dissolution in acetone to remove an insoluble matter by filtration. The acetone was removed under reduced pressure to obtain a residue, which was purified by silica gel column chromatography using chloroform as an eluent to obtain 0.11 g (Yield: 14.7%) of yellow powder of iridium (III) tris{benzo[h]-5,6-dihydroquinoline}.
This compound exhibited a PL (photoluminescence) spectrum having λmax (maximum emission wavelength) of 511 nm and a quantum yield of 0.51 in a solution state. For comparison, when a solution of Ir(ppy) 3 as the above-mentioned conventional luminescent material which was not crosslinked with an alkylene group, different from the metal coordination compound of the present invention, was subjected to measurement of PL spectrum in a similar manner, λmax (maximum emission wavelength) was 510 nm and a quantum yield was 0.40. Further, an organic EL device prepared in Example 3 described hereinafter caused luminescence at a high luminance under application of an electric field. Further, EL spectrum thereof had a λmax (maximum emission wavelength) of 510 nm.
EXAMPLE 2
Synthesis of Ex. Comp. No. 53









In a 3 L (liter)-three-necked flask, 166.0 g (1036 mM) of 1-benzosuberone, 125.0 g (1141 mM) of O-allylhydroxylamine hydrochloride, 93.5 g (1140 mM) of sodium acetate, 158.0 g (1143 mM) of potassium carbonate and 1500 ml of ethanol were placed and stirred for 1.5 hours at 80° C. under heating. The reaction product was cooled to room temperature and subjected to removal of the solvent under reduced pressure to obtain a residue. To the residue, 1500 ml of water was added and extracted three times with 500 ml of ethyl acetate. The organic layer was dried with anhydrous magnesium sulfate and subjected to removal of the solvent under reduced pressure to obtain a pale brown liquid. The liquid was subjected to distilling-off of the solvent under reduced pressure to obtain 221.8 g (Yield: 99.0%) of 1-benzosuberone=oxime=O-allyl=ether having a boiling agent of 75–83° C. (4.0 Pa).









In a 5 L-autoclave, 222.0 g (1022 mM) of 1-benzosuberone=oxime=O-allyl=ether was placed and aerated with oxygen gas, followed by hermetic sealing with a cap and vigorous stirring for 3 days at 190° C. The reaction mixture was cooled to room temperature to provide a high-viscous brown liquid, which was dissolved in 2 liters of chloroform and extracted three times with 500 ml of 5%-hydrochloric acid. The aqueous layer was alkalified with 48%-sodium hydroxide and extracted three times with 500 ml of chloroform. The organic layer was dried with anhydrous magnesium sulfate and subjected to removal of the solvent under reduced pressure, followed by purification by silica gel column chromatography using a mixture solvent of hexane/ethyl acetate=5/1 as an eluent to obtain 19 g of a pale brown liquid. The liquid was purified by using a Kugelrohr distillation apparatus (ball-tube oven) to obtain 13.5 g (Yield: 6.8%) of pale green 3,2′-trimethylene-2-phenylpyridine.









In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heated for 2 hours at 130–140° C. under stirring and bubbling with nitrogen. The glycerol was cooled to 100° C. by standing, and 0.98 g (5.02 mM) of 3,2′-trimethylene-2-phenylpyridine and 0.50 g (1.02 mM) of iridium (III) acetylacetonate were added thereto, followed by stirring for 8 hours at 190–210° C. under heating and nitrogen stream. The reaction product was cooled to room temperature and poured into 300 ml of 1N-hydrochloric acid to obtain a precipitate, which was recovered by filtration and washed with water, followed by dissolution in acetone to remove an insoluble matter by filtration. The acetone was removed under reduced pressure to obtain a residue, which was purified by silica gel column chromatography using chloroform as an eluent to obtain 0.18 g (Yield: 22.7%) of yellow powder of iridium (III) tris{3,2′-trimethylene-2-phenylpyridine}. An organic EL device prepared in Example 6 described hereinafter caused bluish green luminescence under application of an electric field.
EXAMPLES 3–11 AND COMPARATIVE EXAMPLE 1
As each device structure, a device having three-layered organic layers shown in FIG. 1( b ) was used.
On a glass substrate (transparent substrate 15 ), a 100 nm-thick ITO (transparent electrode 14 ) was formed and then patterned. On the ITO electrode, the following organic layers and electrode layers were successively formed in the following film thicknesses in a vacuum chamber at a vacuum of 10 −4 Pa by resistance heating vacuum deposition.
Organic layer 1 (hole-transporting layer 13 ) (40 nm): α-NPD Organic layer 2 (luminescence layer 12 ) (30 nm): CBP/luminescent material (=95/5)

This layer was formed by co-deposition of CBP as a host material with a metal coordination compound shown in Table 2 appearing hereinafter in a weight proportion of 5 wt. % as a luminescent material.
Organic layer 3 (electron-transporting layer 16 ) (30 nm): Alq 3 Metal electrode 1 (15 nm): AlLi alloy (Li content: 1.8 wt. %) Metal electrode 2 (100 nm): Al

After the electrode materials were formed into films, the electrodes were patterned to have an opposing electrode area of 3 mm 2 .
Each device was supplied with an electric field with the ITO side as the anode and the Al side as the cathode by applying a voltage so that a current value became constant, thus measuring a change in luminance with time. A current amount (density) was set to 70 mA/cm 2 and respective devices showed luminances obtained at an initial stage in a range of 80–250 cd/m 2 . Times required for ½ of these luminances, respectively, were evaluated as a luminance half-life (half-time).
For measurement, in order to remove factors for device deterioration due to oxygen or water, the above measurement was performed in a dry nitrogen flow after taking the device out of the vacuum chamber.
In Comparative Example 1, Ir(ppy) 3 described in the above-mentioned article 2 was used as a conventional luminescent material.
The results of current-conduction durability test for the devices using the respective compounds are shown in Table 2. The devices (of the present invention) exhibited clearly larger luminance half-life values than the device using the conventional luminescent material, thus resulting in devices with high durability resulting from a stability of a material used in the present invention.








TABLE 2





Luminescence
Luminance half-


material No.
life (Hr)












Example 3
(1)
950


Example 4
(7)
850


Example 5
(48)
700


Example 6
(53)
900


Example 7
(102)
600


Example 8
(131)
500


Example 9
(302)
800


Example 10
(376)
750


Example 11
(401)
650


Comparative
Ir(ppy) 3
350


Example 1

































EXAMPLE 12
An embodiment of the electroluminescence device of the present invention applied to an active-matrix type color organic EL display using a TFT circuit shown in FIG. 3 will be described with reference to FIG. 2 .
FIG. 2 schematically illustrates an example of a panel structure provided with an organic EL device and drive means. In this example, the number of pixels was set to 128×128 pixels. Incidentally, one pixel was composed of three color pixels comprising a green pixel, a blue pixel and a red pixel.
On a glass substrate, a thin film transistor circuit using polysilicon (referred to as a TFT circuit) was formed by a known method.
In regions corresponding to the respective color pixels, organic layers and a metal electrode layer were formed in the following thicknesses by vacuum deposition with a hand mask, followed by patterning. Organic layer structures corresponding to the respective color pixels are shown below.
Green pixel=α-NPD (40 nm)/CBP:phosphorescent material (=93:7 by weight) (30 nm)/BCP (20 nm)/Alq (40 nm) Blue pixel: α-NPD (50 nm)/BCP (20 nm)/Alq (50 nm) Red pixel: α-NPD (40 nm)/CBP:PtOEP (=93:7 by weight) (30 nm)/BCP (20 nm)/Alq (40 nm)

A luminescence layer for the green pixel was formed by co-deposition of CBP as a host material with a phosphorescent material (Example Compound No. 1) having a weight proportion of 7 wt. %.
In the panel shown in FIG. 2 , a scanning signal driver, a data signal driver and a current supply source are disposed and are connected to gate selection lines, data signal lines and current supply lines, respectively. At intersections of the gate selection lines and data signal lines, a pixel circuit (equivalent circuit) shown in FIG. 3 is disposed, the gate selection lines G 1 , G 2 , G 3 . . . Gn are sequentially selected by the scanning signal driver and in synchronism therewith, image (picture) signals are applied from the data signal driver.
Next, a pixel circuit operation is described with reference to the equivalent circuit shown in FIG. 3 . When a selection signal is applied to a gate selection line, TFT 1 is turned on so that a display signal is supplied from a data signal line to a capacitor Cadd, thereby determining the gate potential of TFT 2 , whereby a current is supplied to an organic luminescence device (abbreviate as EL) disposed at each pixel through a current supply line depending on the gate potential of TFT 2 . The gate potential of TFT 2 is held at Cadd during one frame period, so that the current continually flows from the current supply line to the EL device during the period. As a result, luminescence can be retained during one frame period.
As a result, it has been confirmed that it was possible to display a desired image data, thus resulting in stable display with good image quality.
In this example, as the application to display, the driving scheme using the TFT circuit of an active-matrix scheme was used. However, the switching device used in the present invention need not be particularly restricted, and can also be readily applicable to a single-crystal silicon substrate, an MIM (metal-insulator-metal) device, an a-Si (amorphous silicon)-type TFT circuit, etc.
INDUSTRIAL APPLICABILITY
As described above, a luminescence device using a metal coordination compound represented by the above-mentioned formula (1) as a luminescent material had a high phosphorescence efficiency and could retain high-luminance luminescence for a long period. Further, the metal coordination compound is an excellent material allowing control of emission wavelength, particularly shift to a shorter wavelength. Further, the luminescence device of the present invention is also excellent as a display device.
A high-efficiency luminescence device according to the present invention is applicable to a product requiring energy economization or a high luminance. As applied examples, a display apparatus, an illumination apparatus, a printer light source or a backlight for a liquid crystal display apparatus, etc. are considered. As for a display apparatus, it allows a flat panel display which provides a highly recognizable display at a low energy consumption and is light in weight. As a printer light source, the luminescence device of the present invention can be used-instead of a laser light source of a laser beam printer which is currently extensively used. Independently addressable devices are arranged in an array form to effect a desired exposure on a photosensitive drum thereby forming an image. The apparatus volume can be remarkably reduced by using the devices of the present invention.