U.S. patent application number 10/924903 was filed with the patent office on 2005-02-03 for metal coordination compound, luminescence device and display apparatus.
This patent application is currently assigned to CANON KABUSHIKI KAISHA. Invention is credited to Furugori, Manabu, Kamatani, Jun, Miura, Seishi, Moriyama, Takashi, Okada, Shinjiro, Takiguchi, Takao, Tsuboyama, Akira.
Application Number | 20050027123 10/924903 |
Document ID | / |
Family ID | 26611259 |
Filed Date | 2005-02-03 |
United States Patent
Application |
20050027123 |
Kind Code |
A1 |
Takiguchi, Takao ; et
al. |
February 3, 2005 |
Metal coordination compound, luminescence device and display
apparatus
Abstract
An electroluminescence device having a layer containing a
specific metal coordination compound is provided. The metal
coordination compound is represented by formula (1) below:
ML.sub.mL'.sub.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 and n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial
structure MLm is represented by formula (2) shown below and a
partial structure ML'.sub.n is represented by formula (3) or (4)
shown below: 1 at least one of the optional substituent(s) of the
cyclic groups, and the cyclic groups CyCl and CyC2 includes a
benzofuran structure capable of having a substituent represented by
the following formula (5): 2 The metal coordination compound having
the benzofuran structure is effective in providing high-efficiency
luminescence and long-term high luminance.
Inventors: |
Takiguchi, Takao;
(Setagaya-ku, JP) ; Okada, Shinjiro; (Isehara-shi,
JP) ; Tsuboyama, Akira; (Sagamihara-shi, JP) ;
Miura, Seishi; (Sagamihara-shi, JP) ; Moriyama,
Takashi; (Kawasaki-shi, JP) ; Kamatani, Jun;
(Kawasaki-shi, JP) ; Furugori, Manabu;
(Atsugi-shi, JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Assignee: |
CANON KABUSHIKI KAISHA
Tokyo
JP
|
Family ID: |
26611259 |
Appl. No.: |
10/924903 |
Filed: |
August 25, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10924903 |
Aug 25, 2004 |
|
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|
10095095 |
Mar 12, 2002 |
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Current U.S.
Class: |
546/2 |
Current CPC
Class: |
C09K 11/06 20130101;
C09K 2211/1088 20130101; H01L 51/0084 20130101; C09K 2211/185
20130101; H01L 51/0087 20130101; C07F 15/0033 20130101; C09K
2211/1014 20130101; Y10S 428/917 20130101; C09K 2211/1011 20130101;
H01L 51/0085 20130101; C09K 2211/1029 20130101; C09K 2211/1007
20130101; H01L 51/5012 20130101 |
Class at
Publication: |
546/002 |
International
Class: |
C07F 015/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 14, 2001 |
JP |
072665/2001 |
Feb 20, 2002 |
JP |
043536/2002 |
Claims
What is claimed is:
1. A metal coordination compound represented by formula (1)
below:ML.sub.mL'L.sub.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 and n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a
partial structure MLm is represented by formula (2) shown below and
a partial structure ML'.sub.n is represented by formula (3) or (4)
shown below: 21wherein CyN1 and CyN2 are each cyclic group capable
of having a substituent, including a nitrogen atom and bonded to
the metal atom M via the nitrogen atom; CyC1 and CyC2 are each
cyclic group capable of having a substituent, including a carbon
atom and bonded to the metal atom M via the carbon atom with the
proviso that the cyclic group CyN1 and the cyclic group CyC1 are
bonded to each other via a covalent bond and the cyclic group CyN2
and the cyclic group CyC2 are bonded to each other via covalent
bond; the optional substituent of the cyclic groups is selected
from a halogen atom, 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.dbd.CH-- or --C.ident.C--, and the alkyl group can
include a hydrogen atom that can be optionally replaced with a
fluorine atom, or an aromatic group capable of having a substituent
(that is a halogen atom, a cyano atom, a nitro atom, 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.dbd.CH-- or --C.ident.C--, and the alkyl group can
include a hydrogen atom that can be optionally replaced with a
fluorine atom); 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 optionally replaced with a
fluorine atom, or an aromatic group capable of having a substituent
(that is a halogen atom, a cyano atom, a nitro atom, a
trialkylsilyl group of which the alkyl groups are independently a
linear or branched alkyl group having 1-8 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.dbd.CH-- or --C.ident.C--, and the alkyl group can
include a hydrogen atom that can be optionally replaced with a
fluorine atom; and at least one of the optional substituent(s) of
the cyclic groups, and the cyclic groups CyC1 and CyC2 includes a
benzofuran structure capable of having a substituent represented by
the following formula (5): 22wherein the benzofuran structure of
the formula (5) is bonded to CyN1, CyN2, CyC1 or CyC2 via a single
bond at any one of 2- to 7-positions when the benzofuran structure
is the optional substituent(s) of the cyclic groups, and the
benzofuran structure of the formula (5) is bonded to CyN1 or CyN2
via a single bond at any one of 2- to 7-positions and bonded to the
metal atom M via a single bond at any one of 2- to 7-positions when
the benzofuran structure is CyC1 or CyC2; the optional substituent
of the benzofuran structure of the formula (5) is selected from a
halogen atom, 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.dbd.CH-- or --C.ident.C--, and the alkyl group can include a
hydrogen atom that can be optionally replaced with a fluorine atom,
or an aromatic group capable of having a substituent (that is a
halogen atom, a cyano atom, a nitro atom, 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.dbd.CH-- or --C.ident.C--, and the alkyl group can
include a hydrogen atom that can be optionally replaced with a
fluorine atom) with the proviso that an adjacent pair of
substituents located at 4- to 7-positions of the benzofuran
structure of the formula (5) can be bonded to form a cyclic
structure.
2. A metal coordination compound according to claim 1, wherein n is
0 in the formula (1).
3. A metal coordination compound according to claim 1, including a
partial structure ML'.sub.n represented by the formula (3) in the
formula (1).
4. A metal coordination compound according to claim 1, including a
partial structure ML'.sub.n represented by the formula (4) in the
formula (1).
5. A metal coordination compound according to claim 1, wherein the
cyclic groups CyC1 and CyC2 are independently selected from phenyl
group, thienyl group, thianaphthyl group, naphthyl group, pyrenyl
group, 9-fluorenonyl group, fluorenyl group, dibenzofuranyl group,
dibenzothienyl group, carbazolyl group, or benzofuranyl group, as
an aromatic cyclic group capable of having a substituent with the
proviso that the aromatic cyclic group can include one or two CH
groups that can be replaced with a nitrogen atom.
6. A metal coordination compound according to claim 5, wherein the
cyclic groups CyC1 and Cy2 are independently phenyl group or
benzofuranyl group.
7. A metal coordination compound according to claim 1, wherein the
cyclic groups CyN1 and CyN2 are independently selected from pyridyl
group, pyridazinyl group, and pyrimidinyl group, as an aromatic
cyclic group capable of having a substituent.
8. A metal coordination compound according to claim 7, wherein the
aromatic cyclic group is pyridyl group.
9. A metal coordination compound according to claim 1, wherein the
cyclic groups CyN1, CyN2, CyC1 and CyC2 are independently
non-substituted, or have a substituent selected from a halogen atom
and 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--, --CH.dbd.CH--, --C.ident.C--, or a divalent aromatic group
capable of having a substituent (that is a halogen atom 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--, and the alkyl
group can include a hydrogen atom that can be optionally replaced
with a fluorine atom)), and the alkyl group can include a hydrogen
atom that can be optionally replaced with a fluorine atom}.
10. A metal coordination compound according to claim 1, wherein M
in the formula (1) is iridium.
11. A metal coordination compound according to claim 1, which is
represented by the following formula (6) or (7): 23wherein R.sub.1,
R.sub.2, R.sub.3, R'.sub.3 and R.sub.4 are independently a hydrogen
atom; a fluorine atom; a linear or branched alkyl group of formula:
C.sub.nH.sub.2n+1-- in which n is an integer of 1-20, the alkyl
group can include one or non-neighboring two or more methylene
groups that can be replaced with --O-- and also can include a
hydrogen atom that can be optionally replaced with a fluorine atom;
a phenyl group capable of having a substituent; or a benzofuranyl
group capable of having a substituent; the optional substituent of
phenyl group and benzofuranyl group is a fluorine atom or a linear
or branched alkyl group of formula: C.sub.nH.sub.2n+1-- in which n
is an integer of 1-20, the alkyl group can include one or
non-neighboring two or more methylene groups that can be replaced
with --O-- and also can include a hydrogen atom that can be
optionally replaced with a fluorine atom.
12. An electroluminescence device, comprising: a pair of electrodes
disposed on a substrate, and a luminescence unit comprising at
least one organic compound disposed between the electrodes, wherein
the organic compound comprises a metal coordination compound
represented by the formula (1) in claim 1.
13. An electroluminescence device according to claim 12 wherein a
voltage is applied between the electrodes to emit
phosphorescence.
14. A picture display apparatus, comprising an electroluminescence
device according to claim 12, and a means for supplying electric
signals to the electroluminescence device.
Description
FIELD OF THE INVENTION AND RELATED ART
[0001] The present invention relates to an organic luminescence
device (also called an organic electroluminescence device or
organic EL device) for use in a planar light source, a planar
display, etc. Particularly, the present invention relates to a
novel metal coordination compound and a luminescence device having
a high luminescence efficiency and causing little change with time
by using a metal coordination compound represented by formula (1)
appearing hereinafter.
[0002] An old example of organic luminescence device is, e.g., one
using luminescence of a vacuum-deposited anthracene film (Thin
Solid Films, 94 (1982) 171). In recent years, however, in view of
advantages, such as easiness of providing a large-area device
compared with an inorganic luminescence device, and possibility of
realizing desired luminescence colors by development of various new
materials and drivability at low voltages, an extensive study
thereon for device formation as a luminescence device of a
high-speed responsiveness and a high efficiency, has been
conducted.
[0003] As precisely described in Macromol. Symp. 125, 1-48 (1997),
for example, an organic EL device generally has an organization
comprising a pair of upper and lower electrodes formed on a
transparent substrate, and organic material layers including a
luminescence layer disposed between the electrodes.
[0004] In the luminescence layer, aluminum quinolinol complexes
(inclusive of Alq3 shown hereinafter as a representative example)
having an electron-transporting characteristic and a luminescence
characteristic, are used for example. In a hole-transporting layer,
a material having an electron-donative property, such as a
triphenyldiamine derivative (inclusive of .alpha.-NPD shown
hereinafter as a representative example), is used for example.
[0005] Such a device shows a current-rectifying characteristic such
that when an electric field is applied between the electrodes,
holes are injected from the anode and electrons are injected from
the cathode.
[0006] The injected holes and electrons are recombined in the
luminescence layer to form excitons, which emit luminescence when
they are transitioned to the ground state.
[0007] In this process, the excited states include a singlet state
and a triplet state and a transition from the former to the ground
state is called fluorescence and a transition from the latter is
called phosphorescence. Materials in theses states are called
singlet excitons and triplet excitons, respectively.
[0008] In most of the organic luminescence devices studied
heretofore, fluorescence caused by the transition of a singlet
exciton to the ground state, has been utilized. On the other hand,
in recent years, devices utilizing phosphorescence via triplet
excitons have been studied.
[0009] Representative published literature may include:
[0010] 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
[0011] 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)).
[0012] In these articles, a structure including four organic layers
sandwiched between the electrodes, and the materials used therein
include carrier-transporting materials and phosphorescent
materials, of which the names and structures are shown below
together with their abbreviations.
[0013] Alq3: aluminum quinolinol complex
[0014] .alpha.-NPD:
N4,N4'-di-naphthalene-1-yl-N4,N4'-diphenyl-biphenyl-4,-
4'-diamine
[0015] CBP: 4,4'-N,N'-dicarbazole-biphenyl
[0016] BCP: 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline
[0017] PtOEP: platinum-octaethylporphyrin complex
[0018] Ir(ppy).sub.3: iridium-phenylpyrimidine complex 34
[0019] The above-mentioned Articles 1 and 2 both have reported
structures, as exhibiting a high efficiency, including a
hole-transporting layer comprising .alpha.-NPD, an
electron-transporting layer comprising Alq3, an exciton
diffusion-preventing layer comprising BCP, and a luminescence layer
comprising CBP as a host and ca. 6% of PtOEP or Ir(ppy).sub.3 as a
phosphorescent material dispersed in mixture therein.
[0020] Such a phosphorescent material is particularly noted at
present because it is expected to provide a high luminescence
efficiency in principle for the following reasons. More
specifically, excitons formed by carrier recombination comprise
singlet excitons and triplet excitons in a probability ratio of
1:3. Conventional organic EL devices have utilized fluorescence of
which the luminescence efficiency is limited to at most 25%. On the
other hand, if phosphorescence generated from triplet excitons is
utilized, an efficiency of at least three times is expected, and
even an efficiency of 100%, i.e., four times, can be expected in
principle, if a transition owing to intersystem crossing from a
singlet state having a higher energy to a triplet state is taken
into account.
[0021] However, like a fluorescent-type device, such an organic
luminescence device utilizing phosphorescence is generally required
to be further improved regarding the deterioration of luminescence
efficiency and device stability.
[0022] The reason of the deterioration has not been fully
clarified, but the present inventors consider as follows based on
the mechanism of phosphorescence.
[0023] In the case where the luminescence layer comprises a host
material having a carrier-transporting function and a
phosphorescent guest material, a process of phosphorescence via
triplet excitons may include unit processes as follows:
[0024] 1. transportation of electrons and holes within a
luminescence layer,
[0025] 2. formation of host excitons,
[0026] 3. excitation energy transfer between host molecules,
[0027] 4. excitation energy transfer from the host to the
guest,
[0028] 5. formation of guest triplet excitons, and
[0029] 6. transition of the guest triplet excitons to the ground
state and phosphorescence.
[0030] Desirable energy transfer in each unit process and
luminescence are caused in competition with various energy
deactivation processes.
[0031] Needless to say, a luminescence efficiency of an organic
luminescence device is increased by increasing the luminescence
quantum yield of a luminescence center material.
[0032] Particularly, in a phosphorescent material, this may be
attributable to a life of the triplet excitons which is longer by
three or more digits than the life of a singlet exciton. More
specifically, because it is held in a high-energy excited state for
a longer period, it is liable to react with surrounding materials
and cause polymer formation among the excitons, thus incurring a
higher probability of deactivation process resulting in a material
change or life deterioration.
[0033] A luminescence device is desired to exhibit high efficiency
luminescence and show a high stability. Particularly, it is
strongly desired to provide a luminescence material compound which
is less liable to cause energy deactivation in a long life of
excited energy state and is also chemically stable, thus providing
a longer device life.
SUMMARY OF THE INVENTION
[0034] Accordingly, principal objects of the present invention are
to provide a luminescence material which exhibits a high
luminescence efficiency and retains a high luminance for a long
period, and also provide a luminescence device and a display
apparatus using the same.
[0035] In the present invention, a metal complex is used as a
luminescence material, particularly a novel luminescent metal
complex compound comprising iridium as a center metal and a
benzofuran structure of formula (5) appearing hereinafter as a part
of a ligand or as a substituent of a ligand.
[0036] More specifically, the present invention provides as a
luminescence material a metal coordination compound represented by
formula (1) below:
ML.sub.mL'.sub.n (1),
[0037] 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 and n is 0, 1
or 2 with the proviso that m+n is 2 or 3; a partial structure MLm
is represented by formula (2) shown below and a partial structure
ML.sub.n is represented by formula (3) or (4) shown below: 5
[0038] wherein CyN1 and CyN2 are each cyclic group capable of
having a substituent, including a nitrogen atom and bonded to the
metal atom M via the nitrogen atom; CyC1 and CyC2 are each cyclic
group capable of having a substituent, including a carbon atom and
bonded to the metal atom M via the carbon atom with the proviso
that the cyclic group CyN1 and the cyclic group CyC1 are bonded to
each other via a covalent bond and the cyclic group CyN2 and the
cyclic group CyC2 are bonded to each other via a covalent bond;
[0039] the optional substituent of the cyclic groups is selected
from a halogen atom, 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.dbd.CH-- or --C.ident.C--, and the alkyl group can
include a hydrogen atom that can be optionally replaced with a
fluorine atom, or an aromatic group capable of having a substituent
(that is a halogen atom, a cyano atom, a nitro atom, 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.dbd.CH-- or --C.ident.C--, and the alkyl group can
include a hydrogen atom that can be optionally replaced with a
fluorine atom);
[0040] 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 optionally replaced with a fluorine atom,
or an aromatic group capable of having a substituent (that is a
halogen atom, a cyano atom, a nitro atom, a trialkylsilyl group of
which the alkyl groups are independently a linear or branched alkyl
group having 1-8 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.dbd.CH-- or --C.ident.C--, and the alkyl group can include a
hydrogen atom that can be optionally replaced with a fluorine atom;
and
[0041] at least one of the optional substituent(s) of the cyclic
groups, and the cyclic groups CyC1 and CyC2 includes a benzofuran
structure capable of having a substituent represented by the
following formula (5): 6
[0042] wherein the benzofuran structure of the formula (5) is
bonded to CyN1, CyN2, CyC1 or CyC2 via a single bond at any one of
2- to 7-positions when the benzofuran structure is the optional
substituent(s) of the cyclic groups, and the benzofuran structure
of the formula (5) is bonded to CyN1 or CyN2 via a single bond at
any one of 2- to 7-positions and bonded to the metal atom M via a
single bond at any one of 2- to 7-positions when the benzofuran
structure is CyC1 or CyC2;
[0043] the optional substituent of the benzofuran structure of the
formula (5) is selected from a halogen atom, 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.dbd.CH-- or --C.ident.C--, and
the alkyl group can include a hydrogen atom that can be optionally
replaced with a fluorine atom, or an aromatic group capable of
having a substituent (that is a halogen atom, a cyano atom, a nitro
atom, 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.dbd.CH-- or --C.ident.C--, and
the alkyl group can include a hydrogen atom that can be optionally
replaced with a fluorine atom) with the proviso that an adjacent
pair of substituents located at 4- to 7-positions of the benzofuran
structure of the formula (5) can be bonded to form a cyclic
structure.
[0044] Preferred embodiments of the metal coordination compound of
the formula (1) according to the present invention include the
following:
[0045] A metal coordination compound, wherein n is 0 in the formula
(1).
[0046] A metal coordination compound having a partial structure
ML'.sub.n represented by the formula (3) in the formula (1).
[0047] A metal coordination compound having a partial structure
ML'.sub.n represented by the formula (4) in the formula (1).
[0048] A metal coordination compound wherein the cyclic groups CyC1
in the formula (1) and CyC2 in the formula (3) are independently
selected from phenyl group, thienyl group, thianaphthyl group,
naphthyl group, pyrenyl group, 9-fluorenonyl group, fluorenyl
group, dibenzofuranyl group, dibenzothienyl group, carbazolyl
group, or benzofuranyl group, as an aromatic cyclic group capable
of having a substituent with the proviso that the aromatic cyclic
group can include one or two CH groups that can be replaced with a
nitrogen atom, particularly selected from phenyl group or
benzofuranyl group.
[0049] A metal coordination compound, wherein the cyclic groups
CyN1 in the formula (2) and CyN2 in the formula (3) are
independently selected from pyridyl group, pyridazinyl group, and
pyrimidinyl group, particularly pyridyl group, as an aromatic
cyclic group capable of having a substituent.
[0050] A metal coordination compound, wherein the cyclic groups
CyN1, CyN2, CyC1 and CyC2 are independently non-substituted, or
have a substituent selected from a halogen atom and 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--,
--CH.dbd.CH--, --C.ident.C--, or a divalent aromatic group capable
of having a substituent (that is a halogen atom 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--, and the alkyl
group can include a hydrogen atom that can be optionally replaced
with a fluorine atom)), and the alkyl group can include a hydrogen
atom that can be optionally replaced with a fluorine atom}.
[0051] A metal coordination compound, wherein M in the formula (1)
is iridium.
[0052] A metal coordination compound represented by the following
formula (6) or (7), particularly the formula (7): 7
[0053] wherein R.sub.1, R.sub.2, R.sub.3, R'.sub.3 and R.sub.4 are
independently
[0054] a hydrogen atom; a fluorine atom; a linear or branched alkyl
group of formula: C.sub.nH.sub.2n+1-- in which n is an integer of
1-20, the alkyl group can include one or non-neighboring two or
more methylene groups that can be replaced with --O-- and also can
include a hydrogen atom that can be optionally replaced with a
fluorine atom; a phenyl group capable of having a substituent; or a
benzofuranyl group capable of having a substituent; the optional
substituent of phenyl group and benzofuranyl group is a fluorine
atom or a linear or branched alkyl group of formula:
C.sub.nH.sub.2n+1 -- in which n is an integer of 1-20, the alkyl
group can include one or non-neighboring two or more methylene
groups that can be replaced with --O-- and also can include a
hydrogen atom that can be optionally replaced with a fluorine
atom.
[0055] The present invention also provides an electroluminescence
device, comprising: a pair of electrodes disposed on a substrate,
and a luminescence unit comprising at least one organic compound
disposed between the electrodes, wherein the organic compound
comprises a metal coordination compound represented by the formula
(1) described above.
[0056] In the luminescence device, a voltage is applied between the
electrodes to emit phosphorescence.
[0057] The present invention further provides a picture display
apparatus, comprising an electroluminescence device described above
and a means for supplying electric signals to the
electroluminescence device.
[0058] These and other objects, features and advantages of the
present invention will become more apparent upon a consideration of
the following description of the preferred embodiments of the
present invention taken in conjunction with the accompanying
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0059] FIGS. 1A, 1B and 1C illustrate embodiments of the
luminescence device according to the present invention,
respectively.
[0060] FIG. 2 schematically illustrates a panel structure including
an EL device and drive means.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0061] Basic structures of organic luminescence (EL) devices formed
according to the present invention are illustrated in FIGS. 1A, 1B
and 1C.
[0062] As shown in these figures, an organic luminescence device
generally comprises, on a transparent substrate 15, a 50 to 200
nm-thick transparent electrode 14, a plurality of organic film
layers and a metal electrode 11 formed so as to cover the organic
layers.
[0063] FIG. 1A shows an embodiment wherein the organic luminescence
device comprises a luminescence layer 12 and a hole-transporting
layer 13. The transparent electrode 14 may comprise ITO, etc.,
having a large work function so as to facilitate hole injection
from the transparent electrode 14 to the hole-transporting layer
13. The metal electrode 11 comprises a metal material having a
small work function, such as aluminum, magnesium or alloys of these
elements, so as to facilitate electron injection into the organic
luminescence device.
[0064] The luminescence layer 12 comprises a compound (metal
coordination compound) according to the present invention. The
hole-transporting layer 13 may comprise, e.g., a triphenyldiamine
derivative, as represented by .alpha.-NPD mentioned above, and also
a material having an electron-donative property as desired.
[0065] A device organized above exhibits a current-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 in the luminescence layer 12 to form excitons having
high energy potential, which cause luminescence during transition
to the ground state. In this instance, the hole-transporting layer
13 functions as an electron-blocking layer to increase the
recombination efficiency at the boundary between the luminescence
layer layer 12 and the hole-transporting layer 13, thereby
providing an enhanced luminescence efficiency.
[0066] Further, in the structure of FIG. 1B, an
electron-transporting layer 16 is disposed between the metal
electrode 11 and the luminescence layer 12 in FIG. 1A. As a result,
the luminescence function is separated from the functions of
electron transportation and hole transportation to provide a
structure exhibiting more effective carrier blocking, thus
increasing the luminescence efficiency. The electron-transporting
layer 16, may comprise, e.g., an oxadiazole derivative.
[0067] FIG. 1C shows another desirable form of a four-layer
structure, including a hole-transporting layer 13, a luminescence
layer 12, an exciton diffusion prevention layer 17 and an
electron-transporting layer 16, successively from the side of the
transparent electrode 14 as the anode.
[0068] The luminescence materials used in the present invention are
most suitably metal coordination compounds represented by the
above-mentioned formulae (1) to (5), which are found to cause
high-efficiency luminescence, retain high luminance for a long
period and show little deterioration by current passage.
[0069] The metal coordination compound of the present invention
emits phosphorescence, and its lowest excited state is believed to
be an MLCT* (metal-to-ligand charge transfer) excited state or
.pi.-.pi.* excited state in a triplet state, and phosphorescence is
caused at the time of transition from such a state to the ground
state.
[0070] Hereinbelow, methods for measurement of some properties and
physical values described herein for characterizing the
luminescence material of the present invention will be
described.
[0071] (1) Judgment Between Phosphorescence and Fluorescence
[0072] The identification of phosphorescence was effected depending
on whether deactivation with oxygen was caused or not. A solution
of a sample compound in chloroform after aeration with oxygen or
with nitrogen is subjected to photoillumination to cause
photo-luminescence. The luminescence is judged to be
phosphorescence if almost no luminescence attributable to the
compound is observed with respect to the solution aerated with
oxygen but photo-luminescence is confirmed with respect to the
solution aerated with nitrogen. The phosphorescence of all the
compounds of the present invention has been confirmed by this
method unless otherwise noted specifically.
[0073] (2) Phosphorescence yield (a relative quantum yield, i.e., a
ratio of an objective sample's quantum yield (sample) to a standard
sample's quantum yield (st)) is determined according to the
following formula:
(sample)/ (st)=[Sem(sample)/Iabs(sample)]/[Sem(st)/Iabs(st)],
[0074] 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.
[0075] Phosphorescence yield values described herein are relative
values with respect to a phosphorescence yield =1 of Ir(ppy).sub.3
as a standard sample.
[0076] (3) A Method of Measurement of Phosphorescence Life is as
Follows.
[0077] A sample compound is dissolved in chloroform and spin-coated
onto a quartz substrate in a thickness of ca. 0.1 .mu.m and 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 characteristic of luminescence
intensity is measured.
[0078] When an initial luminescence intensity is denoted by
I.sub.0, a luminescence intensity after t(sec) is expressed
according to the following formula with reference to a luminescence
life z(sec):
I=I.sub.0.multidot.exp(-t/.tau.).
[0079] The luminescence material (metal coordination compound) of
the present invention exhibited high phosphorescence quantum yields
of 0.11 to 0.9 and short phosphorescence lives of 0.1 to 40
.mu.sec. A short phosphorescence life becomes a condition for
causing little energy deactivation and exhibiting an enhanced
luminescence efficiency. More specifically if the phosphorescence
life is long, the number of triplet state molecules maintained for
luminescence is increased, and the deactivation process is liable
to occur, thus resulting in a lower luminescence efficiency
particularly at the time of a high-current density. The material of
the present invention has a relatively short phosphorescence life
thus exhibiting a high phosphorescence quantum yield, and is
therefore suitable as a luminescence material for an EL device.
[0080] As a result of various studies of ours, it has been found
that an organic EL device using the metal coordination compound of
the formula (1) as a principal luminescence material causes
high-efficiency luminescence, retains high luminance for a long
period and shows little deterioration by current passage.
[0081] In the formula (1) representing the metal coordination
compound of the present invention, n may preferably 0 or 1, more
preferably 0. Further, the partial structure ML'n may preferably
comprise the benzofuran structure represented by the
above-mentioned formula (5).
[0082] In the present invention, by incorporating the benzofuran
structure of the formula (5) into the metal coordination compound
of the formula (1), it becomes possible to control an emission
wave-length (particularly to provide a long emission wavelength).
The presence of the benzofuran structure of the formula (5) is
effective in enhancing a solubility of the metal coordination
compound of the present invention in an organic solvent, thus
facilitating a purification thereof by recrystallization or column
chromatography. As a result, the metal coordination compound of the
present invention is suitable as a luminescence material for the
organic EL device.
[0083] Further, as shown in Examples appearing hereinafter, it has
been substantiated that the metal coordination compound of the
present invention exhibited an excellent stability in a continuous
current passage test. This may be attributable to incorporation of
the benzofuran structure of the formula (5) into the molecular
structure of the metal coordination compound of the formula (1)
according to the present invention. More specifically, a change in
intermolecular interaction due to the introduction of the
benzofuran structure of the formula (5) allows an intermolecular
interact-ion of the metal coordination compound with, e.g., a host
material to suppress formation of exciton associates-causing
thermal deactivation, thus reducing a quenching process thereby to
improve phosphorescence yield and device characteristics.
[0084] In the case where CyN1 (or CyN2) is benzofranyl group and
CyC1 (or CyC2) is pyridyl or pyrimidinyl group in the metal
coordination compound of formula (1) of the present invention,
pyridyl or pyrimidinyl group (CyC1 or CyC2) may preferably have a
substituent other than methyl group, methoxy group, butyl group and
fluorine atom when benzofuran group (CyN1 or CyN2) is not
substituted. In another preferred embodiment in the above case,
benzofuran group (CyN1 or CyN2) has a substituent, particularly
trifluoromethyl group or an aromatic group. In still another
preferred embodiment in the above case, the metal coordination
compound has a substituent such as trifluoromethyl group, an
aromatic group or a cyclized group (e.g.,
--(CH.dbd.CH).sub.2--).
[0085] The luminescence device according to the present invention
may preferably be an electroluminescence device of the type wherein
a layer of the metal coordination compound of the formula (1) is
disposed between opposing two electrodes and a voltage is applied
between the electrodes to cause luminescence, particularly
phosphorescence, as shown in FIGS. 1A, 1B and 1C.
[0086] The luminescence device according to the present invention
may be applicable to devices required to allow energy saving and
high luminance, such as those for display apparatus and
illumination apparatus, a light source for printers, and backlight
(unit) for a liquid crystal display apparatus. Specifically, in the
case of using the luminescence device of the present invention in
the display apparatus, it is possible to provide a flat panel
display apparatus capable of exhibiting an excellent energy saving
performance, a high visibility and a good lightweight property.
[0087] For the application to a display, a drive system using a
thin-film transistor (TFT) drive circuit according to an active
matrix-scheme may be used. Hereinbelow, an embodiment of using a
device of the present invention in combination with an active
matrix substrate is briefly described with reference to FIG. 2.
[0088] FIG. 2 illustrates an embodiment of panel structure
comprising an EL device and drive means. The panel is provided with
a scanning signal driver, a data signal driver and a current supply
source which are connected to gate selection lines, data signal
lines and current supply lines, respectively. At each intersection
of the gate selection lines and the data signal lines, a display
pixel electrode is disposed. The scanning signal drive sequentially
selects the gate selection lines G1, G2, G3 . . . Gn, and in
synchronism herewith, picture signals are supplied from the data
signal driver to display a picture (image).
[0089] By driving a display panel including a luminescence layer
comprising a luminescence material of the present invention, it
becomes possible to provide a display which exhibits a good picture
quality and is stable even for a long period display.
[0090] Some synthetic paths for providing a metal coordination
compound represented by the above-mentioned formula (1) are
illustrated below with reference to an iridium coordination
compound (m+n=3) for example: 8
[0091] Other metal coordination compound (M=Pt, Rh and Pd) can also
be synthesized in a similar manner.
[0092] Some specific structural examples of metal coordination
compounds used in the present invention are shown in Tables 1 to
Tables 17 appearing hereinafter, which are however only
representative examples and are not exhaustive. Pi to Bf6 for CyN1,
CyN2, CyC1 and CyC2 shown in Tables 1 to 17 represent partial
structures shown below. 910111213
[0093] Further, aromatic group Ph2 to Bf8 as substituents for CyN1,
CyN2, CyC1 and CyC2 shown in Tables 1 to 17 represent partial
structures shown below. 1415
1 TABLE 1 CyN1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyC1 No M m n CyN1 CyC1
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 1 Ir 3 0 Pi Bf1 H H
-- -- -- -- H H H H -- -- -- -- 2 Ir 3 0 Pi Bf1 CF.sub.3 H -- -- --
-- H H H H -- -- -- -- 3 Ir 3 0 Pi Bf1 CF.sub.3 CF.sub.3 -- -- --
-- H H H H -- -- -- -- 4 Ir 3 0 Pi Bf1 H CF.sub.3 -- -- -- -- H H H
H -- -- -- -- 5 Ir 3 0 Pi Bf1 H NO.sub.2 -- -- -- -- H H H H -- --
-- -- 6 Ir 3 0 Pi Bf1 H Cl -- -- -- -- H H H H -- -- -- -- 7 Ir 3 0
Pi Bf1 H F F -- -- -- -- H H H H -- -- -- -- 8 Ir 3 0 Pi Bf1 H CN
-- -- -- -- H H H H -- -- -- -- 9 Ir 3 0 Pi Bf1 H OCH.sub.3 -- --
-- -- H H H H -- -- -- -- 10 Ir 3 0 Pi Bf1 H Ph2 H H H H H H H H --
-- -- -- 11 Ir 3 0 Pi Bf1 H Ph2 CF.sub.3 H H H H H H H -- -- -- --
12 Ir 3 0 Pi Bf1 H Ph2 H H F F H H H H -- -- -- -- 13 Ir 3 0 Pi Bf1
Ph2 H H H H H H H H H -- -- -- -- 14 Ir 3 0 Pi Bf1 H Np4 H -- -- --
H H H H -- -- -- -- 15 Ir 3 0 Pi Bf1 Tn7 H H H -- -- H H H H -- --
-- -- 16 Ir 3 0 Pi Bf1 H C.sub.4H.sub.9 -- -- -- -- H H H H -- --
-- -- 17 Ir 3 0 Pi Bf1 H H -- -- -- -- H H OCH.sub.3 H -- -- -- --
18 Ir 3 0 Pi Bf1 H H -- -- -- -- H H Cl H -- -- -- -- 19 Ir 3 0 Pi
Bf1 H H -- -- -- -- H H F H -- -- -- -- 20 Ir 3 0 Pi Bf1 H H -- --
-- -- H H C.sub.8H.sub.17 H -- -- -- -- 21 Ir 3 0 Pi Bf1 H H -- --
-- -- H H NO.sub.2 H -- -- -- -- 22 Ir 3 0 Pi Bf1 H H -- -- -- -- H
H Ph2 H H H H H 23 Ir 3 0 Pi Bf1 H H -- -- -- -- H H Ph2 H H
Si(C.sub.3H.sub.7).sub.3 H H 24 Ir 3 0 Pi Bf1 Ph2 H H H H H H H Ph2
H H H H H 25 Ir 3 0 Pi Bf1 H H -- -- -- -- H H Br H -- -- -- -- 26
Ir 3 0 Pi Bf1 H H -- -- -- -- H H Bf7 H H H H H 27 Ir 3 0 Pi Bf1 H
H -- -- -- -- H OC.sub.4H.sub.9 H H -- -- -- -- 28 Ir 3 0 Pi Bf1 H
Ph2 H OCH.sub.2C.sub.5F.sub.11 H H H H H H -- -- -- -- 29 Ir 3 0 Pi
Bf1 H H -- -- -- -- H Br H H -- -- -- -- 30 Ir 3 0 Pi Bf1 H H -- --
-- -- H Si(C.sub.8H1.sub.7).sub.3 H H -- -- -- -- 31 Ir 3 0 Pi Bf2
H H -- -- -- -- H H H H -- -- -- --
[0094]
2 TABLE 2 CyN1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyC1 No M m n CyN1 CyC1
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 32 Ir 3 0 Pi Bf2
CF.sub.3 H -- -- -- -- H H H H -- -- -- -- 33 Ir 3 0 Pi Bf2
CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- -- -- -- 34 Ir 3 0 Pi Bf2
H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 35 Ir 3 0 Pi Bf2 Ph2 H H
H H H H H H H -- -- -- -- 36 Ir 3 0 Pi Bf2 H Np4 H -- -- -- H H H H
-- -- -- -- 37 Ir 3 0 Pi Bf2 Tn7 H H H -- -- H H H H -- -- -- -- 38
Ir 3 0 Pi Bf2 H C.sub.4H.sub.9 -- -- -- -- H H H H -- -- -- -- 39
Ir 3 0 Pi Bf2 H H -- -- -- -- H H OCH.sub.3 H -- -- -- -- 40 Ir 3 0
Pi Bf2 H H -- -- -- -- H H Ph2 H H Si(C.sub.3H.sub.7).sub.3 H H 41
Ir 3 0 Pi Bf2 Ph2 H H H H H H H Ph2 H H H H H 42 Ir 3 0 Pi Bf2 H
Np3 H H -- -- H H H H -- -- -- -- 43 Ir 3 0 Pi Bf2 H Np4 H -- -- --
H H H H -- -- -- -- 44 Ir 3 0 Pi Bf2 H Pe2 H -- -- -- H H H H -- --
-- -- 45 Ir 3 0 Pi Bf2 H Qn2 H H -- -- H H H H -- -- -- -- 46 Ir 3
0 Pi Bf2 H An H -- -- -- H H H H -- -- -- -- 47 Ir 3 0 Pi Bf2 H Bf7
H H H H H H H H -- -- -- -- 48 Ir 3 0 Pi Bf2 Tn5 H H H -- -- H H H
H -- -- -- -- 49 Ir 3 0 Pi Bf2 H Bf8 H H H H H H H H -- -- -- -- 50
Ir 3 0 Pi Bf2 H Tn6 H H -- -- H H H H -- -- -- -- 51 Ir 3 0 Pi Bf3
H H -- -- -- -- Ph2 H H H H OCH.sub.3 H H 52 Ir 3 0 Pi Bf3 H
CF.sub.3 -- -- -- -- Ph2 H H H H C.sub.6H.sub.13 H H 53 Ir 3 0 Pi
Bf3 H CF.sub.3 -- -- -- -- Np3 H H H H H -- -- 54 Ir 3 0 Pi Bf3 H H
-- -- -- -- H H H H -- -- -- -- 55 Ir 3 0 Pi Bf3 CF.sub.3 H -- --
-- -- C.sub.2H.sub.5 H H H -- -- -- -- 56 Ir 3 0 Pi Bf3 CF.sub.3
CF.sub.3 -- -- -- -- C.sub.10H.sub.21 H H H -- -- -- -- 57 Ir 3 0
Pi Bf3 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 58 Ir 3 0 Pi Bf3
H H -- -- -- -- Tn5 H H H H H -- -- 59 Ir 3 0 Pi Bf3 H H -- -- --
-- Np3 H H H H H -- -- 60 Ir 3 0 Pi Bf3 H H -- -- -- -- Np4 H H H H
-- -- -- 61 Ir 3 0 Pi Bf4 H CF.sub.3 -- -- -- -- Ph2 H H H H
C.sub.5H.sub.13 H H
[0095]
3 TABLE 3 CyN1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyC1 No M m n CyN1 CyC1
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 62 Ir 3 0 Pi Bf4 H H
-- -- -- -- C.sub.8H.sub.17 H H H -- -- -- -- 63 Ir 3 0 Pi Bf4 H H
-- -- -- -- Ph2 H H H H H H H 64 Ir 3 0 Pi Bf4 Np4 H H -- -- -- Ph2
H H H H H H H 65 Ir 3 0 Pi Bf4 FL4 H H H H -- Ph2 H H H H H H H 66
Ir 3 0 Pi Bf4 CF.sub.3 CF.sub.3 -- -- -- -- C.sub.15H.sub.31 H H H
-- -- -- -- 67 Ir 3 0 Pi Bf4 H H -- -- -- -- DBT2 H H H H H H -- 68
Ir 3 0 Pi Bf4 H Bf7 H H H H Ph2 H H H H H H H 69 Ir 3 0 Pi Bf4 H
Bf8 H H H H Ph2 H H H H H H H 70 Ir 3 0 Pi Bf4 H Pi3 H H -- -- Ph2
H H H H H H H 71 Ir 3 0 Pi Bf5 H CF.sub.3 -- -- -- -- Ph2 H H H H
C.sub.6H.sub.13 H H 72 Ir 3 0 Pi Bf5 H H -- -- -- -- C.sub.3H.sub.7
H H H -- -- -- -- 73 Ir 3 0 Pi Bf5 CF.sub.3 H -- -- -- --
C.sub.20H.sub.41 H H H -- -- -- -- 74 Ir 3 0 Pi Ph1 H Bf7 H H H H H
H -- -- -- -- -- -- 75 Ir 3 0 Pi Ph1 H Bf7 H H H H H OCH.sub.3 --
-- -- -- -- -- 76 Ir 3 0 Pi Tn1 H Bf7 H H H H H H -- -- -- -- -- --
77 Ir 3 0 Pi Np2 H Bf7 H H H H H H -- -- -- -- -- -- 78 Ir 3 0 Pi
Cn1 H Bf7 H H H H H H -- -- -- -- -- -- 79 Ir 3 0 Pi DBT1 H Bf7 H H
H H H H -- -- -- -- -- -- 80 Ir 3 0 Pi Ph1 H Bf8 H H H H H H -- --
-- -- -- -- 81 Ir 3 0 Pi Ph1 H Bf8 H H H H H H -- -- -- -- -- -- 82
Ir 3 0 Pi Tn2 H Bf8 H H H H H H -- -- -- -- -- -- 83 Ir 3 0 Pi Np2
H Bf8 H H F H H H -- -- -- -- -- -- 84 Ir 3 0 Pi Cn1 H Bf8 H H H H
H H -- -- -- -- -- -- 85 Ir 3 0 Pi Cz H Bf8 H H H H CH3 H -- -- --
-- -- -- 86 Ir 3 0 Pr Bf1 H H -- -- -- -- H H H H -- -- -- -- 87 Ir
3 0 Py1 Bf1 H -- -- -- -- -- H H H H -- -- -- -- 88 Ir 3 0 Py2 Bf1
-- H -- -- -- -- H H H H -- -- -- -- 89 Ir 3 0 Pr Bf2 H H -- -- --
-- H H H H -- -- -- -- 90 Ir 3 0 Py1 Bf2 H -- -- -- -- -- H H H H
-- -- -- -- 91 Ir 3 0 Pi Bf1 H H -- -- -- -- --(CH.dbd.CH)2-- H H
-- -- -- -- 92 Ir 3 0 Pi Bf1 H H -- -- -- -- H --(CH.dbd.CH)2-- H
-- -- -- --
[0096]
4 TABLE 4 CyN1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyC1 No M m n CyN1 CyC1
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 93 Ir 3 0 Pi Bf1 H H
-- -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- 94 Ir 3 0 Pi Bf1 H
CF.sub.3 -- -- -- -- --(CH.dbd.CH)2-- H H -- -- -- -- 95 Ir 3 0 Pi
Bf1 H CF.sub.3 -- -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- 96 Ir 3
0 Pi Bf1 H CF.sub.3 -- -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- 97
Ir 3 0 Pi Bf1 H Np4 H -- -- -- --(CH.dbd.CH)2-- H H -- -- -- -- 98
Ir 3 0 Pi Bf1 H Ph2 H OCH.dbd.CHC.sub.7H.sub.15 H H
--(CH.dbd.CH)2-- H H -- -- -- -- 99 Ir 3 0 Pi Bf1 H Ph2 H
OC.ident.CC.sub.8H.sub.17 H H H --(CH.dbd.CH)2-- H -- -- -- -- 100
Ir 3 0 Pi Bf1 Ph2 H H H H H H H --(CH.dbd.CH)2-- -- -- -- -- 101 Ir
3 0 Pi Bf2 H H -- -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- 102 Ir
3 0 Pi Bf2 H H -- -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- 103 Ir
3 0 Pi Bf2 H H -- -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- 104 Ir
3 0 Pi Bf2 H Np4 H -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- 105 Ir
3 0 Pi Bf2 H Ph2 H H F F H H --(CH.dbd.CH)2-- -- -- -- -- 106 Ir 3
0 Pi Bf1 H Np3 H H -- -- --(CH.dbd.CH)2-- H H -- -- -- -- 107 Ir 3
0 Pi Bf1 H An H -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- 108 Ir 3
0 Pi Bf1 H Pe2 H -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- 109 Ir 3
0 Pi Bf1 H Cl -- -- -- -- --(CH.dbd.CH)2-- H H -- -- -- -- 110 Ir 3
0 Pi Bf1 H Tn8 H H -- -- H --(CH.dbd.CH)2-- H -- -- -- -- 111 Ir 3
0 Pi Bf1 H Pi3 H H -- -- H H --(CH.dbd.CH)2-- -- -- -- -- 112 Ir 3
0 Pi Bf1 H Qn2 H H -- -- --(CH.dbd.CH)2-- H H -- -- -- -- 113 Ir 3
0 Pi Bf1 H Ph2 H OCOC.sub.7H.sub.15 H H --(CH.dbd.CH)2-- H H -- --
-- -- 114 Ir 3 0 Pi Bf1 H Ph2 H CN H H H --(CH.dbd.CH)2-- H -- --
-- -- 115 Ir 3 0 Pi Bf2 H Tn5 H H -- -- H --(CH.dbd.CH)2-- H -- --
-- -- 116 Ir 3 0 Pi Bf2 H Tn6 H H -- -- H H --(CH.dbd.CH)2-- -- --
-- -- 117 Ir 3 0 Pi Bf2 H Tn7 H H -- -- H --(CH.dbd.CH)2-- H -- --
-- -- 118 Ir 3 0 Pi Bf2 H Pi2 H H -- -- H H --(CH.dbd.CH)2-- -- --
-- -- 119 Ir 3 0 Pi Bf2 H Ph2 NO.sub.2 H H H H H --(CH.dbd.CH)2--
-- -- -- -- 120 Ir 3 0 Pi Bf2 H DBF3 H H H -- H H --(CH.dbd.CH)2--
-- -- -- -- 121 Rh 3 0 Pi Bf1 H H -- -- -- -- H H H H -- -- -- --
122 Rh 3 0 Pi Bf1 CF.sub.3 H -- -- -- -- H H H H -- -- -- --
[0097]
5 TABLE 5 CyN1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyC1 No M m n CyN1 CyC1
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 123 Rh 3 0 Pi Bf1
CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- -- -- -- 124 Rh 3 0 Pi Bf1
H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 125 Rh 3 0 Pi Bf1 H
NO.sub.2 -- -- -- -- H H H H -- -- -- -- 126 Rh 3 0 Pi Bf1 H Cl --
-- -- -- H H H H -- -- -- -- 127 Rh 3 0 Pi Bf1 H F F -- -- -- -- H
H H H -- -- -- -- 128 Rh 3 0 Pi Bf1 H CN -- -- -- -- H H H H -- --
-- -- 129 Rh 3 0 Pi Bf1 H OCH.sub.3 -- -- -- -- H H H H -- -- -- --
130 Rh 3 0 Pi Bf1 H Ph2 H H H H H H H H -- -- -- -- 131 Rh 3 0 Pi
Bf2 H H -- -- -- -- H H H H -- -- -- -- 132 Rh 3 0 Pi Bf2 CF.sub.3
H -- -- -- -- H H H H -- -- -- -- 133 Rh 3 0 Pi Bf2 CF.sub.3
CF.sub.3 -- -- -- -- H H H H -- -- -- -- 134 Rh 3 0 Pi Bf2 H
CF.sub.3 -- -- -- -- H H H H -- -- -- -- 135 Rh 3 0 Pi Bf2 Ph2 H H
H H H H H H H -- -- -- -- 136 Rh 3 0 Pi Bf2 H Np4 H -- -- -- H H H
H -- -- -- -- 137 Rh 3 0 Pi Bf2 Tn7 H H H -- -- H H H H -- -- -- --
138 Rh 3 0 Pi Bf2 H C.sub.4H.sub.9 -- -- -- -- H H H H -- -- -- --
139 Rh 3 0 Pi Bf2 H H -- -- -- -- H H OCH.sub.3 H -- -- -- -- 140
Rh 3 0 Pi Bf2 H H -- -- -- -- H H Ph2 H H Si(C.sub.3H.sub.7).sub.3
H H 141 Pt 2 0 Pi Bf1 H H -- -- -- -- --(CH.dbd.CH)2-- H H -- -- --
-- 142 Pt 2 0 Pi Bf1 H H -- -- -- -- H --(CH.dbd.CH)2-- H -- -- --
-- 143 Pt 2 0 Pi Bf1 H H -- -- -- -- H H --(CH.dbd.CH)2-- -- -- --
-- 144 Pt 2 0 Pi Bf2 H Tn5 H H -- -- H --(CH.dbd.CH)2-- H -- -- --
-- 145 Pt 2 0 Pi Bf2 H Tn6 H H -- -- H H --(CH.dbd.CH)2-- -- -- --
-- 146 Pt 2 0 Pi Bf2 H Tn7 H H -- -- H --(CH.dbd.CH)2-- H -- -- --
-- 147 Pt 2 0 Pi Bf2 H Pi2 H H -- -- H H --(CH.dbd.CH)2-- -- -- --
-- 148 Pd 2 0 Pi Bf4 H Pi3 H H -- -- Ph2 H H H H H H H 149 Pd 2 0
Pi Bf5 H CF.sub.3 -- -- -- -- Ph2 H H H H C.sub.6H.sub.13 H H 150
Pd 2 0 Pi Bf1 H H -- -- -- -- H H Ph2 H H Si(C.sub.3H.sub.7).sub.3
H H
[0098]
6 TABLE 6 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 151 Ir 2 1 Pi Bf1 H H -- -- -- -- H H H H -- -- -- --
Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 152 Ir 2 1 Pi Bf1
CF.sub.3 H -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H
H -- -- -- -- -- -- 153 Ir 2 1 Pi Bf1 CF.sub.3 CF.sub.3 -- -- -- --
H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- --
154 Ir 2 1 Pi Bf1 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- Pi Ph1
H H -- -- -- -- H H -- -- -- -- -- -- 155 Ir 2 1 Pi Bf1 H CF.sub.3
-- -- -- -- H H H H -- -- -- -- Pi Np2 H H -- -- -- -- H H -- -- --
-- -- -- 156 Ir 2 1 Pi Bf1 H Ph2 H H H H H H H H -- -- -- -- Pi Ph1
H H -- -- -- -- H H -- -- -- -- -- -- 157 Ir 2 1 Pi Bf2 H H -- --
-- -- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- --
-- 158 Ir 2 1 Pi Bf2 CF.sub.3 H -- -- -- -- H H H H -- -- -- -- Pi
Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 159 Ir 2 1 Pi Bf2
CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H -- --
-- -- H H -- -- -- -- -- -- 160 Ir 2 1 Pi Bf2 H CF.sub.3 -- -- --
-- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- --
161 Ir 2 1 Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- Pi Ph1
CF.sub.3 H -- -- -- -- H H -- -- -- -- -- --
[0099]
7 TABLE 7 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 162 Ir 2 1 Pi Bf2 H Ph2 H H H H H H H H -- -- -- -- Pi
Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 163 Ir 2 1 Pi Bf2 Ph2 H H
H H H H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- --
-- 164 Ir 2 1 Pi Bf2 Tn7 H H H -- -- H H H H -- -- -- -- Pi Ph1 H H
-- -- -- -- H H -- -- -- -- -- -- 165 Ir 2 1 Pi Bf2 H
C.sub.4H.sub.9 -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H -- -- --
-- H H -- -- -- -- -- -- 166 Ir 2 1 Pi Bf2 H H -- -- -- -- H H Ph2
H H Si(C.sub.3H.sub.7).sub.3 H H Pi Ph1 H H -- -- -- -- H H -- --
-- -- -- -- 167 Ir 2 1 Pi Bf2 Ph2 H H H H H H H Ph2 H H H H H Pi
Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 168 Ir 2 1 Pi Bf2 H Qn2 H
H -- -- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- --
-- -- 169 Ir 2 1 Pi Bf2 H Bf7 H H H H H H H H -- -- -- -- Pi Ph1 H
H -- -- -- -- H H -- -- -- -- -- -- 170 Ir 2 1 Pi Bf2 H Bf8 H H H H
H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- --
171 Ir 2 1 Pi Bf3 H H -- -- -- -- Ph2 H H H H OCH.sub.3 H H Pi Ph1
H H -- -- -- -- H H -- -- -- -- -- -- 172 Ir 2 1 Pi Bf3 H CF.sub.3
-- -- -- -- Np3 H H H H H -- -- Pr Ph1 H H -- -- -- -- H H -- -- --
-- -- --
[0100]
8 TABLE 8 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 173 Ir 2 1 Pi Bf4 H CF.sub.3 -- -- -- -- Ph2 H H H H
C.sub.6H.sub.13 H H Py1 Ph1 H -- -- -- -- -- H H -- -- -- -- -- --
174 Ir 2 1 Pi Bf4 H Bf7 H H H H Ph2 H H H H H H H Py2 Ph1 -- H --
-- -- -- H H -- -- -- -- -- -- 175 Ir 2 1 Pi Ph1 H Bf7 H H H H H
OCH.sub.3 -- -- -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- --
-- -- 176 Ir 2 1 Pi Np2 H Bf7 H H H H H H -- -- -- -- -- -- Pi Ph1
H H -- -- -- -- H H -- -- -- -- -- -- 177 Ir 2 1 Pi Tn2 H Bf8 H H H
H H H -- -- -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- --
-- 178 Ir 2 1 Pi Cn1 H Bf8 H H H H H -- -- -- -- -- -- -- Pi Ph1 H
Np3 H H -- -- H H -- -- -- -- -- -- 179 Ir 2 1 Pi Bf1 H H -- -- --
-- --(CH.dbd.CH)2-- H H -- -- -- -- Pi Np2 H H -- -- -- -- H H --
-- -- -- -- -- 180 Ir 2 1 Pi Bf1 H H -- -- -- -- H --(CH.dbd.CH)2--
H -- -- -- -- Pi Ph1 H CF.sub.3 -- -- -- -- H H -- -- -- -- -- --
181 Ir 2 1 Pi Bf1 H H -- -- -- -- H H --(CH.dbd.CH)2-- -- -- -- --
Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 182 Ir 2 1 Pi Bf1
H CF.sub.3 -- -- -- -- --(CH.dbd.CH)2-- H H -- -- -- -- Pi Ph1 H
CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 183 Ir 2 1 Pi Bf1 H
CF.sub.3 -- -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H H --
-- -- -- H H -- -- -- -- -- --
[0101]
9 TABLE 9 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 184 Ir 2 1 Pi Bf1 H CF.sub.3 -- -- -- -- H H
--(CH.dbd.CH)2-- -- -- -- -- Pi Bf2 H CF.sub.3 -- -- -- -- H H H H
-- -- -- -- 185 Ir 2 1 Pi Bf1 H Np4 H -- -- -- --(CH.dbd.CH)2-- H H
-- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 186 Ir 2 1
Pi Bf1 H Ph2 H OCH.dbd.CHC.sub.7H.sub.15 H H --(CH.dbd.CH)2-- H H
-- -- -- -- Pi Ph1 H CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 187
Ir 2 1 Pi Bf1 H Ph2 H OC.ident.CC.sub.8H.sub.17 H H H
--(CH.dbd.CH)2-- H -- -- -- -- Pi Np2 H H -- -- -- -- H H -- -- --
-- -- -- 188 Ir 2 1 Pi Bf1 Ph2 H H H H H H H --(CH.dbd.CH)2-- -- --
-- -- Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 189 Ir 2 1
Pi Bf2 H H -- -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H H
-- -- -- -- H H -- -- -- -- -- -- 190 Ir 2 1 Pi Bf2 H H -- -- -- --
H H --(CH.dbd.CH)2-- -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- --
-- -- -- -- 191 Ir 2 1 Pi Bf2 H H -- -- -- -- H --(CH.dbd.CH)2-- H
-- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 192 Ir 2 1
Pi Bf2 H Np4 H -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- Pi Ph1 H
CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 193 Ir 2 1 Pi Bf2 H Ph2
H H F F H H --(CH.dbd.CH)2-- -- -- -- -- Pi Ph1 H H -- -- -- -- H H
-- -- -- -- -- -- 194 Ir 2 1 Pi Bf1 H Np3 H H -- --
--(CH.dbd.CH)2-- H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- --
-- -- -- --
[0102]
10 TABLE 10 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 195 Ir 2 1 Pi Bf1 H An H -- -- -- H --(CH.dbd.CH)2-- H
-- -- -- -- Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 196
Ir 2 1 Pi Bf1 H Pe2 H -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- Pi
Ph1 H CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 197 Ir 2 1 Pi Bf1
H Cl -- -- -- -- --(CH.dbd.CH)2-- H H -- -- -- -- Pi Ph1 H H -- --
-- -- H H -- -- -- -- -- -- 198 Ir 2 1 Pi Bf1 H Tn8 H H -- -- H
--(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- --
-- -- -- 199 Ir 2 1 Pi Bf1 H Pi3 H H -- -- H H --(CH.dbd.CH)2-- --
-- -- -- Pi DBT1 H H -- -- -- -- H H -- -- -- -- -- -- 200 Ir 2 1
Pi Bf1 H Qn2 H H -- -- --(CH.dbd.CH)2-- H H -- -- -- -- Pi Ph1 H H
-- -- -- -- H H -- -- -- -- -- -- 201 Ir 2 1 Pi Bf1 H Ph2 H
OCOC.sub.7H.sub.15 H H --(CH.dbd.CH)2-- H H -- -- -- -- Pi Bf2 H
CF.sub.3 -- -- -- -- H H H H -- -- -- -- 202 Ir 2 1 Pi Bf1 H Ph2 H
CN H H H --(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H CF.sub.3 -- -- --
-- H H -- -- -- -- -- -- 203 Rh 2 1 Pi Bf2 H Tn6 H H -- -- H H
--(CH.dbd.CH)2-- -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- --
-- -- 204 Rh 2 1 Pi Bf2 H Ph2 NO.sub.2 H H H H H --(CH.dbd.CH)2--
-- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 205 Rh 2 1
Pi Bf2 H DBF3 H H H -- H H --(CH.dbd.CH)2-- -- -- -- -- Pi Bf2 H
CF.sub.3 -- -- -- -- H H H H -- -- -- --
[0103]
11 TABLE 11 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 206 Rh 2 1 Pi Bf2 H H -- -- -- -- H H Ph2 H H
Si(C.sub.3H.sub.7).sub.3 H H Pi Ph1 H H -- -- -- -- H H -- -- -- --
-- -- 207 Rh 2 1 Pi Bf2 Ph2 H H H H H H H Ph2 H H H H H Pi Ph1 H H
-- -- -- -- H H -- -- -- -- -- -- 208 Rh 2 1 Pi Bf2 H Pe2 H -- --
-- H H H H -- -- -- -- Pi Ph1 H GF.sub.3 -- -- -- -- H H -- -- --
-- -- -- 209 Rh 2 1 Pi Bf2 H An H -- -- -- H H H H -- -- -- -- Pi
Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 210 Rh 2 1 Pi Bf2 H Bf8 H
H H H H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- --
-- 211 Ir 1 2 Pi Bf1 H H -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H
-- -- -- -- H H -- -- -- -- -- -- 212 Ir 1 2 Pi Bf1 CF.sub.3 H --
-- -- -- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- --
-- -- 213 Ir 1 2 Pi Bf1 CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- --
-- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 214 Ir 1 2 Pi
Bf1 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H -- -- --
-- H H -- -- -- -- -- -- 215 Ir 1 2 Pi Bf1 H CF.sub.3 -- -- -- -- H
H H H -- -- -- -- Pi Np2 H H -- -- -- -- H H -- -- -- -- -- -- 216
Ir 1 2 Pi Bf2 H H -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H -- --
-- -- H H -- -- -- -- -- --
[0104]
12 TABLE 12 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 217 Ir 1 2 Pi Bf2 CF.sub.3 H -- -- -- -- H H H H -- --
-- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 218 Ir 1 2 Pi
Bf2 CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- -- -- -- Pi Ph1 H H --
-- -- -- H H -- -- -- -- -- -- 219 Ir 1 2 Pi Bf2 H CF.sub.3 -- --
-- -- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- --
-- 220 Ir 1 2 Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- Pi
Ph1 CF.sub.3 H -- -- -- -- H H -- -- -- -- -- -- 221 Ir 1 2 Pi Bf2
H Ph2 H H H H H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- --
-- -- -- -- 222 Ir 1 2 Pi Bf1 H H -- -- -- -- --(CH.dbd.CH)2-- H H
-- -- -- -- Pi Np2 H H -- -- -- -- H H -- -- -- -- -- -- 223 Ir 1 2
Pi Bf1 H H -- -- -- -- H --(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H
CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 224 Ir 1 2 Pi Bf1 H
CF.sub.3 -- -- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- Pi Bf2 H
CF.sub.3 -- -- -- -- H H H H -- -- -- -- 225 Ir 1 2 Pi Bf1 H Np4 H
-- -- -- --(CH.dbd.CH)2-- H H -- -- -- -- Pi Ph1 H H -- -- -- -- H
H -- -- -- -- -- -- 226 Ir 1 2 Pi Bf1 H Ph2 H
OCH.dbd.CHC.sub.7H.sub.15 H H --(CH.dbd.CH)2-- H H -- -- -- -- Pi
Ph1 H CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 227 Ir 1 2 Pi Bf1
H Ph2 H OC.ident.CC.sub.8H.sub.17 H H H --(CH.dbd.CH)2-- H -- -- --
-- Pi Np2 H H -- -- -- -- H H -- -- -- -- -- --
[0105]
13 TABLE 13 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 228 Ir 1 2 Pi Bf1 H Qn2 H H -- -- --(CH.dbd.CH)2-- H H
-- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 229 Ir 1 2
Pi Bf1 H Ph2 H OCOC.sub.7H.sub.15 H H --(CH.dbd.CH)2-- H H -- -- --
-- Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 230 Ir 1 2 Pi
Bf1 H Ph2 H CN H H H --(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H
CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 231 Ir 1 2 Pi Bf2 H Tn6
H H -- -- H H --(CH.dbd.CH)2-- -- -- -- -- Pi Ph1 H H -- -- -- -- H
H -- -- -- -- -- -- 232 Ir 1 2 Pi Bf2 H Ph2 NO.sub.2 H H H H H
--(CH.dbd.CH)2-- -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- --
-- -- 233 Ir 1 2 Pi Bf2 H DBF3 H H H -- H H --(CH.dbd.CH)2-- -- --
-- -- Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- 234 Ir 1 2
Pi Bf2 Ph2 H H H H H H H Ph2 H H H H H Pi Ph1 H H -- -- -- -- H H
-- -- -- -- -- --
[0106]
14 TABLE 14 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 CyN1-R2 CyN2
CyC1-R3 CyC1-R4 CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 CyN1 CyC1 CyN2-R1
CyN2-R2 CyC2 No M m n CyN2 CyC2 CyC2-R3 CyC2-R4 CyC2-R'3 CyC2-R'4
R5 R6 R7 R8 235 Rh 1 2 Pi Bf2 H Pe2 H -- -- -- H H H H -- -- -- --
Pi Ph1 H CF.sub.3 -- -- -- -- H H -- -- -- -- -- -- 236 Rh 1 2 Pi
Bf2 H An H -- -- -- H H H H -- -- -- -- Pi Ph1 H H -- -- -- -- H H
-- -- -- -- -- -- 237 Rh 1 2 Pi Bf2 H Bf8 H H H H H H H H -- -- --
-- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- -- 238 Rh 1 2 Pi Bf1
Ph2 H H H H H H H --(CH.dbd.CH)2-- -- -- -- -- Pi Bf2 H CF.sub.3 --
-- -- -- H H H H -- -- -- -- 239 Pt 1 1 Pi Bf2 H H -- -- -- -- H
--(CH.dbd.CH)2-- H -- -- -- -- Pi Ph1 H H -- -- -- -- H H -- -- --
-- -- -- 240 Pd 1 1 Pi Bf2 H H -- -- -- -- H H --(CH.dbd.CH)2-- --
-- -- -- Pi Ph1 H H -- -- -- -- H H -- -- -- -- -- --
[0107]
15 TABLE 15 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 E CyN1 CyC1
CyC1-R3 CyC1-R4 R5 R6 R7 R8 E R" R"' CyN1-R2 G No M m n G R" R"'
CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 241 Ir 2 1 Pi Bf1 H H -- -- -- -- H H
H H -- -- -- -- CH.sub.3 -- -- -- -- -- -- CH.sub.3 -- -- -- -- --
-- 242 Ir 2 1 Pi Bf1 CF.sub.3 H -- -- -- -- H H H H -- -- -- --
CF.sub.3 -- -- -- -- -- -- CF.sub.3 -- -- -- -- -- -- 243 Ir 2 1 Pi
Bf1 CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- -- -- -- CH.sub.3 --
-- -- -- -- -- CH.sub.3 -- -- -- -- -- -- 244 Ir 2 1 Pi Bf1 H
CF.sub.3 -- -- -- -- H H H H -- -- -- -- Ph2 -- -- H H H H Ph2 --
-- H H H H 245 Ir 2 1 Pi Bf1 H Ph2 H H H H H H H H -- -- -- -- Ph2
-- -- H C.sub.3H.sub.7 H H Ph2 -- -- H C.sub.3H.sub.7 H H 246 Ir 2
1 Pi Bf2 H H -- -- -- -- H H H H -- -- -- -- CH.sub.3 -- -- -- --
-- -- FL5 CH.sub.3 CH.sub.3 H H H -- 247 Ir 2 1 Pi Bf2 CF.sub.3 H
-- -- -- -- H H H H -- -- -- -- Tn5 -- -- H H -- -- Tn5 -- -- H H
-- -- 248 Ir 2 1 Pi Bf2 CF.sub.3 CF.sub.3 -- -- -- -- H H H H -- --
-- -- Tn6 -- -- H H -- -- Tn6 -- -- H H -- -- 249 Ir 2 1 Pi Bf2 H
CF.sub.3 -- -- -- -- H H H H -- -- -- -- CH.sub.3 -- -- -- -- -- --
CH.sub.3 -- -- -- -- -- -- 250 Ir 2 1 Pi Bf2 H Ph2 H H H H H H H H
-- -- -- -- CF.sub.3 -- -- -- -- -- -- CF.sub.3 -- -- -- -- -- --
251 Ir 2 1 Pi Bf2 Ph2 H H H H H H H H H -- -- -- -- Np3 -- --
CH.sub.3O H -- -- Np3 -- -- CH.sub.3O H -- --
[0108]
16 TABLE 16 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 E CyN1 CyC1
CyC1-R3 CyC1-R4 R5 R6 R7 R8 E R" R"' CyN1-R2 G No M m n G R" R"'
CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 252 Ir 2 1 Pi Bf2 Tn7 H H H -- -- H H
H H -- -- -- -- Np4 -- -- F -- -- -- Np4 -- -- F -- -- -- 253 Ir 2
1 Pi Bf2 H C.sub.4H.sub.9 -- -- -- -- H H H H -- -- -- -- Tn7 -- --
CH.sub.3 H -- -- Tn7 -- -- CH.sub.3 H -- -- 254 Ir 2 1 Pi Bf2 H H
-- -- -- -- H H Ph2 H H Si(C.sub.3H.sub.7).sub.3 H H Tn8 -- -- H H
-- -- Tn8 -- -- H H -- -- 255 Ir 2 1 Pi Bf2 Ph2 H H H H H H H Ph2 H
H H H H Pe2 -- -- H -- -- -- Pe2 -- -- H -- -- -- 256 Ir 2 1 Pi Bf2
H Qn2 H H -- -- H H H H -- -- -- -- Pi2 -- -- H H -- -- Pi2 -- -- H
H -- -- 257 Ir 2 1 Pi Bf2 H Bf7 H H H H H H H H -- -- -- -- Pi3 --
-- CH.sub.3 CH.sub.3 H H Pi3 -- -- CH.sub.3 CH.sub.3 H H 258 Ir 2 1
Pi Bf2 H Bf8 H H H H H H H H -- -- -- -- FL4 -- -- H H H -- FL4 --
-- H H H -- 259 Ir 2 1 Pi Bf3 H H -- -- -- -- Ph2 H H H H OCH.sub.3
H H FL5 C2H5 C2H5 H H H -- FL5 (CH2)5Ph3 (CH2)5Ph3 H H H -- 260 Ir
2 1 Pi Bf4 H CF.sub.3 -- -- -- -- Ph2 H H H H C.sub.6H.sub.13 H H
DBF2 -- -- H H H -- DBF2 -- -- H H H -- 261 Ir 2 1 Pi Ph1 H Bf7 H H
H H H OCH.sub.3 -- -- -- -- -- -- DBT3 -- -- H H H -- DBT3 -- -- H
H H -- 262 Rh 2 1 Pi Bf1 H H -- -- -- -- --(CH.dbd.CH)2-- H H -- --
-- -- CH.sub.3 -- -- -- -- -- -- CH.sub.3 -- -- -- -- -- --
[0109]
17 TABLE 17 CyN1 R5 R6 R7 R8 CyC1 R5 R6 R7 R8 CyN1-R1 E CyN1 CyC1
CyC1-R3 CyC1-R4 R5 R6 R7 R8 E R" R"' CyN1-R2 G No M m n G R" R"'
CyC1-R'3 CyC1-R'4 R5 R6 R7 R8 263 Rh 2 1 Pi Bf1 H H -- -- -- -- H
--(CH.dbd.CH)2-- H -- -- -- -- CF.sub.3 -- -- -- -- -- -- CF.sub.3
-- -- -- -- -- -- 264 Rh 2 1 Pi Bf1 H H -- -- -- -- H H
--(CH.dbd.CH)2-- -- -- -- -- Qn2 -- -- H H -- -- Qn2 -- -- H H --
-- 265 Rh 2 1 Pi Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- Np3
-- -- H H -- -- Np3 -- -- H H -- -- 266 Pt 1 1 Pi Bf1 H CF.sub.3 --
-- -- -- H H --(CH.dbd.CH)2-- -- -- -- -- CH.sub.3 -- -- -- -- --
-- CH.sub.3 -- -- -- -- -- -- 267 Pt 1 1 Pi Bf1 H Np4 H -- -- --
--(CH.dbd.CH)2-- H H -- -- -- -- CF.sub.3 -- -- -- -- -- --
CF.sub.3 -- -- -- -- -- -- 268 Pd 1 1 Pi Bf1 H Ph2 H
OCH.dbd.CHC.sub.7H.sub.15 H H --(CH.dbd.CH)2-- H H -- -- -- --
CH.sub.3 -- -- -- -- -- -- CH.sub.3 -- -- -- -- -- -- 269 Pd 1 1 Pi
Bf2 H CF.sub.3 -- -- -- -- H H H H -- -- -- -- CF.sub.3 -- -- -- --
-- -- CF.sub.3 -- -- -- -- -- -- 270 Ir 1 2 Pi Bf1 H Ph2 H
OC.ident.CC.sub.8H.sub.17 H H H --(CH.dbd.CH)2-- H -- -- -- --
CH.sub.3 -- -- -- -- -- -- CH.sub.3 -- -- -- -- -- --
[0110] In the case where the metal coordination compound of the
formula (1) is used as a luminescent material, the metal
coordination compound used singly (as a single luminescent
material) or in combination with another luminescent material (host
compound).
[0111] In the latter case, the resultant luminescence material
(composition or mixture) may preferably contain the metal
coordination compound of the formula (1) in an amount of at most 50
wt. %, more preferably 0.1-20 wt. %. Above 50 wt. %, a resultant
luminescence strength is undesirably be lowered due to quenching
with an increasing concentration in some cases.
[0112] Hereinbelow, the present invention will be described more
specifically based on Examples.
EXAMPLE 1
Synthesis of Example Compound No. 34
[0113] 16
[0114] In a 100-ml-three-necked flask, 2.80 g (15.4 mM) of
2-chloro-5-trifluoromethylpyridine, 2.50 g (15.4 mM) of
2-benzofuranylboronic acid, 14 ml of toluene, 7 ml of ethanol and
14 ml of 2M-sodium carbonate aqueous solution were placed and
stirred at room temperature under nitrogen stream, and 0.55 g (0.48
mM) of tetrakis(triphenylphosphine)palladium (0) was added thereto.
Thereafter, reflux under stirring for 4 hours was performed under
nitrogen stream. After the reaction, the reaction mixture was
cooled on an ice bath and stirred at room temperature after
addition of ethyl acetate and saturated saline water. The organic
layer was washed with water and dried with anhydrous magnesium
sulfate, and the solvent was removed under reduced pressure to
obtain a residue. The residue was purified by alumina column
chromatography (eluent: toluene) and recrystallized from methanol
to obtain 0.72 g of 2-(5-trifluoromethylpyridine-2-yl)benzofuran
(Yield: 17.7%). 17
[0115] In a 100 ml-four-necked flask, 25 ml of glycerol was placed
and heated at 130-140.degree. C. under stirring and bubbling with
nitrogen for 2 hours. Then, the glycerol was cooled by standing
down to 100.degree. C., and 0.70 g (2.66 mM) of
2-(5-trifluoromethylpyridine-2-yl- )benzofuran and 0.23 g (0.47 mM)
of iridium (III) acetylacetonate were added, followed by 7 hours
and 10 minutes of heating at 192-230.degree. C. under stirring and
nitrogen stream. The reaction product was cooled to room
temperature and injected into 150 ml of 1N-hydrochloric acid to
form a precipitate, which was filtered out, washed with water, and
dissolved in acetone to remove the insoluble content. The acetone
was distilled off under reduced pressure to obtain a residue. The
residue was washed with methanol and purified by silica gel column
chromatography with toluene as the eluent to obtain 0.11 g
(yield=23.4%) of red powdery
tris[2-(benzofuran-2-yl)-5-trifluoromethyl-pyridine-C.sup.3,N]iridium
(III).
[0116] A toluene solution of the compound exhibited a
photoluminescence spectrum showing .lambda.max (maximum emission
wavelength)=622 nm and a quantum yield of 0.12.
EXAMPLES 2-10
[0117] Each of luminescence devices having a layer structure shown
in FIG. 1B were prepared in the following manner.
[0118] On a 1.1 mm-thick glass substrate (transparent substrate
15), a 100 nm-thick film (transparent electrode 14) of ITO (indium
tin oxide) was formed by sputtering, followed by patterning to form
a stripe electrode including 100 lines each having a width of 100
nm and a spacing with an adjacent line of 10 nm (i.e., electrode
pitch of 110 nm).
[0119] On the ITO-formed substrate, three organic layers and two
metal electrode layers shown below were successively formed by
vacuum (vapor) deposition using resistance heating in a vacuum
chamber (10.sup.-4 Pa).
[0120] Organic layer 1 (hole transport layer 13) (40 nm):
.alpha.-NPD
[0121] Organic layer 2 (luminescence layer 12) (30 nm):
co-deposited film of CBP:metal complex (metal coordination compound
shown in Table 18) (95:5 by weight)
[0122] Organic layer 3 (electron transport layer 16) (30 nm):
Alq3
[0123] Metal electrode layer 1 (metal electrode 11) (15 nm): Al--Li
alloy (Li=1.8 wt. %)
[0124] Metal electrode layer 2 (metal electrode 11) (100 nm):
Al
[0125] The above-deposited metal electrode layers 1 and 2 (Al--Li
layer and Al layer) had a stripe electrode pattern including 100
lines each having a width of 100 nm and a spacing of 10 nm
(electrode pitch=110 nm) and arranged so that the stripe electrode
pattern intersected with that of the ITO electrode at right angles
to form a matrix of pixels each having an effective electrode area
of 3 mm.sup.2 comprising 20 ITO lines-bundled together at a
lead-out portion and 15 Al (Al--Li) lines bundled together at a
lead-out portion.
[0126] Each of the thus-prepared luminescence devices was taken out
of the vacuum-chamber and was subjected to a continuous
energization (current passage) test in an atmosphere of dry
nitrogen gas stream so as to remove device deterioration factors,
such as oxygen and moisture (water content).
[0127] The continuous energization test was performed by
continuously applying a voltage at a constant current density of 70
mA/cm.sup.2 to the luminescence device having the ITO (transparent)
electrode (as an anode) and the Al (metal) electrode (as a
cathode), followed by measurement of emission luminance
(brightness) with time so as to determine a time (luminance
half-life) required for decreasing an initial luminance (80-250
cd/m.sup.2) to 1/2 thereof.
[0128] The results are shown in Table 18 appearing hereinafter.
COMPARATIVE EXAMPLE 1
[0129] A comparative luminescence device was prepared and evaluated
in the same manner as in Examples 2-10 except that the Ir complexes
(metal coordination compounds shown in Table 185) was changed to
Ir-phenylpyrimidine complex (Ir(ppy).sub.3) shown below. 18
[0130] The results are also also shown in Table 18 below.
18 TABLE 18 Ex. No. Compound No. Luminance half-life (Hr) Ex. 2 4
800 Ex. 3 10 900 Ex. 4 31 750 Ex. 5 34 900 Ex. 6 92 800 Ex. 7 115
650 Ex. 8 135 750 Ex. 9 156 850 Ex. 10 238 600 Comp. Ex. 1
Ir(ppy).sub.3 350
[0131] As is apparent from Table 18, compared with the conventional
luminescence device using Ir(ppy).sub.3, the luminescence devices
using the metal coordination compounds of formula (1) according to
the present invention provide longer luminance half-lives, thus
resulting in an EL device having a high durability (luminance
stability) based on a good stability of the metal coordination
compound of formula (1) of the present invention.
EXAMPLE 11
[0132] A color organic EL display apparatus shown in FIG. 2 was
prepared in the following manner.
[0133] An active matrix substrate had a planar structure basically
similar to a structure described in U.S. Pat. No. 6,114,715.
[0134] Specifically, on a 1.1 mm-thick glass substrate, top
gate-type TFTs of polycrystalline silicon were formed in an
ordinary manner and thereon, a flattening film was formed with
contact holes for electrical connection with a pixel electrode
(anode) at respective source regions, thus preparing an active
matrix substrate with a TFT circuit.
[0135] On the active matrix substrate, a 700 nm-thick pixel
electrode (anode) of ITO having a large work function was formed in
a prescribed pattern. On the ITO electrode, prescribed organic
layers and a 100 nm-thick Al electrode (cathode) were successively
formed by vacuum deposition with a hard mask, followed by
patterning to form a matrix of color pixels (128.times.128
pixels).
[0136] The respective organic layers corresponding to three color
pixels (red (R) green (G) and blue (B)) were consisting of the
following layers.
[0137] <R pixel region>
[0138] .alpha.-NPD (40 nm)/CBP: Ex. Comp. No. 34 (93:7 by weight)
(30 nm)/BCP (20 nm)/Alq 3 (40 nm)
[0139] <G pixel region>
[0140] .alpha.-NPD (50 nm)/Alq 3 (50 nm)
[0141] <B pixel region>
[0142] .alpha.-NPD (50 nm)/BCP (20 nm)/Alq 3 (50 nm)
[0143] When the thus-prepared color organic EL display apparatus
was driven, desired color image data can be displayed stably with
good image qualities.
EXAMPLE 12
Synthesis of Ex. Comp. No. 31
[0144] It is easy to synthesize the following compound in the same
manner as in Example 1 except for using 2-bromopyridine (made by
Tokyo Kasei Kogyo K.K.) instead of
2-chloro-5-trifluoromethylpyridine in Example 1.
[0145] Tris[2-(benzofuran-2-yl)pyridine-C.sup.3,N]iridium
(III).
EXAMPLE 13
Synthesis of Ex. Comp. No. 32
[0146] It is easy to synthesize the following compound in the same
manner as in Example 1 except for using
2-chloro-4-trifluoromethylpyridine (made by Florochem USA) instead
of 2-chloro-5-trifluoromethylpyridine in Example 1.
[0147]
Tris[2-(benzofuran-2-yl)-4-trifluoromethyl-pyridine-C.sup.3,N]iridi-
um (III).
EXAMPLE 14
Synthesis of Ex. Comp. No. 33
[0148] It is easy to synthesize the following compound in the same
manner as in Example 1 except for using
2-chloro-4,5-bis(trifluoro-methyl)pyridi- ne (made by Oakwood
Products Inc.) instead of 2-chloro-5-trifluoromethylpy- ridine in
Example 1.
[0149]
Tris[2-(benzofuran-2-yl)-4,5-bis(trifluoro-methyl)pyridine-C.sup.3,
N]iridium (III).
EXAMPLE 15
Synthesis of Ex. Comp. No. 35
[0150] It is easy to synthesize the following compound in the same
manner as in Example 16 except for using 4-phenyl-2-bromopyridine
(made by General Intermediates of Canada) instead of
2-chloro-5-trifluoromethylpyr- idine in Example 1.
[0151] Tris[2-(benzofuran-2-yl)-4-pyridine-C.sup.3,N]-iridium
(III).
EXAMPLE 16
Synthesis of Ex. Comp. No. 36
[0152] It is easy to synthesis the following compound in the same
manner as in Example 1 except that
2-(benzofuran-2-yl)-5-bromopyridine was synthesized from
2,5-dibromopyridine (made by Tokyo Kasei Kogyo K.K.) and
2-benzofuranboronic acid (made by Aldrich Co.) and is reacted with
1-naphthylboronic acid (made by Tokyo Kasei Kogyo) to obtain
2-(benzofuran-2-yl)-5-(naphthalene-1-yl)pyridine, which is used
instead of 2-(5-trifluoromethylpyridine-2-yl)benzofuran.
[0153]
Tris[2-(benzofuran-2-yl)-5-(naphthalene-1-yl)pyridine-C.sup.3,N]iri-
dium (III).
EXAMPLE 17
Synthesis of Ex. Comp. No. 42
[0154] It is easy to synthesize the following compound in the same
manner as in Example 16 except for using 2-naphthylboronic acid
(made by Tokyo Kasei Kogyo K.K.) instead of 1-naphthylboronic acid
in Example 16.
[0155]
Tris[2-(benzofuran-2-yl)-5-(naphthalene-2-yl)pyridine-C.sup.3,N]iri-
dium (III).
EXAMPLE 18
Synthesis of Ex. Comp. No. 47
[0156] It is easy to synthesize the following compound in the same
manner as in Example 1 except for reacting 2 equivalent amount of
2-benzofuran boronic acid (made by Aldrich Co.) with
2,5-dibromopyridine (made by Tokyo Kasei Kogyo K.K.) to synthesis
2,5-bis(benzofuran-2-yl)pyridine, which is used instead of
2-(5-trifluoromethylpyridine-2-yl)benzofuran, in Example 1.
[0157] Tris[2,5-bis(benzofuran-2-yl)pyridine-C.sup.3,N]iridium
(III).
EXAMPLE 19
Synthesis of Ex. Comp. No. 50
[0158] It is easy to synthesis the following compound in the same
manner as in Example 1 except that
2-(benzofuran-2-yl)-5-bromopyridine was synthesized from
2,5-dibromopyridine (made by Tokyo Kasei Kogyo K.K.) and
2-benzofuranboronic acid (made by Aldrich Co.) and is reacted with
3-thiopheneboronic acid (made by Aldrich Co.) to obtain
2-(benzofuran-2-yl)-5-(thiophene-3-yl)pyridine, which is used
instead of 2-(5-trifluoromethylpyridine-2-yl)benzofuran.
[0159] Tris[2-(benzofuran-2-yl)-5-(thiophene-3-yl)pyridine-C.sup.3,
N]iridium (III).
EXAMPLE 20
[0160] An organic EL device shown in FIG. 1C was prepared in the
following manner.
[0161] On a 100 nm-thick patterned ITO electrode (anode) formed on
a 1.1 mm-thick no-alkali glass substrate, a 40 nm-thick charge
transport layer of .alpha.-NPD was formed by vacuum deposition
(10.sup.-4 Pa) at a deposition rate of 0.1 nm/sec. On the charge
transport layer, a 40 nm-thick luminescence layer (co-deposited
film) of CBP: iridium complex of Ex. Comp. No. 34 prepared in
Example 1 (97:3 by weight) was formed by co-vacuum deposition at
deposition rates of 0.1 nm/sec (for CBP) and 0.08 nm/sec (for the
iridium complex) by controlling heating conditions of deposition
vessel. On the luminescence layer, a 10 nm-thick exciton diffusion
prevention layer of BCP (Bathocuproine) was formed by vacuum
deposition at a deposition rate of 0.1 nm/sec, and or the exciton
diffusion prevention layer, a 20 nm-thick electron transport layer
of Alq 3 was formed by vacuum deposition at a deposition rate of
0.1 nm/sec. Thereafter, or the electron transport layer, a 150
nm-thick aluminum electrode (cathode) was formed by vacuum
deposition at a deposition rate of 1 nm/sec.
[0162] The thus-prepared organic EL device exhibited an EL spectrum
showing .lambda.max=625 nm and luminescent efficiencies of 1.5 lm/W
at a luminance of 100 cd/m.sup.2.
EXAMPLE 21
Synthesis of Ex. Comp. No. 62
[0163] 19
[0164] In a 2 liter-three-necked flask, 145.8 g (718 mM) of
5-bromo-2-hydroxybenzyl alcohol, 246.5 g (718 mM) of triphenyl
phosphine.HBr, and 730 ml of acetonitrile were placed and refluxed
under stirring for 3 hours. The reaction liquid was cooled down to
room temperature to precipitate a crystal of
5-bromo-2-hydroxybenzyltriphenylp- hosphonium bromide (I), which
was recovered by filtration (Yield: 362.0 g (95.5%)).
[0165] In a 1 liter-three-necked flask, 50.0 g (94.7 mM) o the
phosphonium bromide (I), 31.1 g (104 mM) of 1-nonanoic acid
anhydride, 450 ml of toluene and 39.6 g (392 mM) of triethylamine
were placed and refluxed under stirring for 6 hours. The reaction
liquid was cooled down to room temperature to precipitate a
crystal, which was filtered out. The solvent of the filtrate was
distilled off under reduced pressure to obtain a residue. The
residue was purified by silica gel column chromatography (eluent:
hexane) to a colorless oily product of 2-octyl-5-bromobenzofuran
(II) (Yield: 25.1 g (85.8%)).
[0166] In a 500 ml-three-necked flask, 19.0 g (61.5 mM) of
2-octyl-5-bromobenzofuran (II) and 190 ml of anhydrous
tetrahydrofuran (THF) were placed. To the mixture, 45 ml (72.0 mM)
of 1.6 M-n-butyllithium solution in hexane was added dropwise under
argon stream at -70.degree. C. or below in 30 min., followed by
stirring at that temperature for 4 hours. To the resultant mixture,
a solution of 17.8 g (171 mM) of trimethylborate in 70 ml of
anhydrous THF was added dropwise at -70.degree. C. or below in 20
min., and stirred at that temperature for 2 hours. The system was
heated up to room temperature and stirred for 17 hours. To the
reaction mixture, 100 ml of 10%-hydrochloric acid was added
dropwise, followed by extraction with ether. The organic layer was
washed with water and dried with anhydrous sodium sulfate, followed
by distilling-off of the solvent under reduced pressure to obtain a
residue. The residue was purified by silica gel column
chromatography (eluent: hexane/ethyl acetate=4/1) to obtain a white
crystal of 2-octylbenzofuran-5-boronic acid (III) (Yield: 10.8 g
(64.1%)).
[0167] It is easy to synthesize the following compound in the same
manner as in Example 1 except for using 2-octylbenzofuran-5-boronic
acid (III) instead of 2-benzofuran boronic acid in Example 1.
[0168] Tris[2-(2-octylbenzofuran-5-yl)pyridine-C.sup.3,N]iridium
(III).
EXAMPLE 22
Synthesis of Ex. Comp. No. 61
[0169] It is easy to synthesis the following compound in the same
manner as in Example 1 except for using, instead of
2-(5-trifluoromethylpyridine- -2-yl)benzofuran,
2-phenyl-5-(5-trifluoromethylpyridine-2-yl)benzofuran synthesized
in the same manner as in Example 21 except that
2-phenyl-5-bromobenzofuran was synthesized from benzoic acid
chloride used instead of 1-nonanoic acid and
2-phenyl-5-(5-trifluoromethyl-pyridin- e-2-yl)benzofuran was
synthesized from 2-phenyl-5-bromobenzofuran.
[0170]
Tris[2-(2-phenylbenzofuran-5-yl)-5-trifluoro-methylpyridine-C.sup.3-
,N]iridium (III).
EXAMPLE 23
Synthesis of Ex. Comp. No. 72
[0171] 4-bromo-2-hydroxybenzyl alcohol (IV) is synthesized from
4-aminosalicylic acid (made by Aldrich Co.) in the following
reaction scheme, and 4-bromo-2-hydroxybenzyltriphenylphosphon
bromide (V) is synthesized in the same manner as in Example 21.
20
[0172] It is easy to synthesize the following compound in the same
manner as in Example 21 except for using 1-butanoic acid anhydrate
instead of 1-nonanoic acid anhydrate in Example 21.
[0173] Tris[2-(2-propylbenzofuran-6-yl)pyridine-C.sup.5,N]iridium
(III).
[0174] As described above, according-to the present invention, the
metal coordination compound of the formula (1) characterized by the
benzofuran structure of the formula (5) as a partial structure is
an excellent material which exhibits a high emission quantum
efficiency. The electroluminescence device (luminescence device) of
the present invention using, as a luminescent center material, the
metal coordination compound of the formula (1) is an excellent
device which not only allows high-efficiency luminescence but also
retains a high luminance for a long period and shows little
deterioration by current passage. Further, the display apparatus
using the electroluminescence device of the present invention
exhibits excellent display performances.
* * * * *