U.S. patent application number 10/937906 was filed with the patent office on 2005-03-31 for compound derived from cyclopentadienone, preparation method thereof and el element using the same.
This patent application is currently assigned to Korea Institute of Science and Technology. Invention is credited to Cho, Hyun-Nam, Jung, Sung Hyun, Lee, Seung-Eun, Park, Seok-Jin.
Application Number | 20050067955 10/937906 |
Document ID | / |
Family ID | 34374209 |
Filed Date | 2005-03-31 |
United States Patent
Application |
20050067955 |
Kind Code |
A1 |
Cho, Hyun-Nam ; et
al. |
March 31, 2005 |
Compound derived from cyclopentadienone, preparation method thereof
and EL element using the same
Abstract
Disclosed are a compound represented by the following formula
(1), which is derived from cyclopentadienone and can be used as a
core material for an organic electroluminescence element or other
optical devices, and preparation method thereof, and an EL element
using the same.
Inventors: |
Cho, Hyun-Nam; (Seoul,
KR) ; Jung, Sung Hyun; (Seoul, KR) ; Park,
Seok-Jin; (Seoul, KR) ; Lee, Seung-Eun;
(Seoul, KR) |
Correspondence
Address: |
DARBY & DARBY P.C.
P. O. BOX 5257
NEW YORK
NY
10150-5257
US
|
Assignee: |
Korea Institute of Science and
Technology
Seoul
KR
|
Family ID: |
34374209 |
Appl. No.: |
10/937906 |
Filed: |
September 10, 2004 |
Current U.S.
Class: |
313/510 ;
546/255; 546/256; 548/143; 548/266.2; 548/440; 548/527; 549/59 |
Current CPC
Class: |
C07C 13/567 20130101;
C09K 2211/1007 20130101; H01L 51/0072 20130101; C09K 2211/1014
20130101; C09K 2211/1092 20130101; C07C 13/72 20130101; H01L
51/0068 20130101; C07C 49/792 20130101; C07C 2601/10 20170501; H01L
51/0058 20130101; H01L 51/0071 20130101; C09K 2211/1011 20130101;
H01L 51/0059 20130101; C07C 49/683 20130101; C09K 2211/1029
20130101; C07C 2603/94 20170501; C07D 209/86 20130101; C09K
2211/1088 20130101; C09K 2211/1048 20130101; H01L 51/005 20130101;
C07C 49/753 20130101; C07C 251/84 20130101; C09K 11/06 20130101;
C07C 43/2055 20130101; C07C 2603/18 20170501; C07C 2603/40
20170501; C07D 333/08 20130101; C07C 211/54 20130101; C07C 2603/42
20170501; H01L 51/0052 20130101 |
Class at
Publication: |
313/510 ;
546/256; 546/255; 548/266.2; 548/143; 548/440; 548/527;
549/059 |
International
Class: |
C07D 049/14; C07D
413/14 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 27, 2003 |
KR |
10-2003-0067197 |
Claims
What is claimed is:
1. A compound represented by the following formula (1): 25wherein m
is an integer of 0-5; X is S, CR.sub.1R.sub.2,
CR.sub.1.dbd.CR.sub.1R.sub.2, C.dbd.NR.sub.1 or
C.dbd.NNR.sub.1R.sub.2; R.sub.1, R.sub.2, R.sub.3, R.sub.1',
R.sub.2' and R.sub.3' may be the same with or different from each
other, and are independently selected from the group consisting of
hydrogen, C.sub.1-C.sub.22 aliphatic alkyl group, C.sub.1-C.sub.22
alicyclic alkyl and alkoxy group, and C.sub.6-C.sub.18 aryl and
aryloxy; and Ar is an aromatic or heteroaromatic group selected
from the group consisting of phenylene, naphthalene, anthracene,
fluorene, thiophene, pyrrole, pyridine, aryloxadiazole, triazole,
carbazole, arylamine, arylsilane and derivatives thereof.
2. The compound according to claim 1, wherein R.sub.1, R.sub.2,
R.sub.3, R.sub.1', R.sub.2' and R.sub.3' are independently selected
from the group consisting of hydrogen, methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, pentyl, hexyl, ethylhexyl, heptyl,
octyl, isooctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl,
dococyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy,
buthoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl,
cyanoethyl, carboxymethyl, phenyl, phenoxy, tolyl, benzyl,
naphthyl, anthrancenyl and derivatives thereof.
3. The compound according to claim 1, wherein Ar is selected from
the group consisting of the substituents having the following
structures: 2627wherein R.sub.1, R.sub.2 and R.sub.3 are
independently selected from the group consisting of hydrogen,
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl,
ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl,
hexadecyl, octadecyl, dococyl, cyclopropyl, cyclopentyl,
cyclohexyl, methoxy, ethoxy, buthoxy, hexyloxy, methoxyethoxyethyl,
methoxyethoxyethoxyethyl, cyanoethyl, carboxymethyl, phenyl,
phenoxy, tolyl, benzyl, naphthyl, anthrancenyl and a derivative
thereof.
4. A preparation method of a compound represented by formula (1),
using a compound of formula (3) or (4) as a starting material:
28wherein m is an integer of 0-5; X is S, CR.sub.1R.sub.2,
CR.sub.1.dbd.CR.sub.1R.sub.2, C.dbd.NR.sub.1 or
C.dbd.NNR.sub.1R.sub.2; R.sub.1, R.sub.2, R.sub.3, R.sub.1',
R.sub.2', R.sub.3' and R.sub.4 may be the same with or different
from each other and are independently selected from the group
consisting of hydrogen, C.sub.1-C.sub.22 aliphatic alkyl group,
C.sub.1-C.sub.22 alicyclic alkyl and alkoxy group, and
C.sub.6-C.sub.18 aryl and aryloxy; and Ar is an aromatic or
heteroaromatic group selected from the group consisting of
phenylene, naphthalene, anthracene, fluorene, thiophene, pyrrole,
pyridine, aryloxadiazole, triazole, carbazole, arylamine,
arylsilane and derivatives thereof.
5. An EL element, comprising a compound according to claim 1 in a
light-emitting layer.
6. The EL element according to 5, in construction of
anode/light-emitting layer/cathode, anode/hole transport
layer/light-emitting layer/electron transport layer/cathode, or
anode/electron injection layer/hole transport layer/light-emitting
layer/electron transport layer/electron injection layer/cathode.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a compound derived from
cyclopentadienone, which can be used as a core material for an
organic electroluminescence (referred to as `EL`, hereinafter)
element or for other optical devices, to a preparation method
thereof, and to an EL element using the same.
[0003] 2. Description of the Background Art
[0004] Since green light-emitting phenomenon using
tris(8-hydroxy-quinolin- ato)aluminum (referred to as `Alq3`,
hereinafter) as a light-emitting material has been known by Tang et
al. (See Appl. Phys. Lett., 51, p913 (1987)) of Eastman Kodak, USA,
numerous organic compounds for organic EL materials have been
developed.
[0005] Currently used light-emitting materials are divided into a
metal complex such as Alq3 well known as a fluorescent material
(See Chem. Lett., p.593 (1997); and IEEE Trans Electron Devices,
44, p.1208 (1997)), and a phosphorescent material (See Nature, 403,
p.750 (2000); and Synth. Met., 122, p.203 (2001)). Various organic
compounds have been reported as an organic single molecule
light-emitting material or a core material for other organic ELs
(See Chem. Rev., 171, p.161 (1998); Phys. World, 12, p.27 (1999);
J. Mater. Chem., 10, p.1 (2000); and Mater. Sci. Eng., R39, p.143
(2002)).
[0006] Aside from the organic single molecule light-emitting
material, many researches have been conducted on polymer-based
light-emitting materials. For example, since professor Friend et
al. in Cambridge university of United Kingdom reported first
light-emitting phenomenon of poly(phenylenevinylene) (Nature, 347,
p.539 (1990)), a lot of polymer light-emitting materials have been
reported (See Angew. Chem. Int. Ed., 37, p.402 (1998); Nature, 397,
p.121 (1999); Prog. Polym. Sci., 25, p.1089 (2000); and Adv.
Mater., 12, p.1737 (2000)).
[0007] Examples in which a cyclopentadienones or its derivative is
used as an organic EL material are exceedingly rare, but there is
an example that a cyclopentadienone compound substituted with a
phenyl group is used as a light-emitting material (Appl. Phys.
Lett., 56, p.799 (1990)). In addition, there is an example that a
polyphenylene group polymer substituted with a plurality of phenyl
groups (See J. Polym. Sci., Part B. 4, p.791 (1966); J. Polym.
Sci., Part A-1, 5, p.2721 (1967); J.Polym. Sci., Part B, 7, p.519
(1969); Macromolecules, 5, p.49 (1972); Macromolecules, 28, p.124
(1995); Macromolecules, 33, p.3535 (2000)), which is obtained by a
polymerization of a compound having bis-acetylene group (or
referred to as `diethynyl group`) and a compound having
bis-cyclopentadienone group (See J. Org. Chem., 28, p2725 (1963);
Chem. Rev., 65, p261 (1965); J. Org. Chem., 30, p3354 (1965); and
U.S. Pat. No. 4,400,540) through Diels-Alder reaction, is used as a
light-emitting material.
[0008] However, it has only been reported that such polymers can be
applied as a photoreceptor (See U.S. Pat. No. 5,882,829) or as a
dielectric (See U.S. Pat. No. 5,965,679) in a microelectronics
industry, especially in the field of integrated circuits. That is,
there are few known as compounds derived from cyclopentadienone,
and there are even fewer examples that such compounds are used as
an organic EL material.
SUMMARY OF THE INVENTION
[0009] Therefore, an object of the present invention is to provide
a compound derived from cyclopentadienone, which can be used as an
organic light-emitting material, a preparation method thereof, and
an EL element using the same.
[0010] The foregoing and other objects, features, aspects and
advantages of the present invention will become more apparent from
the following detailed description of the present invention when
taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying drawings, which are included to provide a
further understanding of the invention and are incorporated in and
constitute a unit of this specification, illustrate embodiments of
the invention and together with the description serve to explain
the principles of the invention.
[0012] In the drawings:
[0013] FIG. 1 is .sup.1H NMR spectrum of the compound [M-5];
[0014] FIG. 2 is .sup.1H NMR spectrum of the compound [M-17];
[0015] FIG. 3 is ultraviolet-visible and photoluminescence spectra
of the compound [M-5];
[0016] FIG. 4 is ultraviolet-visible and photoluminescence spectra
of the compound [M-8];
[0017] FIG. 5 is ultraviolet-visible and photoluminescence spectra
of the compound [M-9];
[0018] FIG. 6 is ultraviolet-visible and PL spectra of the compound
[M-17]; and
[0019] FIG. 7 is an EL spectrum of the compound [M-4].
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] As a result of carrying out constant researches in order to
use a compound derived from cyclopentadienone as an organic EL
material, the inventors of the present invention have synthesized
novel compounds through various reactions, and discovered that they
can be used as a light-emitting material for an organic EL
element.
[0021] Therefore, the present invention is directed to a compound
derived from a compound having one or more cyclopentadienone group,
which is represented by the following formula (1), to a preparation
method thereof, and to an organic EL element using the same. 1
[0022] wherein m is an integer of 0-5;
[0023] X is S, CR.sub.1R.sub.2, CR.sub.1.dbd.CR.sub.1R.sub.2,
C.dbd.NR.sub.1 or C.dbd.NNR.sub.1R.sub.2;
[0024] R.sub.1, R.sub.2, R.sub.3, R.sub.1', R.sub.2' and R.sub.3'
may be the same with or different from each other, and
independently selected from the group consisting of hydrogen,
C.sub.1-C.sub.22 aliphatic alkyl group, C.sub.1-C.sub.22 alicyclic
alkyl and alkoxy group, and C.sub.6-C.sub.18 aryl and aryloxy;
and
[0025] Ar is an aromatic or heteroaromatic group selected from the
group consisting of phenylene, naphthalene, anthracene, fluorene,
thiophene, pyrrole, pyridine, aryloxadiazole, triazole, carbazole,
arylamine, arylsilane and derivatives thereof, but not limited
thereto.
[0026] More specifically, R.sub.1, R.sub.2, R.sub.3, R.sub.1',
R.sub.2' and R.sub.3' may be independently selected from the group
consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, pentyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl,
nonyl, decyl, dodecyl, hexadecyl, octadecyl, dococyl, cyclopropyl,
cyclopentyl, cyclohexyl, methoxy, ethoxy, buthoxy, hexyloxy,
methoxyethoxyethyl, methoxy-ethoxyethoxyethyl, cyanoethyl,
carboxymethyl, phenyl, phenoxy, tolyl, benzyl, naphthyl,
anthrancenyl and derivatives thereof, and preferable examples of Ar
include substituents having the following structures: 23
[0027] wherein R.sub.1, R.sub.2 and R.sub.3 are the same as defined
in the above formula (1).
[0028] The compound of the formula (1) in accordance with the
present invention can be prepared by various reactions, for
example, as shown in the following Reaction Schemes 1 to 4 using
the compound represented by the following formula (3) or (4) as a
starting material: 4 5 6 7 8
[0029] In formulae (3) and (4), and Reaction Schemes 1 to 4, m,
R.sub.1, R.sub.2, R.sub.3, R.sub.1', R.sub.2', R.sub.3' and Ar are
the same as those defined in formula (1), and Ar' is the same as Ar
as defined in formula (1), but Ar and Ar' may be different from
each other. R.sub.4 is the same as those defined for R.sub.1,
R.sub.2 and R.sub.3.
[0030] In preparation of the compound of formula (1) in accordance
with the present invention, besides the methods through reactions
represented by the above Reaction Schemes 1 to 4, it can be
prepared using any starting materials through any routes, so long
as the final products are the same. In other word, in preparation
of the compound of formula (1), it is not necessary to specifically
limit a starting material, a solvent, a reaction temperature,
concentration, a catalyst or the like, and likewise yield of the
product.
[0031] The present invention is also directed to an application of
the compound of formula (1) as a material for an organic EL element
or other optical devices. Thus, the organic EL element or other
optical devices in accordance with the present invention comprise
the compound represented by formula (1) as a core material.
[0032] In the present invention, the organic EL element and other
optical devices using the compound represented by formula (1) can
be prepared by any conventional methods known in the art. In a
typical method, the compound of the present invention may be formed
into a thin film by a well-known method such as vacuum depositing
or spin coating, and such film may be directly used as an EL
material.
[0033] In construction, an EL element according to the present
invention can include not only a typical type of
anode/light-emitting layer/cathode, in which a light-emitting layer
material is inserted between an anode and a cathode, but also a
type of anode/hole transport layer/light-emitting layer/electron
transport layer/cathode, or a type of anode/electron injection
layer/hole transport layer/light-emitting layer/electron transport
layer/electron injection layer/cathode, in which a hole transport
layer and/or an electron transport layer (See Japanese Laid-Open
Patent Publication Nos. 2-135361; 3-152184; and 6-207170) are also
used. However, in the present invention, there is no limitation on
the construction of an EL element.
[0034] As an anode, a material in which a metal or metallic oxide
such as indium-tin oxide (refer to as `ITO`, hereinafter), gold,
copper, tin oxide or zinc oxide, or an organic semi-conducting
compound such as polypyrrole, polyaniline or polythiophene is
coated onto a transparent substrate such as glass, transparent
plastic or quartz usually at a thickness of 10 nm to 1 .mu.m can be
used. As a cathode, a metal such as sodium, magnesium, calcium,
aluminum, indium, silver, gold or copper, or alloys thereof can be
used.
[0035] Examples of a hole transport layer may include
polyvinylcarbazole,
2,5-bis(4'-diethylaminophenyl)-1,3,4,-oxadiazole or
N,N'-diphenyl-N,N'-(3-methyl-phenyl)-1,1'-biphenyl-4,4'-diamine
(TPD), and examples of an electron transport layer may include any
known compound such as tris(8-hydroxyquinolinato)aluminum,
2-(4'-tert-butylphenyl)-5-(4"-biphenyl)-1,3,4-oxa-diazole or
2,4,7-trinitro-9-fluoreneone. Those compounds may be used in the
form of a thin film by applying them with any known thin film
forming method, for example, vacuum depositing, spin coating,
casing or LB method.
EXAMPLES
[0036] The present invention will now be described in more detail
with reference to the following examples. However, examples are to
illustrate the present invention, not to limit the scope of the
present invention thereto.
Example 1
Reaction of tetraphenylcyclopentadienone with
1.4-diethynyl-2,5-dimethoxyb- enzene (Synthesis of [M-1])
[0037] 9
[0038] 2.0 g (5.25 mmol) of tetraphenylcyclopentadienone and 0.27 g
(2.5 mmol) of 1.4-diethynyl-2.5-dimethoxybenzene were put into a
100 ml two-neck round bottom flask equipped with a stirrer, a
thermometer and a reflux condenser under an argon atmosphere, and
50 ml of xylene was added thereto. The temperature of the reaction
mixture was gradually raised to 180.degree. C., and then, the
resultant was stirred at 180.degree. C. for 24 hours. When the
reaction was completed, the reaction mixture was cooled down to
room temperature and then gradually dropped into ethanol, to obtain
white solid. The solid was filtered, dried and re-crystallized from
a mixture of chloroform/ethanol to obtain white solid. This solid
was filtered and then dried sufficiently in a vacuum oven at
40.degree. C. to give 0.84 g (37% yield) of [M-1], of which melting
point was 340-342.degree. C.
[0039] .sup.1H NMR(CDCl.sub.3), .delta.=3.28(s, 6H, --OCH.sub.3)
6.58-7.58(m, 44H, aromatic)
[0040] Ultraviolet (hereinafter, referred to as `UV`) absorption
maximum wavelength of the product in chloroform was 305 nm, and
maximum PL wavelength was 410 nm.
Example 2
Reaction of 7,9-diphenyl-8H-cyclophene[a]acenaphtylene-8-one with
1.4-diethynyl-2.5-dimethoxybenzene (Synthesis of [M-2])
[0041] 10
[0042] 1.42 g (4 mmol) of
7,9-diphenyl-8H-cyclophene[a]acenaphtylene-8-one and 0.22 g (2
mmol) of 1.4-diethynyl-2.5-dimethoxybenzene were put into a 100 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and 50 ml of
xylene was added thereto. The temperature of the resultant was
gradually raised to 180.degree. C., and then the reaction mixture
was stirred at 180.degree. C. for 24 hours. When the reaction was
completed, the reaction mixture was cooled down to room temperature
and then gradually dropped into ethanol to obtain a light green
solid. This solid was filtered, dried and then re-crystallized from
a mixture of chloroform/ethanol to obtain a light green solid. This
solid was filtered, and then dried sufficiently in a vacuum oven at
40.degree. C. to give 0.69 g (40% yield) of [M-2], of which melting
point was 370-372.degree. C.
[0043] .sup.1H NMR(CDCl.sub.3), .delta.=3.44(s, 6H, --OCH.sub.3)
6.58-8.14(m, 36H, aromatic)
[0044] In chloroform, maximum UV absorption wavelength of the
product was 335 nm, and maximum PL wavelength was 470 nm.
Example 3
Reaction of 1.3-diphenyl-2H-cyclopenta[l]phenanthrene-2-one with
1.4-diethynyl-2,5-dimethoxybenzene (Synthesis of [M-3])
[0045] 11
[0046] 1.6 g (4 mmol) of
1.3-diphenyl-2H-cyclopenta[l]phenanthrene-2-one and 0.22 g (2 mmol)
of 1.4-diethynyl-2,5-dimethoxybenzene were put into a 100 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and 50 ml of
xylene was added thereto. The temperature of the resultant was
gradually raised to 180.degree. C., and the resultant was stirred
at 180.degree. C. for 24 hours. When the reaction was completed,
the reaction mixture was cooled down to room temperature and then
gradually dropped into ethanol to obtain white solid. This solid
was filtered, dried and then re-crystallized from a mixture of
chloroform/ethanol to obtain white solid. This solid was filtered,
and then dried sufficiently in a vacuum oven at 40.degree. C. to
give 0.59 g (35% yield) of [M-3], of which melting point was
379-381.degree. C.
[0047] .sup.1H NMR(CDCl.sub.3), .delta.=3.12(s, 6H, --OCH.sub.3),
6.46(s, 2H, aromatic), 6.99-7.69(m, 34H, aromatic), 8.37-8.42(d,
4H, aromatic)
[0048] In chloroform, maximum UV absorption wavelength of the
product was 303 nm, and maximum PL wavelength was 420 nm.
Example 4
Reaction of tetraphenylcyclopentadienone with
2.7-diethynyl-9.9'-di-n-hexy- lfluorene (Synthesis of [M-4])
[0049] 12
[0050] 0.5 g (1.3 mmol) of tetraphenylcyclopentadienone and 1.27 g
(3.3 mmol) of 2.7-diethynyl-9.9'-di-n-hexylfluorene were put into a
100 ml two-neck round bottom flask equipped with a stirrer, a
thermometer and a reflux condenser under an argon atmosphere, and
10 ml of xylene was added thereto. The temperature of the resultant
was gradually raised to 180.degree. C., and the reaction mixture
was then stirred at 180.degree. C. for 24 hours. When the reaction
was completed, the reaction mixture was cooled down to room
temperature and then gradually dropped into a mixture of
acetone/methanol (800 ml/200 ml), so as to precipitate a solid. The
precipitated solid was filtered, dissolved in chloroform again and
re-precipitated into methanol, to obtain purified solid. This solid
was filtered, thoroughly washed with methanol, and then dried
sufficiently in a vacuum oven at 40.degree. C. to give 1.06 g (75%
yield) of white solid [M-4], of which melting point was
157-160.degree. C.
[0051] .sup.1H NMR(CDCl.sub.3), .delta.=0.11-0.38(br, s, CH.sub.3),
0.76-1.22(br, m, CH.sub.2), 1.38-1.60(br, s, CCH.sub.2),
6.65-7.61(m, aromatic)
[0052] In chloroform, maximum UV absorption wavelength of the
product was 327 nm, and maximum PL wavelength was 377 nm.
Example 5
Reaction of tetraphenylcyclopentadienone with
2.7-diethynyl-9.9'-spyrobifl- uorene (Synthesis of [M-5])
[0053] 13
[0054] 1.54 g (4 mmol) of tetraphenylcyclopentadienone and 0.72 g
(2 mmol) of 2.7-diethynyl-9.9'-spyrobifluorene were put into a 100
ml two-neck round bottom flask equipped with a stirrer, a
thermometer and a reflux condenser under an argon atmosphere, and
50 ml of xylene was added thereto. The temperature of the resultant
was gradually raised to 180.degree. C., and the reaction mixture
was then stirred at 180.degree. C. for 24 hours. When the reaction
was completed, the reaction mixture was cooled down to room
temperature and then gradually dropped into ethanol to obtain white
solid. This solid was filtered, dried and then re-crystallized from
a mixture of chloroform/ethanol to obtain white solid. This solid
was filtered and then dried sufficiently in a vacuum oven at
40.degree. C. to give 1.01 g (47% yield) of [M-5], of which melting
point was 390-393.degree. C. FIG. 1 shows .sup.1H NMR spectrum of
the compound [M-5].
[0055] .sup.1H NMR(CDCl.sub.3), .delta.=6.32-7.65(m, 54H,
aromatic)
[0056] In chloroform, maximum UV absorption wavelength of the
product was 300 nm, and maximum PL wavelength was 416 nm.
Example 6
Reaction of 7,9-diphenyl-8H-cyclophene[a]acenaphtylene-8-one with
2,7-diethynyl-9.9'-spyrobifluorene (Synthesis of [M-6])
[0057] 14
[0058] 1.4 g (4 mmol) of
7,9-diphenyl-8H-cyclophene[a]acenaphtylene-8-one and 0.72 g (2
mmol) of 2.7-diethynyl-9.9'-spyrobifluorene were put into a 100 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and 50 ml of
xylene was added thereto. The temperature of the resultant was
gradually raised to 180.degree. C., and the reaction mixture was
then stirred at 180.degree. C. for 24 hours. When the reaction was
completed, the reaction mixture was cooled down to room temperature
and then gradually dropped into ethanol to obtain yellow solid.
This solid was filtered, dried and then re-crystallized from a
mixture of chloroform/ethanol to obtain yellow solid. This solid
was filtered and then dried sufficiently in a vacuum oven at
40.degree. C. to give 0.96 g (47% yield) of [M-6], of which melting
point was 330-331.degree. C.
[0059] .sup.1H NMR(CDCl.sub.3), .delta.=6.51-7.72(m, 48H,
aromatic)
[0060] In chloroform, maximum UV absorption wavelength of the
product was 310 nm, and maximum PLwavelength was 420 nm.
Example 7
Reaction of 1.3-diphenyl-2H-cyclopenta[l]phenanthrene-2-one with
2,7-diethynyl-9.9'-spyribifluorene (Synthesis of [M-7])
[0061] 15
[0062] 2.93 g (7.6 mmol) of
1.3-diphenyl-2H-cyclopenta[l]phenanthrene-2-on- e and 0.9 g (2.5
mmol) of 2,7-diethynyl-9.9'-spyrobifluorene were put into a 100 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and 50 ml of
xylene was added thereto. The temperature of the resultant was
gradually raised to 180.degree. C., and the reaction mixture was
then stirred at 180.degree. C. for 24 hours. When the reaction was
completed, the reaction mixture was cooled down to room temperature
and then gradually dropped into ethanol to obtain white solid. This
solid was filtered, dried and then re-crystallized from a mixture
of chloroform/ethanol to obtain white solid. This solid was
filtered and then dried sufficiently in a vacuum oven at 40.degree.
C. to give 1.15 g (43% yield) of [M-7], of which melting point was
392-394.degree. C.
[0063] .sup.1H NMR(CDCl.sub.3), .delta.=7.46-8.13(m, 52H,
aromatic)
[0064] In chloroform, maximum UV absorption wavelength of the
product was 312 nm, and maximum PL wavelength was 424 nm.
Example 8
Reaction of tetraphenylcyclopentadienone with
3,6-diethynyl-9-ethylcarbazo- l (Synthesis of [M-8])
[0065] 16
[0066] 1.54 g (4 mmol) of tetraphenylcyclopentadienone and 0.39(2
mmol) of 3,6-diethynyl-9-ethylcarbazole were put into a 100 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and 50 ml of
xylene was added thereto. The temperature of the resultant was
gradually raised to 180.degree. C., and the reaction mixture was
then stirred at 180.degree. C. for 24 hours. When the reaction was
completed, the reaction mixture was cooled down to room temperature
and then gradually dropped into ethanol to obtain brown solid. This
solid was filtered, dried and then re-crystallized from a mixture
of chloroform/ethanol to obtain brown solid. This solid was
filtered and then dried sufficiently in a vacuum oven at 40.degree.
C. to give 0.66 g (33% yield) of [M-8], of which melting point was
280-283.degree. C.
[0067] .sup.1H NMR(CDCl.sub.3), .delta.=1.43(t, 2H, --CH.sub.2),
4.23(q, 3H, CH.sub.3), 6.91-7.30(m, 44H, aromatic), 7.73(s, 2H,
aromatic), 7.95(s, 2H, aromatic)
[0068] In chloroform, maximum UV absorption wavelength of the
product was 313 nm, and maximum PL wavelength was 397 nm.
Example 9
Reaction of 7,9-diphenyl-8H-cyclophene[a]acenaphtylene-8-one with
3,6-diethynyl-9-ethylcarbazole (Synthesis of [M-9])
[0069] 17
[0070] 1.4 g (4 mmol) of
7,9-diphenyl-8H-cyclophene[a]acenaphtylene-8-one and 0.39 g (2
mmol) of 2.7-diethynyl-9-ethylcarbazole were put into a 100 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and 50 ml of
xylene was added thereto. The temperature of the resultant was
gradually raised to 180.degree. C., and the reaction mixture was
then stirred at 180.degree. C. for 24 hours. When the reaction was
completed, the reaction mixture was cooled down to room temperature
and then gradually dropped into ethanol to obtain yellow solid.
This solid was filtered, dried and then re-crystallized from a
mixture of chloroform/ethanol to obtain yellow solid. This solid
was filtered and then dried sufficiently in a vacuum oven at
40.degree. C. to give [M-8] 0.68 g (35% yield) of [M-9], of which
melting point was 275-276.degree. C.
[0071] .sup.1H NMR(CDCl.sub.3), .delta.=1.43(t, 2H, --CH.sub.2),
4.23(q, 3H, CH.sub.3), 6.74(d, 2H, aromatic), 7.13-7.98(m, 38H,
aromatic)
[0072] In chloroform, maximum UV absorption wavelength of the
product was 322 nm, and maximum PL wavelength was 480 nm.
Example 10
Synthesis of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)-9,9'-spyrobiflu-
orene [M-12]
[0073] 18
[0074] Synthesis of 2,7-bis(phenylethynyl)-9,9'-spyrobifluorene
[M-10]
[0075] 10 g (21.09 mmol) of 2.7-dibromo-9.9'-spyrobifluorene, 0.43
g (0.63 mmol) of bistriphenylphosphine palladium dichloride and
0.12 g (0.63 mmol) of copper iodide were put into a 500 ml
three-neck round bottom flask equipped with a stirrer, a
thermometer and a reflux condenser under an argon atmosphere, and
then 300 ml of piperidine was added thereto so as to dissolve the
resultant. 5.38 g (52.61 mmol) of phenylacetylene was gradually
dropped thereto at room temperature. After completion of the
dropping, the temperature of the reaction mixture was gradually
raised to 110.degree. C. and then stirred at 110.degree. C. for 12
hours. When the reaction was completed, the reaction mixture was
cooled down to room temperature. Generated salt was filtered off,
and then the filtrate was concentrated under a reduced pressure.
The residue was dissolved in dichloromethane, washed with water
several times and then dried with anhydrous magnesium sulfate,
which was then filtered off. The solvent was removed, and the
residue was re-crystallized from a mixture of ethyl acetate and
hexane to obtain yellow crystal, which was dried sufficiently in a
vacuum oven at 40.degree. C. to give 6.52 g (59.7% yield) of
[M-10], of which melting point was 210-212.degree. C.
[0076] .sup.1H NMR (CDCl.sub.3), .delta.=6.74-6.78(d, 2H,
aromatic), 6.90(s, 2H, aromatic), 7.10-7.18(t, 2H, aromatic),
7.24-7.28(m, 6H, aromatic), 7.36-7.42(m, 6H, aromatic),
7.52-7.57(d, 2H, aromatic) 7.79-7.88(t, 4H, aromatic).
[0077] Synthesis of 2,7-bis(phenylglyoxalyl)-9,9'-spyrobifluorene
[M-11]
[0078] 6.41 g (12.40 mmol) of [M-10] was put into a 1 L three-neck
round bottom flask equipped with a stirrer and dissolved in 150 ml
of dichloromethane, and 300 ml of water was then added thereto.
0.62 g of tetrabutylammonium bromide, 2.50 g of sodium bicarbonate
and 12.50 g of potassium permanganate were added into the above
reaction flask, and the resultant was stirred for 48 hours. When
the reaction was completed, an ice-bath was installed, and then 18
g of sodium bisulfite and 9 ml of hydrochloric acid were gradually
added to the reaction mixture, and the resultant was additionally
stirred for 30 minutes. The reaction mixture was filtered, and
filtrate was then extracted with dichloromethane. The organic
extract was washed with water several times and then dried with
anhydrous magnesium sulfate, and then solvent was removed to obtain
yellow solid. This solid was re-crystallized from ethyl acetate to
give yellow crystal, which was filtered and then dried sufficiently
in a vacuum oven at 40.degree. C. to give 3.61 g (50% yield) of
[M-11], of which melting point was 134-136.degree. C.
[0079] .sup.1H NMR (CDCl.sub.3), .delta.=6.67-6.70(d, 2H,
aromatic), 7.09-7.16(t, 2H, aromatic), 7.38-7.63(m, 10H, aromatic),
7.87-8.01(m, 10H, aromatic).
[0080] Synthesis of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)-9,9'-spy-
ro-bifluorene [M-12]
[0081] 3.50 g (6.0 mmol) of [M-11] was put into a 1 L three-neck
round bottom flask equipped with a stirrer, a thermometer and a
reflux condenser under an argon atmosphere, and 350 ml of ethanol
and 150 ml of butanol were added thereto, and the resultant was
then heated to 120.degree. C. so as to dissolve the starting
material. To the resulting solution, 2.78 g (13.2 mmol) of
1.3-diphenyl-2-propaneone, 0.25 g of potassium hydroxide and 4.7 ml
of water were added. The resultant was then reacted at 120.degree.
C. for 12 hours. After the reaction was completed, the temperature
of the reaction mixture was gradually cooled down to 0.degree. C.
to give a dark brown solid, which was filtered and then washed with
cold ethanol. After filtering, this solid was dried sufficiently in
a vacuum oven at 40.degree. C. to give 2.51 g (44.6% yield) of
[M-12], of which melting point was 192-195.degree. C.
[0082] .sup.1H NMR (CDCl.sub.3), .delta.=6.14(s, 1H, aromatic),
6.48-6.52(d, 2H, aromatic), 6.73-6.76(d, 3H, aromatic),
6.98-7.30(m, 30H, aromatic), 7.47-7.60(d, 4H, aromatic)
Example 11
Reaction of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)-9,9'-spyrobifluo-
rene with 4-ethynyl-N,N-ditolylaniline (Synthesis of [M-13])
[0083] 19
[0084] 0.5 g (0.54 mmol) of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)--
9,9'-sprobifluorene) and 0.48 g (1.61 mmol) of
4-ethynyl-N,N-ditolylanilin- e were put into a 100 ml two-neck
round bottom flask equipped with a stirrer, a thermometer and a
reflux condenser under an argon atmosphere, and 10 ml of
cyclohexylbenzene was added thereto. The temperature of the
reaction mixture was gradually raised to 200.degree. C., and the
resultant was then stirred at 200.degree. C. for 24 hours. When the
reaction was completed, the reaction mixture was cooled down to
room temperature and then gradually dropped into a mixture of
acetone/methanol (800 ml/200 ml), so as to precipitate a solid. The
precipitated solid was filtered, dissolved in chloroform again, and
then re-precipitated into methanol to give a purified solid. This
solid was filtered, thoroughly washed with a methanol and then
dried sufficiently in a vacuum oven at 40.degree. C. to give 0.43 g
(54% yield) of brown solid [M-13].
Example 12
Reaction of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)-9,9'-spyrobifluo-
rene with 3-ethynyl-9-ethylcarbazole (Synthesis of [M-14])
[0085] 20
[0086] 0.5 g (0.54 mmol) of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)--
9,9'-spyrobifluorene and 0.24 g (1.08 mmol) of
3-ethynyl-9-ethylcarbazole were put into a 100 ml two-neck round
bottom flask equipped with a stirrer, a thermometer and a reflux
condenser under an argon atmosphere, and 10 ml of xylene was put
thereto. The temperature of the resultant was gradually raised to
180.degree. C., and the reaction mixture was stirred at 180.degree.
C. for 24 hours. When the reaction was completed, the reaction
mixture was cooled down to room temperature and then gradually
dropped into a mixture of acetone/methanol (800 ml/200 ml)), so as
to precipitate a solid. The precipitated solid was filtered,
dissolved in chloroform again, and re-precipitated into methanol to
obtain a purified solid. This solid was filtered, thoroughly washed
with a methanol and then dried sufficiently in a vacuum oven at
40.degree. C. to give 0.44 g (63% yield) of the product [M-14] as
white solid.
Example 13
Synthesis of 1,4-bis(2,4,5-triphenylthiophene)-2,5-dimethoxybenzene
[M-15]
[0087] 21
[0088] 1.00 g (1.33 mmol) of
1,4-bis(2,4,5-triphenylcyclopentadienon-3-yl)-
-2,5-dimethoxybenzene and 0.20 g (5.88 mmol) of sulfur were put
into a 50 ml ampoule flask equipped with a stirrer and a
thermometer, and the flask was then sealed. The resultant was
reacted at 350.degree. C. for 48 hours. When the reaction was
completed, the temperature was dropped down to room temperature,
and then the ampoule was opened. The resultant was extracted with
chloroform, and organic extract was washed with water several times
and then dried with anhydrous magnesium sulfate. The solvent was
removed to obtain a dark brown solid, which was re-crystallized
from a mixture of ethyl acetate and hexane, to give brown crystal.
This solid was dried sufficiently in a vacuum oven at 40.degree. C.
to give 0.58 g (57.4% yield) of [M-15].
Example 14
Synthesis of 2,7-bis(2,4,5-triphenylthiophene)-9,9'-dihexylfluorene
[M-16]
[0089] 22
[0090] 0.80 g (0.84 mmol) of
2,7-bis(2,4,5-triphenylcyclopentadienon-3-yl)-
-9,9'-di-n-hexylfluorene and 0.13 g (3.82 mmol) of sulfur were put
into a 50 ml ampoule flask equipped with a stirrer and thermometer,
and the flask was then sealed. The resultant was reacted at
350.degree. C. for 48 hours. When the reaction was completed, the
temperature was dropped down to room temperature, and the ampoule
was then opened. The reaction mixture was extracted with
chloroform, and then organic extract was washed with water several
times and then dried with anhydrous magnesium sulfate. The solvent
was removed to obtain a dark brown solid, which was re-crystallized
from a mixture of ethyl acetate and hexane to give brown crystal.
This solid was dried sufficiently in a vacuum oven at 40.degree. C.
to give 0.53 g (66.4% yield) of [M-16].
[0091] In chloroform, maximum UV absorption wavelength of the
product was 280 nm, and maximum PL wavelength was 436 nm.
Example 15
Synthesis of 2,3,4,5-tetraphenylcyclopentadiene hydrazone
[M-17]
[0092] 23
[0093] 2.0 g (5.2 mmol) of tetraphenylcyclopentadienone was put
into a 500 ml two-neck round bottom flask equipped with a stirrer,
a thermometer and a reflux condenser under an argon atmosphere, and
100 ml of diethylene glycol was added thereto so as to dissolve the
starting material. 20 ml of hydrazine hydrate and 5.20 g of
hydrazine dihydrochloride were added to the above flask, and the
resultant was reacted at 200.degree. C. for 12 hours. When the
reaction was completed, the temperature was gradually dropped down
to 0.degree. C., and the reaction mixture was gradually poured into
500 ml of water to precipitate yellow solid. This solid was
filtered, washed with water and then washed again with cold
methanol three times. The solid was dried and then re-crystallized
from ethyl acetate and hexane, to give white solid. This solid was
filtered and then dried sufficiently in a vacuum oven at 40.degree.
C. to give 0.78 g (40.6% yield) of [M-17], of which melting point
was 134-136.degree. C. FIG. 2 shows .sup.1H NMR spectrum of the
compound [M-17].
[0094] .sup.1H NMR (CDCl.sub.3), .delta.=4.27(s, 2H, NH.sub.2),
6.75-6.83(m, 4H, aromatic), 6.98-7.01(m, 4H, aromatic),
7.13-7.25(m, 10H, aromatic), 7.35-7.39(m, 2H, aromatic)
[0095] In chloroform, maximum UV absorption wavelength of the
product was 252 nm, and maximum PL wavelength was 373 nm.
Example 16
Synthesis of 1,4-bis(2,3,5-triphenylcyclopentadiene
hydrazone)benzene [M-18]
[0096] 24
[0097] 3.5 g (5.2 mmol) of
1,4-bis(triphenylcyclopentadienone)benzene was put into a 500 ml
two-neck round bottom flask equipped with a stirrer, a thermometer
and a reflux condenser under an argon atmosphere, and was dissolved
in 100 ml of diethylene glycol. 20 ml of hydrazine hydrate and 5.20
g of hydrazine dihydro chloride were added to the above flask, and
the resultant was reacted at 200.degree. C. for 12 hours. When the
reaction was completed, the temperature was gradually dropped down
to 0.degree. C., and the reaction mixture was gradually put into
500 ml of water to precipitate yellow solid. This solid was
filtered, washed with water and then washed again with cold
methanol three times. The solid was dried and then re-crystallized
from ethyl acetate and hexane to give white solid. This solid was
filtered and then dried sufficiently in a vacuum oven at 40.degree.
C. to give 0.78 g (21% yield) of [M-18].
Example 17
[0098] Test of Ultraviolet-Visible, Photoluminescence and EL
Properties
[0099] The compounds prepared in Examples were respectively
dissolved in chloroform, and obtained solutions were then filtered
through a micro filter in size of 0.2 micron. Ultraviolet-visible
(hereinafter, referred to as `UV-Vis`) and photoluminescence
(hereinafter, referred to as `PL`) properties of the compound
according to the present invention were determined in a manner that
a UV-Vis spectrum was observed first, and then PL spectrum was
observed at a wavelength in which UV-Vis peak shows maximum
value.
[0100] FIGS. 3 to 6 show UV-Vis and PL spectra of the compounds
[M-5], [M-8], [M-9] and [M-17], respectively.
[0101] FIG. 7 shows EL spectrum of an element comprising the
compound [M-4], in construction of
ITO/m-MTDATA/NPB/M-4/Alq3/LiF/Al.
[0102] As described above, according to the present invention, a
compound that is derived from a compound having a cyclopentadienone
group according to the present invention and that can be used as an
organic light-emitting material, its preparation method and an EL
element using the same are provided. The compound of the present
invention. can be applied as a core material of an organic EL
element or the like. Besides, the compounds of the present
invention can be applied for an optical switch, a sensor, a module,
a waveguide, a material for an optical storage or amplification, a
nonlinear optical material, a transistor, a laser, an optical
conductor, a photoreceptor, an optical refracting material, a
piezoelectric material, a magnetic material, a dielectric material
or the like since they exhibit PL properties, nonliear optical
properties, photo and electric conductivity and the like.
[0103] As the present invention may be embodied in several forms
without departing from the spirit or essential characteristics
thereof, it should also be understood that the above-described
embodiments are not limited by any of the details of the foregoing
description, unless otherwise specified, but rather should be
construed broadly within its spirit and scope as defined in the
appended claims, and therefore all changes and modifications that
fall within the metes and bounds of the claims, or equivalence of
such metes and bounds are therefore intended to be embraced by the
appended claims.
* * * * *