CA2464604A1 - Organic luminescent compounds and methods of making and using same - Google Patents
Organic luminescent compounds and methods of making and using same Download PDFInfo
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Abstract
The invention provides organic compounds of the general structures (1A), (1B) and (1C) that are photoluminescent and electroluminescent, emitting intense blue light.
The invention further provides methods of synthesizing such compounds, methods of producing photoluminescence and electroluminescence, methods of applying the compounds in thin films, and uses of the compounds of the invention in luminescent probes, electroluminescent displays and as pH probes and metal ion detectors.
The invention further provides methods of synthesizing such compounds, methods of producing photoluminescence and electroluminescence, methods of applying the compounds in thin films, and uses of the compounds of the invention in luminescent probes, electroluminescent displays and as pH probes and metal ion detectors.
Description
ORGANIC LUMINESCENT COMPOUNDS AND
METHODS OF MAKING AND USING SAME
FIELD OF THE INVENTION
The invention relates to organic compounds having luminescent properties, and to methods of synthesizing and using such compounds. The invention more particularly relates to compounds having photoluminescent and/or electroluminescent properties, and to synthesis and uses of same. The invention also relates to compounds having photo-receptor properties due to their ability to separate charges. The invention also relates to compounds having photon harvesting properties. The invention also relates to compounds that visibly display detection of metal ions or acid. The invention further relates to compounds that can provide a molecular switch.
BACKGROUND OF THE INVENTION
Production of devices based on electroluminescent display is a rapidly growing, billion dollar industry. Bright and efficient organic light-emitting diode (OLED) devices and electroluminescent (EL) devices have attracted considerable interest due to their potential application for flat panel displays (e.g., television and computer monitors).
OLED based displays offer advantages over the traditional liquid crystal displays, such as: wide viewing angle, fast response, lower power consumption, and lower cost. However, several challenges still must be addressed before OLEDs become truly affordable and attractive replacements for liquid crystal based displays. To realize full color display applications, it is essential to have the three fundamental colors of red, green, and blue provided by emitters with sufficient color purity and sufficiently high emission efficiency.
In general, when a potential is applied across an OLED, holes are said to be injected from an anode into a hole transporting layer (HTL) while electrons are injected from a cathode into an electron transporting layer (ETL). The holes and electrons migrate to an ETL/HTL interface.
Materials for these transporting layers are chosen so that holes are preferentially transported by the HTL, and electrons are preferentially transported by the ETL,. At th.e ETL/HTL interface, the holes and electrons recombine to give excited molecules which radiatively relax, producing an EL emission that can range from blue to near-infrared (Koene, 1998).
In providing one of the key color components for electroluminescent display devices, blue luminescent compounds are among the mast sought-after materials by industry around the world.
Two alternative ways in which blue luminescence can be achieved are: (i) providing a molecule which emits blue color (emitter), and (ii) doping an emitter such that the combination yields blue luminescence. Conveniently, the emitter can be an inorganic metal ion such as, for example, lanthanide, which emits blue light via d to f or f to f electronic transitions, or an organic molecule which has conjugated ~t bonds and emits blue light via ~ to ~ or ~ to ra electronic transitions.
A common problem with blue emitters is their lack of fang term stability in OLEDs.
OLEDs generally suffer from a gradual intensity decrease of the blue hue, which results in gradual deterioration of the color purity of the display, and ultimately failure of the device.
Television and computer monitors must perform consistently for at least five years in order to be commercially feasible. Even this modest expectation is a big challenge for currently available OLEDs.
There are several blue luminescent inorganic coordination compounds known (U.S.
Patent No. 6,500,569, U.S. Patent No. 6,312,835, Yang, 2001, Jia et al., 2003); however, in some cases, due to a propensity for oxidation and/or hydrolysis reactions, such complexes are not very stable in solution. One family of known inorganic blue emitters, lanthanide ions, have low emission efficiency and require the use of a host (generally an inorganic salt), which mazes it difficult to process them into thin films.
Thus, blue luminescent materials that are organic in nature are desirable due to their increased stability, solubility and ability to form thin films. A number of organic blue emitters axe known to date (Shirota, 2000, Yang, 2001, Wu et al., 2001, and Liu et al., 2000). Many of these have poor luminescence efficiency and poor stability. Some are luminescent polymers that are difficult to apply in films using chemical vapor deposition (CVD) or vacuum deposition, processes known to produce superior films for electroluminescent displays.
Even the best blue emitters currently available do not have the long term stability desired for commercial devices.
The limitations discussed above could restrict the market for OLED products, despite their many superior aspects as compared with liquid crystal displays.
Therefore, in order for OLEDs to become truly feasible, there is a need for stable, organic emitters.
BRIEF STATEMENT OF THE INVENTION
In a first aspect, the invention provides a compound having a general formula (lA):
METHODS OF MAKING AND USING SAME
FIELD OF THE INVENTION
The invention relates to organic compounds having luminescent properties, and to methods of synthesizing and using such compounds. The invention more particularly relates to compounds having photoluminescent and/or electroluminescent properties, and to synthesis and uses of same. The invention also relates to compounds having photo-receptor properties due to their ability to separate charges. The invention also relates to compounds having photon harvesting properties. The invention also relates to compounds that visibly display detection of metal ions or acid. The invention further relates to compounds that can provide a molecular switch.
BACKGROUND OF THE INVENTION
Production of devices based on electroluminescent display is a rapidly growing, billion dollar industry. Bright and efficient organic light-emitting diode (OLED) devices and electroluminescent (EL) devices have attracted considerable interest due to their potential application for flat panel displays (e.g., television and computer monitors).
OLED based displays offer advantages over the traditional liquid crystal displays, such as: wide viewing angle, fast response, lower power consumption, and lower cost. However, several challenges still must be addressed before OLEDs become truly affordable and attractive replacements for liquid crystal based displays. To realize full color display applications, it is essential to have the three fundamental colors of red, green, and blue provided by emitters with sufficient color purity and sufficiently high emission efficiency.
In general, when a potential is applied across an OLED, holes are said to be injected from an anode into a hole transporting layer (HTL) while electrons are injected from a cathode into an electron transporting layer (ETL). The holes and electrons migrate to an ETL/HTL interface.
Materials for these transporting layers are chosen so that holes are preferentially transported by the HTL, and electrons are preferentially transported by the ETL,. At th.e ETL/HTL interface, the holes and electrons recombine to give excited molecules which radiatively relax, producing an EL emission that can range from blue to near-infrared (Koene, 1998).
In providing one of the key color components for electroluminescent display devices, blue luminescent compounds are among the mast sought-after materials by industry around the world.
Two alternative ways in which blue luminescence can be achieved are: (i) providing a molecule which emits blue color (emitter), and (ii) doping an emitter such that the combination yields blue luminescence. Conveniently, the emitter can be an inorganic metal ion such as, for example, lanthanide, which emits blue light via d to f or f to f electronic transitions, or an organic molecule which has conjugated ~t bonds and emits blue light via ~ to ~ or ~ to ra electronic transitions.
A common problem with blue emitters is their lack of fang term stability in OLEDs.
OLEDs generally suffer from a gradual intensity decrease of the blue hue, which results in gradual deterioration of the color purity of the display, and ultimately failure of the device.
Television and computer monitors must perform consistently for at least five years in order to be commercially feasible. Even this modest expectation is a big challenge for currently available OLEDs.
There are several blue luminescent inorganic coordination compounds known (U.S.
Patent No. 6,500,569, U.S. Patent No. 6,312,835, Yang, 2001, Jia et al., 2003); however, in some cases, due to a propensity for oxidation and/or hydrolysis reactions, such complexes are not very stable in solution. One family of known inorganic blue emitters, lanthanide ions, have low emission efficiency and require the use of a host (generally an inorganic salt), which mazes it difficult to process them into thin films.
Thus, blue luminescent materials that are organic in nature are desirable due to their increased stability, solubility and ability to form thin films. A number of organic blue emitters axe known to date (Shirota, 2000, Yang, 2001, Wu et al., 2001, and Liu et al., 2000). Many of these have poor luminescence efficiency and poor stability. Some are luminescent polymers that are difficult to apply in films using chemical vapor deposition (CVD) or vacuum deposition, processes known to produce superior films for electroluminescent displays.
Even the best blue emitters currently available do not have the long term stability desired for commercial devices.
The limitations discussed above could restrict the market for OLED products, despite their many superior aspects as compared with liquid crystal displays.
Therefore, in order for OLEDs to become truly feasible, there is a need for stable, organic emitters.
BRIEF STATEMENT OF THE INVENTION
In a first aspect, the invention provides a compound having a general formula (lA):
XB_ X, a i Z
n (lA) where X5, X6 and X' are each independently selected from the group consisting of carbon and nitrogen;
n is a number from 0-2;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl; and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrile group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
In some embodiments, X5, X6 and X' may be each independently selected from the group consisting of a substituted carbon, an unsubstituted carbon and an unsubstituted nitrogen. In some embodiments, at least one of X5, X6 and X' is nitrogen. In some embodiments, X5, X6 and X' are nitrogen.
In a second aspect, the invention provides a compound having a general formula ( 1 B):
SP
Z
n Tq (1B) where Xg, X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
m is a number from 0-10;
Q, S and T are the same or different and are selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
p and q are the same or different and are a number between 0-~;
r is a number between 0-4;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyrid;yl, bipyridyl, indyl, and quinolinyl;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite graup, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
In some embodiments, Xg is selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon; X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 0 to 4. In some embodiments, X$
is nitrogen; X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 1 to 4.
In a third aspect, the invention provides a compound having a general formula ( 1 C):
jN Z2 m Q~
( 1 C) where Z2, Z3 and Z4 are each independently a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl;
m is a number from 0-10;
Q is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
r is a number between 0 and 4;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
In another aspect, the invention provides a photoluminescent or electroluminescent compound having a formula selected from the group consisting of 1-pyrenyl-2,2'-dipyridylamine (2), 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3), 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4), 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5) and QNPB (6).
Compounds of the invention may be photoluminescent and/or electroluminescent.
Compounds of the invention may be hole transporters.
In further aspect, the invention provides a method of synthesizing a compound of general formula (lA), comprising a step selected from the group consisting of 1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3P04+ 1,2-transdiaminocyclohexane + 1,4-dioxane 1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-brornopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid 4-( 1-pyrenyl)phenyl-2,2'-dipyridylamine(3 );
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4);
4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-BuLi 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5); and p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi p-N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + NazC03 ~ QNPB (6).
In further aspect, the inventian provides a method of synthesizing a compound of general ___.___.. .~..~.. _~~ ..-~~.- ~..~-.~.~ ~ ..n _.~~...._-__-._._r___. __ formula (1B), comprising a step selected from the group consisting of 1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3P04+ 1,2-transdiaminocyclohexane + 1,4-dioxane 1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-bromopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine(3);
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid 3 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4); and 4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-Buhi 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5).
In further aspect, the invention provides a method of synthesizing a compound of general formula (1C), comprising a step selected from the group consisting of p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi p N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + Na2C03 -~ QNPB (6).
In further aspects, the invention provides compositions comprising a compound of the invention, an organic polymer and a solvent.
In still further aspects, the invention provides a photoluminescent product or an electroluminescent product comprising a compound of the invention. The product may be a flat panel display device. The product may be a luminescent probe.
In another aspect, the invention provides a method of producing electroluminescence, comprising the steps of providing an electroluminescent compound of the invention and applying a voltage across said compound so that said compound electroluminesces.
In other aspects, the invention provides electroluminesce~nt devices for use with an applied voltage.
A first such device comprises: a first electrode, an emitter which is an electroluminescent compound of the invention, and a second, transparent electrode, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
A second such device comprises: a first electrode, a second, transparent electrode, an electron transport layer adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is an electroluminescent compound of the invention interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
A third such device comprises: a first electrode, a second, transparent electrode, a layer which is both an emitter and an electron transporter which is an electroluminescent compound of the invention and which is located adjacent the first electrode, and a hole transport layer which is interposed between the emitter and electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
A fourth such device comprises: a first electrode, a secomd, transparent electrode, a layer which is all of an emitter, an electron transporter and a hole transporter which is an electroluminescent compound of the invention and which is interposed between the first and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
A fifth such device comprises: a first electrode, a second, transparent electrode, an electron transport layer which is a compound of the invention and which is located adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
A sixth such device comprises: a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, a hole transport layer which is a compound of the invention and which is located adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an el,ectrie field so that the emitter electroluminesces.
A seventh such device comprises: a first electrode, a second, transparent electrode, a layer which is both an electron transporter and an emitter which is located adjacent the first electrode, and a hole transport layer which is a compound of the invention and which is interposed between _........__.._.___" "", s~.,rnaa,asw~ r.~~., ~s~aamawma, ~~aaxn~~~...._...
_~_~.__ ...,am,",A"~,., .._... .___._ the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
An eighth such device comprises: a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, anal a layer which is both an emitter and a hole transporter which is a compound of the invention and which is interposed between the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
In another aspect, the invention provides a method of detecting metal ions, comprising the steps of providing a photoluminescent compound of the invention, and detecting photoluminescence of said compound, wherein contact with a metal ion quenches said photoluminescence of said compound. The metal ions may be selected from the group consisting of Zn2+, Cu2+, Ni2+y Cdz+, HgZ+ and Ag+.
In another aspect, the invention provides a method of detecting acid, comprising the steps of providing a photolutninescent compound of the invention, and detecting photoluminescence of said compound, wherein protonation of said compound changes the state of said compound's photoluminescence.
In another aspect, the invention provides a method of harvesting photons, comprising the steps of providing a compound of the invention, and providing light such that photons strike said compound and charge separation occurs in said compound. In some embodiments, the separated charges may recombine and photons be released. In some embodiments, the separated charges may migrate to respective electrodes to produce a potential difference.
In another aspect, the invention provides a method of separating charges, comprising the steps of providing a compound of the invention, and providing light such that photons strike said compound and charge separation occurs in said compound. In some embodiments, the separated charges may recombine and photons be released. In some embodiments;
the separated charges may migrate to respective electrodes to produce a potential difference.
In other aspects, the invention provides a photocopier, a photovoltaic device, a photoreceptor, a solar cell and a semiconductor employing the afore-mentioned methods of harvesting photons and/or separating charges.
In another aspect, the invention provides a molecular switch comprising a compound of the invention that is capable of existing in more than one luminescent state, wherein acid, base, and/or incident light produces a change in the luminescent state of said compound. The invention further provides a circuit comprising such a molecular switch.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention and to show more clearly how it may be carried into effect, reference will now be made by way of example to the accompanying drawings, which illustrate aspects and features according to preferred embodiments of the present invention, and in which:
Figure 1 shows a preferred embodiment of a three layer electroluminescent (EL) display device according to the invention.
Figure 2 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 1-pyrenyl-2,2'-dipyridylamine (2) as a solid.
Figure 3 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 1-pyrenyl-2,2'-dipyridylamine (2) in a CHZC12 solution at a concentration of 2.55 x 10-6 M at 298K.
Figure 4 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) as a solid.
Figure 5 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) in a CHZC12 solution at a concentration of 2.55 x 106 M at 298K.
Figure 6 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-(4'(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4) as a solid.
Figure 7 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4) in a CHzCl2 solution at a concentration of 2.55 x 10-6 M at 298K.
Figure 8 shows an electroluminescence spectrum produced by compound 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) in a two layer EL device described in Example 6.
Figure 9 shows the crystal structure of compound (2).
Figure 10 shows the crystal structure of compound (3).
Figure 11 shows the crystal structure of compound (4).
Figure 12 shows the (-) photoluminescence (PL) spectrum of compound (4) and the (- - -) electroluminescence (EL) spectrum of compound (4) produced by a solid-state filin at 298K.
Figure 13 shows the dependence of Luminance (L) and Current Density (J) on Voltage (V) of a film of compound (4) in a two layer EL device of the following configuration: TfO/NPB
(40 nm)/compound(4) (40 nm)/LiF (1 nm)/Al, where NPB is the hole transport layer, compound (4) is both the emitter and electron transport layer and LiF is added to improve contact between the electron transport layer and the cathode.
Figure 14 shows the excitation (lower wavelength) and the emission (higher wavelength) spectra of compound (5) as a solid-state film (-) at 298K and as a CHzCl2 solution (CI) at a concentration of 10'S M at 298K.
Figure 15A is a cyclic voltametry diagram starting with the reduction of compound (5) in a mixture of CHZC12 and CH3CN. This figure provides information about the Lowest Unoccupied Molecular Orbital (LUMO) of the molecule and indicates promising electron transport properties of the molecule.
Figure 15B is a cyclic voltametry diagram starting with the oxidation of compound (S) in a mixture of CHZC12 and CH3CN. This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transport properties of the molecule.
Figure 16 shows the dependence of Luminance (L) and Current (I) on Voltage (V) of a single layer EL device of compound (4) prepared with the following configuration:
ITO/compound (4) (60 nm)/LiF(0.5 nm)/Al(140nm), where compound (4) is the hole transport layer, emitter and electron transport layer and LiF is added to improve contact between the film and the cathode.
Figure 17A shows the dependence of Current Density (J) on Voltage (V) of a film of compound (6) in a single layer EL device of the following configuration:
ITO/compound (6) (90 nm)/LiF (0.5 nm)/Al, where compound (6) is all of electron transport layer, emitter and hole transport layer and LiF is added to improve contact between the film and the cathode.
Figure 17B shows the dependence of Luminance (L) on Voltage (V) of a film of compound (6) in a single layer EL device of the following configuration:
ITO/compound (6) (90 nm)/LiF (0.5 nm)/Al, where compound (6) is all of electron transport layer, emitter and hole transport layer and LiF is added to improve contact between the film and the cathode.
Figure 18 shows the (-) photoluminescence spectrum of compound (6) and the (- --) electroluminescence spectrum of compound (6) produced by a single layer EL
device of the following configuration: ITO/compound (6) (90 nm)/LiF (0.5 nrn)/Al, where compound (6) is all of electron transport layer, emitter and hole transport layer and LiF is added to improve contact between the film and the cathode.
Figure 19A shows the dependence of Current Density (J) on Voltage ('~ of a film of compound (6) in a double layer EL device of the following configuration:
ITO/compound (6) (30, 60, 90, 120 nm)/Alq3 (40 nm)/LiF (0.5 nm)/Al, where compound (6) is the hole transport layer and Alq3 is both emitter and electron transport layer and LiF is added to improve contact . ~..~.,. ~ . .. ~e..,~.,. . ~* ~ *.~~ fi .. . . ., m._. .....,.. . ___..-m_ .
. ..- _.~ . .u.~..m ._.__ _._..__.
."n.'~A4H d , . ~,.,R:r~.tR~'WC..34.n.n:y'e,.,Fi"X~a.e s~.~a~,urr'~~" vw.wemx .R...a~.A..wrn.. ~ a..;..*myaww..n~
between the film and the cathode.
Figure 19B shows the dependence of Luminance (L) on Voltage (V) of a film of compound (6) in a double layer EL device of the following configuration:
ITO/compound (6) (30, 60, 90, 120 nm)/Alq3 (40 nm)lLiF (0.5 nm)/Al, where compound (6) is the hole transport layer and Alq3 is both emitter and electron transport layer and LiF is added to improve contact between the film and the cathode.
Figure 20 shows the crystal structure of (6).
Figure 21 is a cyclic voltammetry diagram starting with the oxidation of compound (6) in CHZCIz. This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transpou properties of the molecule.
DETAILED DESCRIPTION OF THE INVENTION
In a first aspect of the invention, a stable organic compound of the general formula (1A) is provided:
x= ~
~" \ /
\ /
(lA) where X5, X6 and X' are each independently selected from the soup consisting of carbon and nitrogen;
n is a number from 0-2;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl (preferred substituent examples la-lm are pictured below); and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
Preferably a compound of general formula (lA) exhibits intense luminescence, which may be photoluminescence and/or electroluminescence.
In preferred embodiments of compounds of the general formula (lA), X5, X6 and X' are each independently a substituted or unsubstituted carbon or an unsubstituted nitrogen. In some embodiments, one or two of X5, X6 and X' are nitrogen. In a preferred embodiment, X5, X6 and X' are all nitrogen. A synthetic scheme depicting the preparation of such compounds is pictured in Schemes 1 and 2; working examples of detailed synthetic procedures are provided in Examples 1 - 4.
/ \ ~ \
\ I / \ I /
1a 1-naphthyl 1b 2-naphthyl 1c 9-anthryl 1 d 9-phenanthryl 1e 1-pyrenyl ~t ~-pyrenyl ,g 4-pyrenyl 1 h biphenyl 1 i phenyl / ~ \
1j indyl 1k quinolinyl ~\N N~ ~ 1~ / N
1 L pyridyl 1 m 4, 4'-bipyridyl _ ._. ._. ~ y_ F. . ._k.~ > _~> E,,.v7~ ~ ~..:">~g~~~a>~~.~ >.~ .n~.. _ _._..
.~x..~.m.>,.> , .~.mr_..._.._.___.~.a~ , ~~~.~.~.~~T. _.___ _~_.~.~~_x~
In another aspect of the invention, a stable organic compound of the general formula (1B) is provided:
s_ Z
n Tq (1B) where Xg, X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
m is a number from 0-10, preferably I-4, most preferably 2;
Q, S and T are the same or different and are selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite group, -CF3 and an aliphatic group having I-24 carbon atoms which may be straight, branched or cyclic;
p and q are the same or different and are a number between 0-5;
r is a number between 0-4;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl (preferred substituent examples la-Im are pictured above); and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
Preferably a compound of general formula ( I B) exhibits intense luminescence, which may be photoluminescence and/or electroluminescence.
IS
A preferred embodiment of the invention, particularly for hole transporting properties, is described by the general formula (IB), where X$ is nitrogen;
X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 1-4.
Another preferred embodiment of the invention is described by the general formula (1B), where X$ is selected from the group consisting of a substituted. or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 0 to 4.
.._....._ _...__.__. . _., ,.,.~~r ,e_~,._~,~,,:~:~,~ ~,r~..,.~.~ _._._._ .._m....~~. ~._.._. ,.~.....: ...___..__ ._______.~.~.~,~..~
In another aspect of the invention, a stable organic compound of the general formula (1C) is provided:
N. a Z2 o ;~
~r (1C) where m is a number from 0-10, preferably 1-4, most preferably 2;
Q is selected from the group consisting of aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
r is a number between 0-4;
Z2, Z3 and Z4 may be the same or different substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl (preferred substituent examples la-lm are pictured above); and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
Preferably a compound of general formula (1C) exhibits intense luminescence, which may be photoluminescence and/or electroluminescence.
In a preferred embodiment of compounds of the general formula (1 C), Z3 is phenyl, Z4 is napthyl, m is 2 and ZZ is substituted quinolyl. A synthetic scheme depicting the preparation of such compound is pictured in Scheme 3; a working example of detailed synthetic procedures is provided in Example 5.
. . _ __ _ ....... , . ~.. ~u.,.. ~,"~~~ . ~._. a ~.~,,~. ...r~ ~ ...... _.
_.. _ .. __ _ ~....~.... . _.
As used herein "aliphatic" includes alkyl, alkenyl and alkynyl. An aliphatic group may be substituted or unsubstituted. It may be straight chain, branched chain or cyclic.
As used herein "aryl" includes heteroaryl and may be substituted or unsubstituted.
Preferred aryl groups for Q, S, and T are Z.
As used herein "unsubstituted" refers to any open valence of an atom being occupied by hydrogen.
As used herein "substituted" refers to the structure having one or more substituents.
Scheme 1. Preparation of example compounds of the general formula (lA).
aPA, Cul, K3P04, '~ N
N
Br H2N NH2 % ~S
Pd(PPh3)4, NaOH
N ~ B(OH)2 1 or 2 Scheme 2. Preparation of a further example compound of the general formula (lA).
BULi, B~OMB)g ~-mvnwNycmc ..,...._< ~. , . __., ;, nw ~ ~ ..w. m." ~,. 2fiLWNe. ._,..;r-mnx,TJns ~z-r. , _ _,::n,urtit%
.wn..az~:~Fp'F%cn~rtwms:.d:~u4..,.:~.r.,w....a~v..__.___..«,.......m._.A.....~o -..mn,a.....,.,.»..._,_,".,m._.".~.,..~.~u..",.."...sww.vr~,.mm~rcm~w~.,......-.---,.___.. _.e. .w..~....>,:...».,9meur Scheme 3. Preparation of an example compound of the general formula 1 C.
/ \ / ~ ~~ /
LiBu N \ / \ ~~ ~ N \ / \ /
B(i-OPr)3 \ ~ \ /
Br Pd(Otac)2 PPh3 NazCO 3 N
OMe /
I \ / /_\ OMe \ l \ iN
(6) ._.._ _ __ _ _._.._. ~~.~~. ~,...~,~: ~.~,~m _n___ __ Thus, the invention provides, for example, compounds 1-pyrerryl-2,2'-dipyridylamine (2), 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3), 4-[4'-(1-pyrenyl)biphenyl)-2,2'-dipyridylamine (4), 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5), and QNPB (6) which have the following structures:
_ _ _._ ..~~..~~w . .._t~-~,. #._--_ __-~-1-pyrenyl-2,2'-dipyridylamine (2) / \
N
N-_ (2) 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) / \
/ \ ~
N
N \ N
(3) 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4) (4) 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5) (5) 4-(1-naphthylphenylamino)-4'-(5-(8-methoxyquinolinyl))biphenyl (~NPB) (6) '_ N ~ / ~ ~ ,_\ OMe ~ /N
n (lA) where X5, X6 and X' are each independently selected from the group consisting of carbon and nitrogen;
n is a number from 0-2;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl; and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrile group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
In some embodiments, X5, X6 and X' may be each independently selected from the group consisting of a substituted carbon, an unsubstituted carbon and an unsubstituted nitrogen. In some embodiments, at least one of X5, X6 and X' is nitrogen. In some embodiments, X5, X6 and X' are nitrogen.
In a second aspect, the invention provides a compound having a general formula ( 1 B):
SP
Z
n Tq (1B) where Xg, X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
m is a number from 0-10;
Q, S and T are the same or different and are selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
p and q are the same or different and are a number between 0-~;
r is a number between 0-4;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyrid;yl, bipyridyl, indyl, and quinolinyl;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite graup, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
In some embodiments, Xg is selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon; X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 0 to 4. In some embodiments, X$
is nitrogen; X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 1 to 4.
In a third aspect, the invention provides a compound having a general formula ( 1 C):
jN Z2 m Q~
( 1 C) where Z2, Z3 and Z4 are each independently a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl;
m is a number from 0-10;
Q is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
r is a number between 0 and 4;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
In another aspect, the invention provides a photoluminescent or electroluminescent compound having a formula selected from the group consisting of 1-pyrenyl-2,2'-dipyridylamine (2), 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3), 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4), 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5) and QNPB (6).
Compounds of the invention may be photoluminescent and/or electroluminescent.
Compounds of the invention may be hole transporters.
In further aspect, the invention provides a method of synthesizing a compound of general formula (lA), comprising a step selected from the group consisting of 1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3P04+ 1,2-transdiaminocyclohexane + 1,4-dioxane 1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-brornopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid 4-( 1-pyrenyl)phenyl-2,2'-dipyridylamine(3 );
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4);
4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-BuLi 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5); and p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi p-N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + NazC03 ~ QNPB (6).
In further aspect, the inventian provides a method of synthesizing a compound of general ___.___.. .~..~.. _~~ ..-~~.- ~..~-.~.~ ~ ..n _.~~...._-__-._._r___. __ formula (1B), comprising a step selected from the group consisting of 1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3P04+ 1,2-transdiaminocyclohexane + 1,4-dioxane 1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-bromopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine(3);
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid 3 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4); and 4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-Buhi 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5).
In further aspect, the invention provides a method of synthesizing a compound of general formula (1C), comprising a step selected from the group consisting of p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi p N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + Na2C03 -~ QNPB (6).
In further aspects, the invention provides compositions comprising a compound of the invention, an organic polymer and a solvent.
In still further aspects, the invention provides a photoluminescent product or an electroluminescent product comprising a compound of the invention. The product may be a flat panel display device. The product may be a luminescent probe.
In another aspect, the invention provides a method of producing electroluminescence, comprising the steps of providing an electroluminescent compound of the invention and applying a voltage across said compound so that said compound electroluminesces.
In other aspects, the invention provides electroluminesce~nt devices for use with an applied voltage.
A first such device comprises: a first electrode, an emitter which is an electroluminescent compound of the invention, and a second, transparent electrode, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
A second such device comprises: a first electrode, a second, transparent electrode, an electron transport layer adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is an electroluminescent compound of the invention interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
A third such device comprises: a first electrode, a second, transparent electrode, a layer which is both an emitter and an electron transporter which is an electroluminescent compound of the invention and which is located adjacent the first electrode, and a hole transport layer which is interposed between the emitter and electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
A fourth such device comprises: a first electrode, a secomd, transparent electrode, a layer which is all of an emitter, an electron transporter and a hole transporter which is an electroluminescent compound of the invention and which is interposed between the first and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
A fifth such device comprises: a first electrode, a second, transparent electrode, an electron transport layer which is a compound of the invention and which is located adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
A sixth such device comprises: a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, a hole transport layer which is a compound of the invention and which is located adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an el,ectrie field so that the emitter electroluminesces.
A seventh such device comprises: a first electrode, a second, transparent electrode, a layer which is both an electron transporter and an emitter which is located adjacent the first electrode, and a hole transport layer which is a compound of the invention and which is interposed between _........__.._.___" "", s~.,rnaa,asw~ r.~~., ~s~aamawma, ~~aaxn~~~...._...
_~_~.__ ...,am,",A"~,., .._... .___._ the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
An eighth such device comprises: a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, anal a layer which is both an emitter and a hole transporter which is a compound of the invention and which is interposed between the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
In another aspect, the invention provides a method of detecting metal ions, comprising the steps of providing a photoluminescent compound of the invention, and detecting photoluminescence of said compound, wherein contact with a metal ion quenches said photoluminescence of said compound. The metal ions may be selected from the group consisting of Zn2+, Cu2+, Ni2+y Cdz+, HgZ+ and Ag+.
In another aspect, the invention provides a method of detecting acid, comprising the steps of providing a photolutninescent compound of the invention, and detecting photoluminescence of said compound, wherein protonation of said compound changes the state of said compound's photoluminescence.
In another aspect, the invention provides a method of harvesting photons, comprising the steps of providing a compound of the invention, and providing light such that photons strike said compound and charge separation occurs in said compound. In some embodiments, the separated charges may recombine and photons be released. In some embodiments, the separated charges may migrate to respective electrodes to produce a potential difference.
In another aspect, the invention provides a method of separating charges, comprising the steps of providing a compound of the invention, and providing light such that photons strike said compound and charge separation occurs in said compound. In some embodiments, the separated charges may recombine and photons be released. In some embodiments;
the separated charges may migrate to respective electrodes to produce a potential difference.
In other aspects, the invention provides a photocopier, a photovoltaic device, a photoreceptor, a solar cell and a semiconductor employing the afore-mentioned methods of harvesting photons and/or separating charges.
In another aspect, the invention provides a molecular switch comprising a compound of the invention that is capable of existing in more than one luminescent state, wherein acid, base, and/or incident light produces a change in the luminescent state of said compound. The invention further provides a circuit comprising such a molecular switch.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention and to show more clearly how it may be carried into effect, reference will now be made by way of example to the accompanying drawings, which illustrate aspects and features according to preferred embodiments of the present invention, and in which:
Figure 1 shows a preferred embodiment of a three layer electroluminescent (EL) display device according to the invention.
Figure 2 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 1-pyrenyl-2,2'-dipyridylamine (2) as a solid.
Figure 3 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 1-pyrenyl-2,2'-dipyridylamine (2) in a CHZC12 solution at a concentration of 2.55 x 10-6 M at 298K.
Figure 4 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) as a solid.
Figure 5 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) in a CHZC12 solution at a concentration of 2.55 x 106 M at 298K.
Figure 6 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-(4'(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4) as a solid.
Figure 7 shows the excitation (lower wavelength) and emission (higher wavelength) photoluminescence spectra of 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4) in a CHzCl2 solution at a concentration of 2.55 x 10-6 M at 298K.
Figure 8 shows an electroluminescence spectrum produced by compound 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) in a two layer EL device described in Example 6.
Figure 9 shows the crystal structure of compound (2).
Figure 10 shows the crystal structure of compound (3).
Figure 11 shows the crystal structure of compound (4).
Figure 12 shows the (-) photoluminescence (PL) spectrum of compound (4) and the (- - -) electroluminescence (EL) spectrum of compound (4) produced by a solid-state filin at 298K.
Figure 13 shows the dependence of Luminance (L) and Current Density (J) on Voltage (V) of a film of compound (4) in a two layer EL device of the following configuration: TfO/NPB
(40 nm)/compound(4) (40 nm)/LiF (1 nm)/Al, where NPB is the hole transport layer, compound (4) is both the emitter and electron transport layer and LiF is added to improve contact between the electron transport layer and the cathode.
Figure 14 shows the excitation (lower wavelength) and the emission (higher wavelength) spectra of compound (5) as a solid-state film (-) at 298K and as a CHzCl2 solution (CI) at a concentration of 10'S M at 298K.
Figure 15A is a cyclic voltametry diagram starting with the reduction of compound (5) in a mixture of CHZC12 and CH3CN. This figure provides information about the Lowest Unoccupied Molecular Orbital (LUMO) of the molecule and indicates promising electron transport properties of the molecule.
Figure 15B is a cyclic voltametry diagram starting with the oxidation of compound (S) in a mixture of CHZC12 and CH3CN. This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transport properties of the molecule.
Figure 16 shows the dependence of Luminance (L) and Current (I) on Voltage (V) of a single layer EL device of compound (4) prepared with the following configuration:
ITO/compound (4) (60 nm)/LiF(0.5 nm)/Al(140nm), where compound (4) is the hole transport layer, emitter and electron transport layer and LiF is added to improve contact between the film and the cathode.
Figure 17A shows the dependence of Current Density (J) on Voltage (V) of a film of compound (6) in a single layer EL device of the following configuration:
ITO/compound (6) (90 nm)/LiF (0.5 nm)/Al, where compound (6) is all of electron transport layer, emitter and hole transport layer and LiF is added to improve contact between the film and the cathode.
Figure 17B shows the dependence of Luminance (L) on Voltage (V) of a film of compound (6) in a single layer EL device of the following configuration:
ITO/compound (6) (90 nm)/LiF (0.5 nm)/Al, where compound (6) is all of electron transport layer, emitter and hole transport layer and LiF is added to improve contact between the film and the cathode.
Figure 18 shows the (-) photoluminescence spectrum of compound (6) and the (- --) electroluminescence spectrum of compound (6) produced by a single layer EL
device of the following configuration: ITO/compound (6) (90 nm)/LiF (0.5 nrn)/Al, where compound (6) is all of electron transport layer, emitter and hole transport layer and LiF is added to improve contact between the film and the cathode.
Figure 19A shows the dependence of Current Density (J) on Voltage ('~ of a film of compound (6) in a double layer EL device of the following configuration:
ITO/compound (6) (30, 60, 90, 120 nm)/Alq3 (40 nm)/LiF (0.5 nm)/Al, where compound (6) is the hole transport layer and Alq3 is both emitter and electron transport layer and LiF is added to improve contact . ~..~.,. ~ . .. ~e..,~.,. . ~* ~ *.~~ fi .. . . ., m._. .....,.. . ___..-m_ .
. ..- _.~ . .u.~..m ._.__ _._..__.
."n.'~A4H d , . ~,.,R:r~.tR~'WC..34.n.n:y'e,.,Fi"X~a.e s~.~a~,urr'~~" vw.wemx .R...a~.A..wrn.. ~ a..;..*myaww..n~
between the film and the cathode.
Figure 19B shows the dependence of Luminance (L) on Voltage (V) of a film of compound (6) in a double layer EL device of the following configuration:
ITO/compound (6) (30, 60, 90, 120 nm)/Alq3 (40 nm)lLiF (0.5 nm)/Al, where compound (6) is the hole transport layer and Alq3 is both emitter and electron transport layer and LiF is added to improve contact between the film and the cathode.
Figure 20 shows the crystal structure of (6).
Figure 21 is a cyclic voltammetry diagram starting with the oxidation of compound (6) in CHZCIz. This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transpou properties of the molecule.
DETAILED DESCRIPTION OF THE INVENTION
In a first aspect of the invention, a stable organic compound of the general formula (1A) is provided:
x= ~
~" \ /
\ /
(lA) where X5, X6 and X' are each independently selected from the soup consisting of carbon and nitrogen;
n is a number from 0-2;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl (preferred substituent examples la-lm are pictured below); and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
Preferably a compound of general formula (lA) exhibits intense luminescence, which may be photoluminescence and/or electroluminescence.
In preferred embodiments of compounds of the general formula (lA), X5, X6 and X' are each independently a substituted or unsubstituted carbon or an unsubstituted nitrogen. In some embodiments, one or two of X5, X6 and X' are nitrogen. In a preferred embodiment, X5, X6 and X' are all nitrogen. A synthetic scheme depicting the preparation of such compounds is pictured in Schemes 1 and 2; working examples of detailed synthetic procedures are provided in Examples 1 - 4.
/ \ ~ \
\ I / \ I /
1a 1-naphthyl 1b 2-naphthyl 1c 9-anthryl 1 d 9-phenanthryl 1e 1-pyrenyl ~t ~-pyrenyl ,g 4-pyrenyl 1 h biphenyl 1 i phenyl / ~ \
1j indyl 1k quinolinyl ~\N N~ ~ 1~ / N
1 L pyridyl 1 m 4, 4'-bipyridyl _ ._. ._. ~ y_ F. . ._k.~ > _~> E,,.v7~ ~ ~..:">~g~~~a>~~.~ >.~ .n~.. _ _._..
.~x..~.m.>,.> , .~.mr_..._.._.___.~.a~ , ~~~.~.~.~~T. _.___ _~_.~.~~_x~
In another aspect of the invention, a stable organic compound of the general formula (1B) is provided:
s_ Z
n Tq (1B) where Xg, X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
m is a number from 0-10, preferably I-4, most preferably 2;
Q, S and T are the same or different and are selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite group, -CF3 and an aliphatic group having I-24 carbon atoms which may be straight, branched or cyclic;
p and q are the same or different and are a number between 0-5;
r is a number between 0-4;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl (preferred substituent examples la-Im are pictured above); and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a vitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
Preferably a compound of general formula ( I B) exhibits intense luminescence, which may be photoluminescence and/or electroluminescence.
IS
A preferred embodiment of the invention, particularly for hole transporting properties, is described by the general formula (IB), where X$ is nitrogen;
X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 1-4.
Another preferred embodiment of the invention is described by the general formula (1B), where X$ is selected from the group consisting of a substituted. or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
X9 and X'° are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 0 to 4.
.._....._ _...__.__. . _., ,.,.~~r ,e_~,._~,~,,:~:~,~ ~,r~..,.~.~ _._._._ .._m....~~. ~._.._. ,.~.....: ...___..__ ._______.~.~.~,~..~
In another aspect of the invention, a stable organic compound of the general formula (1C) is provided:
N. a Z2 o ;~
~r (1C) where m is a number from 0-10, preferably 1-4, most preferably 2;
Q is selected from the group consisting of aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
r is a number between 0-4;
Z2, Z3 and Z4 may be the same or different substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl (preferred substituent examples la-lm are pictured above); and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
Preferably a compound of general formula (1C) exhibits intense luminescence, which may be photoluminescence and/or electroluminescence.
In a preferred embodiment of compounds of the general formula (1 C), Z3 is phenyl, Z4 is napthyl, m is 2 and ZZ is substituted quinolyl. A synthetic scheme depicting the preparation of such compound is pictured in Scheme 3; a working example of detailed synthetic procedures is provided in Example 5.
. . _ __ _ ....... , . ~.. ~u.,.. ~,"~~~ . ~._. a ~.~,,~. ...r~ ~ ...... _.
_.. _ .. __ _ ~....~.... . _.
As used herein "aliphatic" includes alkyl, alkenyl and alkynyl. An aliphatic group may be substituted or unsubstituted. It may be straight chain, branched chain or cyclic.
As used herein "aryl" includes heteroaryl and may be substituted or unsubstituted.
Preferred aryl groups for Q, S, and T are Z.
As used herein "unsubstituted" refers to any open valence of an atom being occupied by hydrogen.
As used herein "substituted" refers to the structure having one or more substituents.
Scheme 1. Preparation of example compounds of the general formula (lA).
aPA, Cul, K3P04, '~ N
N
Br H2N NH2 % ~S
Pd(PPh3)4, NaOH
N ~ B(OH)2 1 or 2 Scheme 2. Preparation of a further example compound of the general formula (lA).
BULi, B~OMB)g ~-mvnwNycmc ..,...._< ~. , . __., ;, nw ~ ~ ..w. m." ~,. 2fiLWNe. ._,..;r-mnx,TJns ~z-r. , _ _,::n,urtit%
.wn..az~:~Fp'F%cn~rtwms:.d:~u4..,.:~.r.,w....a~v..__.___..«,.......m._.A.....~o -..mn,a.....,.,.»..._,_,".,m._.".~.,..~.~u..",.."...sww.vr~,.mm~rcm~w~.,......-.---,.___.. _.e. .w..~....>,:...».,9meur Scheme 3. Preparation of an example compound of the general formula 1 C.
/ \ / ~ ~~ /
LiBu N \ / \ ~~ ~ N \ / \ /
B(i-OPr)3 \ ~ \ /
Br Pd(Otac)2 PPh3 NazCO 3 N
OMe /
I \ / /_\ OMe \ l \ iN
(6) ._.._ _ __ _ _._.._. ~~.~~. ~,...~,~: ~.~,~m _n___ __ Thus, the invention provides, for example, compounds 1-pyrerryl-2,2'-dipyridylamine (2), 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3), 4-[4'-(1-pyrenyl)biphenyl)-2,2'-dipyridylamine (4), 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5), and QNPB (6) which have the following structures:
_ _ _._ ..~~..~~w . .._t~-~,. #._--_ __-~-1-pyrenyl-2,2'-dipyridylamine (2) / \
N
N-_ (2) 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) / \
/ \ ~
N
N \ N
(3) 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4) (4) 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5) (5) 4-(1-naphthylphenylamino)-4'-(5-(8-methoxyquinolinyl))biphenyl (~NPB) (6) '_ N ~ / ~ ~ ,_\ OMe ~ /N
(6) (Note that this same substituent, 2,2'-dipyridylamine (dpa), is called deprotonated di-2-pyridylamine in U.S. Patents No. 6,500,569 and No. 6,312,835 by Borne of the present inventors.) The invention provides compounds that are photoluminescent and, in at least some embodiments of the invention, electroluminescent; they can produce intense light.
The invention also provides a method of producing photoluminescence comprising the steps of providing a photoluminescent compound of the invention having a formula as set out above; and irradiating said photoluminescent compound with radiation of a wavelength suitable for exciting the compound to photoluminescence.
The invention further provides a method of producing electroluminescence comprising the steps of providing an electroluminescent compound of the invention having a fomrmla as set out above; and applying a voltage across said electroluminescent compound.
The invention further provides an electroluminescent device for use with an applied voltage, comprising: a first electrode, an emitter (e.g., phosphor) which is an electroluminescent compound of the invention, and a second, transparent electrode, wherein a voltage is applied between the two electrodes to produce an electric field across the emitter.
'The emitter consequently eleetroluminesces. In some embodiments of the invention, the device includes one or more charge transport layers interposed between the emitter and one or both of the electrodes.
For example, spacing of a preferred embodiment of the device, called for the purposes of the present specification a "three layer EL device", is: first electrode, first charge transport layer, emitter, second charge transport layer, and second, transparent electrode.
In certain embodiments of the invention, the device includes one or more compounds of the invention acting as one or more charge transport layers and~'or emitters) interposed 'between the electrodes.
In one embodiment of the invention, called for the purposes of the present specification a "two layer EL device", the spacing is: first electrode, charge transport layer, emitter/second charge transport layer, and second electrode. A working example of a two layer EL device is described in Example 6, refernng to Figure 8. Here, compound. 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) acted as both an emitter and a charge (electron) transport layer.
In another embodiment of the invention, called for the purposes of the present specification a "one layer EL device", the spacing is: first electrode, first charge transport layer/emitter/second charge transport layer, second electrode. A working example of a one layer EL device is described in Example 7, and luminance and current produced are shown graphically ..,,.r .., . y" 5, n x.. ...... r.u.r..y_.,~ ' r~IR,rT,aF'z;:c . ,..,. ..,o..
rx:zwm. e........ . _.....~,...... ~ . . .....
. ~ki~ r'~~4GAP6~r~~"~W ~ASSeer.~.~" c.. ~ ~7....-~..~,».,-.,.,.~......»..".a.,..":,....w,r... ...r...r....,.~._...-..-_ _ , .
_..__.._.....r..,w~.n..~~.w...~,.,..
in Figure 16. Similarly, the luminance and current density for a single layer EL device of compound (6) are shown graphically in Figures 17A and 17B.
An advantage of preferred compounds of the invention is that they are highly soluble in common organic solvents such as toluene, diethyl ether, tetrahydrofuran (THF), and dichloromethane. This permits the compounds to be blended easily and conveniently with organic polymers. The role of the organic polymer in such a mixture is at least two-fold: First, a polymer can provide protection for the compound from air degradation. Second, a polymer host matrix permits the use of a spin-coating or dip-coating process as an alternative way to make films. Although spin-coating and dip-coating processes may not produce as high quality films as those produced by chemical vapor deposition or vacuum deposition, they are often much faster and more economical.
Accordingly, the invention further provides methods of applying compounds as described above to a surface. These methods include solvent cast from solution, electrochemical deposition, vacuum vapor deposition, chemical vapor deposition, spin coating and dip coating.
The compounds may be applied alone or with a carrier. In some embodiments of the invention, they are applied in a composition including an organic polymer. Such compositions are also encompassed by the invention.
As an example of this application, compounds of the invention are expected to form a clear transparent solution with the weakly luminescent polymer poly(N
vinylcarbazole) (PVK) in CHZC12/C6HSC1. This can be converted to a transparent film by evaporating the toluene solvent via either a dip-coating or spin-coating process. Films obtained. in this way are stable. (Jertain polymers such as, for example, PVK, are expected to further enhance the luminescence of an emitter in the film.
The invention provides a method of producing electroluminescence comprising the steps of providing an electroluminescent compound of the invention having the general formula (lA), (1B) or (1C) as set out above; and applying a voltage across said electroluminescent compound so that the compound electroluminesces.
According to the invention, electroluminescent devices for use with an applied voltage are provided. In general, such a device has a first electrode, an emitter which is an electroluminescent compound of the invention, and a second, transparent electrode, wherein a voltage is applied between the two electrodes to produce an electric field across the emitter of sufficient strength to cause the emitter to electroluminesce. Preferably, the first electrode is of a metal, such as, for example, aluminum, which reflects light emitted by the compound; whereas the second, transparent electrode permits passage of emitted light therethrough. The transparent electrode is preferably of indium tin oxide (ITO) glass or an equivalent known in the art. Here, the first electrode is the cathode and the second electrode is the anode.
Referring to Figure 1, a preferred embodiment of an electroluminescent device of the invention is shown. The emitter is interposed between an electron transport layer (e.g., tris-(8-hydroxyquinoline)aluminum (Alq3) or 2-(biphenyl-4-yl)-5-(4-tent-butyl phenyl)-1,3,4-oxadiazole (PBD)) adjacent the first metal electrode and a hole transport layer (e.g., N,N'-di-1-naphthyl-N,N'-diphenylbenzidiine (NPB)) adjacent the second, transparent electrode. The choice; of the materials employed as charge transport layers will depend uporA the specific properties of the particular emitter employed. The hole transport layer or the electron transport layer may also function as a supporting layer. The device is connected to a voltage source such that an electric field of sufficient strength is applied across the emitter. Light, :preferably blue light, consequently emitted from the compound of the invention passes through the transparent electrode. Some emitters may additionally function as an electron transport material and/or as a hole transport material in the device. Although some of the compounds of the invention may act in all three capacities, the best efficiency may be obtained by limiting the compound's role to one or two. Furthermore, a compound of the invention may act as a charge transport layer fir another emitter which may or may not also be a compound of the invention.
In some embodiments of the invention, the device includes one or more charge transport layers interposed between the emitter and one or both of the electrodes. Such charge transport layers) are employed in prior art systems with inorganic salt emitters to reduce the voltage drop across the emitter. In a first example of such a device, layers are arranged in a sandwich in the following order: first electrode, charge transport layer, emitter, second charge transport layer, and second, transparent electrode. In a preferred embodiment of this type, a substrate of glass, quartz or the like is employed. A reflective metal layer (corresponding to the first electrode) is deposited on one side of the substrate, and an insulating charge transport layer is deposited on the other side. The emitter layer which is a compound of the invention is deposited on the charge transport layer, preferably by vacuum vapor deposition, though other methods may be equally effective. A transparent conducting electrode (e.g., ITO) is then deposited on the emitter layer.
An effective voltage is applied to produce electroluminescence of the emitter.
In a second example of an EL device of the invention, a second charge transport layer is employed, and the sandwich layers are arranged in the following order: first electrode, first charge transport layer, emitter, second charge transport layer and second, transparent electrode.
Electroluminescent devices of the invention may include one or more of the blue-emitting compounds described herein. In some embodiments of the invention, an electroluminescent .___ . _ .w._ ~., _ _.,.,~~~,._ ,. ~. .~.. __..__ . . . , ,.,<
device such as a flat panel display device may include not only a blue-emitting phosphor as described herein, but may be a multiple-color display device including one or more other phosphors. The other phosphors may emit in other light ranges, e.g., red, green, andlor be "stacked" relative to each other. Convenient materials, structures and uses of electroluminescent display devices are described in Rack et al., 1996.
For photoluminescence, the compounds absorb energy from ultraviolet radiation and emit visible light near the ultraviolet end of the visible spectrum e.g., in the blue region. For electroluminescence, the absorbed energy is from an applied electric field. It is expected that the luminescence of compounds of the unvention can be readily quenched by the addition of acid or metal cations such as Zn2+, Cuz+, Ni~+ Cd2+, Hgz+, Ag+ and H+ (Pang et al., 2001, Yang et al., 2001 ).
The invention further provides methods employing compounds of the invention to harvest photons, and corresponding devices for such use. Spectroscopic studies have demonstrated that compounds of the invention have high efficiency to harvest photons and produce highly polarized electronic transitions. In general, when such compounds are excited by light, a charge separation occurs within the molecule; a first portion of the molecule has a negative charge and a second portion has a positive charge. Thus the first portion acts as an electron donor and the second portion as an electron acceptor. If recombination of the charge separation occurs, a photon is produced and luminescence is observed. In photovoltaic devices, recombination of the charge separation does not occur; instead the charges move toward an anode and a cathode to produce a potential difference, from which current can be produced.
Molecules with the ability to separate charges upon light initiation are useful for applications such as photocopiers, photovoltaic devices and photoreceptors.
Organic photoconductors provided by the present invention are expected to be useful in such applications, due to their stability and ability to be spread into thin films. Related methods are encompassed by the invention.
Organic semiconducting materials can be used in the manufacture of photovoltaic cells that harvest light by photoinduced charge separation. To realize an efficient photovoltaic device, a large interfacial area at which effective dissociation of excitons occurs must be created; thus an electron donor material is mixed with an electron acceptor material. (Here, an exciton is a mobile combination of an electron and a hole in an excited crystal, e.g., a semiconductor.) Organic luminescent compounds as semiconductors are advantageous due to their long lifetime, efficiency, low operating voltage and low cost.
Photocopiers use a light-initiated charge separation to attract positively-charged molecules of toner powder onto a drum that is negatively charged.
The invention further provides methods employing compounds of the invention to detect metal ions. The change in the luminescence upon coordination of metal ions may be useful for detection of gunpowder residue, bomb making activity, and/or environmental contamination such as heavy metal contamination of food or soil or water, as well as for detection of sites of meteor impact and even interplanetary exploration.
The invention further provides methods employing compounds of the invention to detect acid. This aspect of the invention is expected to be useful for a variety of applications, including, without limitation, pH sensors, as well as detection of contamination, particularly environmental contamination (e.g., acidity of lakes, soil, etc.).
The invention further provides molecular switches employing compounds as described above, and methods of use thereof.
Information processing systems of current computers are based on semiconductor logic gates or switches (Tang et al.,1987). By reducing the switching elements to a molecular level, the processing capability and memory density of computers could be increased by several orders of magnitude and the power input could be decreased significantly (Leung et ad., 2000).
Candidates for this purpose are molecules that are capable of undergoing reversible transformations in response to chemical, electrical and/or optical stimulation, and producing readily detectable optical signals in the process. For example, t:he respective neutral forms of compounds of the invention (2), (3), (4), (5) and (6), when in solution, emit blue luminescence.
The neutral forms can be easily converted to the non-luminescent protonated forms by the addition of acid. These can be switched back to the depronated forms by the addition of a base.
Three-state molecular circuits based on (2), (3) and (4) with OH-, H+and ultraviolet light as inputs and visible light as outputs have been established.
Example 1 to Example 5 below provide detailed descriptions of the syntheses of compounds (2), (3), (4), (5) and (6) respectively. As would be apparent to a person of ordinary skill in the art, other functionalities may be included in derivatives according to the invention.
Alternatively, starting materials may be modified to include, but are not limited to, funetionalities such as ether, epoxide, ester, amide or the like. Such functionalities may in some cases confer desirable physical or chemical properties, such as increased stability or luminescence.
WORKING EXAMPLES
All starting materials were purchased from Aldrich Chemical Company and used without further purification. Solvents were freshly distilled over appropriate drying reagents. All experiments were carried out under a dry nitrogen atmosphere using standard Schlenk Techniques unless otherwise stated. Thin Layer Chromatography was carried out on SiO2 (silica gel F2S4, Whatman). Flash chromatography was carried out on silica (siliica gel 60, 70-230 mesh). 'H and'3C spectra were recorded on a Broker Avance 300 spectrometer operating at 300 and 75.3 MHz respectively. Excitation and emission spectra mere recorded on a Photon.
Technologies International QuantaMaster Model 2 spectrometer. Spin coating was done on Chemat Technology spin-coater KW-4A and vacuum deposition using a modified Edwards manual diffusion pump. The EL spectra for compound (3) (see Figure 8) were taken using Ocean Optics HR2000 and all data involving current, voltage and lumiinosity using a Keithley 238 high current source measure unit. The EL spectra for compound (4) (see Figure 12) were taken using a Photo Research - 6S0 Spectra Colorimeter. Data collection for the X-ray crystal structural determinations were performed on a Broker SMART CCD 1000 X-ray diffractometer with graphite-monochromated molybdenum Ka radiation (~. = 0.710'73 !~) at 298K and the data were processed on a Pentium PC using the Broker AXS Windows NT SHELXTL software package (version 5.10). Elemental analyses were performed by Canadian Microanalytical Service Ltd., (Delta, British Columbia, Canada). Melting points were determined on a Fisher-Johns melting point apparatus. Syntheses of precursors p-{2,2'-dipyridylamino)phenylboronic acid and p-(2,2'-dipyridylamino)biphenylboronic acid were based on a modified literature method (Jia et al., 2003).
Example 1: 1-pyrenyl-2, 2 dipyridylamine (2). The mixture of 0.145 g, 1-bromopyrene (O.S mmol), 0.10 g 2,2 dipyridylamine (O.S8 mmol), 0.125 g Cu~I, 0.235 g K3P04, 0.033 mL 1,2-transdiaminocyclohexane and 1mL 1,4-dioxane was stirred at 110°C for 24 hours. After cooling to room temperature, the mixture was extracted with dichloromethane (3 x 1 SmL). The solvent was evaporated under reduced pressure. The residue was subjected to column chromatography on silica gel (CH3COOEt/Hexane, 2:1) to afford a white compound {2) in 39%
yield. The molecular structure of (2) was confirmed by X-ray crystallography, the structure is pictured in Figure 9. 'H NMR in CDZC12 at 2S°C: 8 ppm = 8.31(d, J = 8.1, 1H), 8.27(m, 3H), 8.19 (m, 3H), 8.06(m, 3H), 7.95 (d, J = 8.1, 1H), 7.56 (m, 2H), 7.08(td, d = 8.~4, 0.9, 2H), 6.94(ddd, J == 7.2, 4.8, 1H). 13C NMR in CDZCIz at 2S°C, ~ ppm: 159.08, 148.72, 139.16, 137.94, 131.81, 131.62, 131.12, 129.65, 128.91, 128.71, 128.20, 127.83, 126.94, 126.71, 126.53, 126.11, 125.94, 125.33, 123.45, 118.27, 116.57. Elemental analysis calculated. for C26H,~N3 : C, 84.1, H, 4.58, 11.32.
Found: C, 83.84, 4.72, 11.35. See Table 1 for ~.max values for the emission and excitation of (2) as well as its quantum efficiency. See Figure 2 for the photoluminescence spectra of (2) as a solid, and Figure 3 for the photoluminescence spectra of (2) as a solution.
(It is of interest that intermolecular quenching does not appear to be a factor when tlhis compound is in the solid state;
rather, it is still luminescent.) Table 1. Excitation, emission and photoluminescent quantum efficiency of compounds (2), (3), (4), (5) and (6) in CHZCIz at ambient temperature.
Compound Excitation e~",~ Emission ~.max Quantum Efficiency 2 360 nm 415 mn 70%
3 350 nm 433 ntn 72%
4 350 nm 437 nm 76%
362 nm 454 nm >40%
6 354 nm 442 nm 31%
Example 2: Synthesis of 4-(1-pyrenyl)phenyl-2.2'-dipyridylarnine (3). A
mixture of l-bromopyrene (0.5 g, 1.78 mmol), Pd(PPh3)4 (0.062 g , 0.054 mmol) and toluene(40 mL) was stirred for 10 minutes under NZ(g). A solution ofp-(2,2'-dipyridylamino)phenylboronic acid (0.57 g, 1.96 mmol) in 20 mL EtOH and a solution of NaOH (0.8 g) in 20 mL H20 were added.
The resulting mixture was heated and stirred at reflux for 24 hours and was then allowed to cool to room temperature. The water layer was separated and extracted with methylene chloride (CHzCl2) (3 x 15 mL). The combined organic layers were dried. over MgS04, and evaporated under reduced pressure. Purification of the crude product was performed by column chromatography (THF:Hexane, 3:2) and afforded (3) as a white solid in 83%
yield. The molecular structure of (3) was confirmed by X-ray crystallography, the structure is pictured in Figure 10. 1H NMR in CD2C12 at 2~°C: 8 ppm = 8.40(ddd, J = 4.8, 1.8, 0.9, 2H), 8.36(d, J = 9.3, 1H), 8.27(m, 3H), 8.11(m, SH), 7.68(m, 4H), 7.40(d, J = 8.4, 2H), 7.19(d, J =
8.1, 2H), 7.05(ddd, J = 7.2, 4.8, 0.9,2 H). 13C NMR in CDZC12 at 25C, 8 ppm: 158.91, 149.11, 145.16, 138.56, 138.17,137.80, 132.27, 132.18, 131.68, 131.27, 130.13, 129.09, 128.35, 128.12, 128.06, 127.58, 126.75, 125.88, 125.8, 125.63, 125.60, 125.42, 119.02, 118.63, 117.90.
Elemental analysis calculated for C32H21N3~1~3H2O;C, 84.77, H, 4.78, N, 9.27. Found: C, 84.89, 4.76, 9.42. See Table 1 for emission and excitation ~,m~ values and quantum efficiency of compound (3). See Figure 4 for the photoluminescence spectra of (3) as a solid, and Figure 5 for the photoluminescence spectra of (3) as a solution.
Example 3: Synthesis of 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridyYamine (4). 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine was prepared by the same procedure as that used to prepare (4) above. From 1-bromopyrene (0.2983 g, 1.045 mmol), Pd(PPh3)4 (0.036 g , 0.031 mmol), p-(2,2'-dipyridylamino)biphenylboronic acid (0.4218 g, 1.149 mmol) and NaOH(0.5 g) was obtained (4) as a white solid in 71.4% yield. The molecular structure of (4) was confirmed by X-ray crystallography, the structure is pictured in Figure 11. 1H NMR in CDZC12 at 2S°C: b ppm = 8.36(ddd, J = 4.8, 1.8, 0.9, 2H), 8.32(d, J = 1.5, 1H), 8.26, (m,3H), 8.11(m, SH), 7.88(dd, J = 1.8, 6.6, 2H), 7.78(m, 4H), 7.66(m, 2H), 7.33(dt, J = 9.0, 2.4, 2H), 7.14(d, J = 8.4, 2H), 7.02(ddd, J = 7.2, 4.8, 0.9, 2H). '3C NMR in CDzCl2 at 25°C, 8 ppm 158.79, 149.07, 146.40, 140.74, 140.03, 138.12, 138.00, 132.66, 132.53, 132.18, 131.74e, 131.67, 131.31, 130.04, 129.13, 128.71, 128.30, 128.17, 128.07, 127.54, 126.77, 125.87, 125.81, 125.2, 125.40, 118.97, 117.76, 116.22, 112.06. Elemental analysis calculated for C38Hz5N3: C, 87.19, H, 4.78, N, 8.03. Found:
C, 87.56, H, 4.94, N, 8.28. See Table 1 for emission and excitation ~.max values and quantum efficiency of compound (4). See Fi~ure 6 for the luminescence spectra of (4) as a solid, and Figure 7 for the luminescence spectra of (4) as a solution. The photoluminescence spectra is overlaid with an electroluminescence spectrum in Figure 12. Luminance-voltage and current density-voltage diagrams of (4) in a 2-layer EL device are shown in Figure 13.
Figure 16 shows the luminance-voltage and current-voltage diagrams of (4) in a single layer EL
device.
Example 4. Synthesis of 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5): To a THF
(20m1) of 4-Iodo-4'-diphenylaminobiphenyl (Koene et al. 1998) (O.Sg, 1.l2mmol) was added a hexane solution of n-BuLi (0.77m1, 1.23mmo1) at -78°C. After being stirred for 1 h at this temperature, B(OMe)3 (0.2m1, 2.Smmol) was added. After the mixture was stirred for another 1 h at -~78°C, it was warmed to ambient temperature and stirred overnight. The solution was partitioned between saturated aqueous NH4Cl (30 mL) and CHZC12 (30 mL). The adueous layer was extracted further with dichloromethane (2 X 30 mL) and the combined organic layers were dried over MgS04.
The solvent was evaporated under vacuum to provide the boronic acid in 96%
yield. A mixture of 1-bromopyrene (0.258, 0.89mmo1), Pd(PPh3)4 (0.0318 , 0.027 mmol) and toluene (40 ml) was stirred for 10 min. The above boronic acid (0.368, 0.98 mmol) in 15 ml EtOH
and NazC',03(0.48 g) in 15 ml H20 were subsequently added. The mixture was stirred and refluxed for 24 h and then allowed to cool to room temperature. The water layer was separated and extracted with CHZC12 (3 x 15 ml). The combined organic layers were dried over MgS04, and the solvents were evaporated under reduced pressure. Purification of the crude product by column chromatography (CHZCI2:Hexane, 1:3) afforded (5) as colorless solid in 88% yield. 'H NMR in CD3Cl (8, ppm, 25°C): 8.29 (d, J = 6.9, 1H), 8.26(d, J = 5.7, 1H), 8.22 (t, J = 7.8, 2H), 8.02 - 8.13(m, SH), 7.80 (d, J = 8.1, 2H), 7.72 (d, J = 8.4, 2H), 7.63 (d, J = 8.4, 2H), 7.3 - 7.35(m, 4 H), 7.19 - 7.24 (m, 6H), 7.09 (t, J = 7.2, 2H). See Table 1 for emission and excitation ~,m~
values and quantum efficiency of compound (5) and Figure 14 for the photoluminescence spectra of (5) as a solid, and as a solution. Figure 15A shows a cyclic voltametry diagram starting with the reduction of (5) in a mixture of CHZCIz and CH3CN. This figure provides information about the Lowest Unoccupied Molecular Orbital (LUMO) of the molecule and indicates promising electron transport properties of the molecule. Figure 15B shows a cyclic voltametry diagram starting with the oxidation of (5) in a mixture of CHZCIz and CH3CN. This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transport properties of the molecule.
Example 5. Synthesis of 4-(1-naphthylphenylamino)-4"-{5-(8-methoxyquinolinyl))biphenyl (QNPB) (6): p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide (1.55 g, 3.12 mmol) was reacted with butyl lithium (2.14 mL of 1.0 M solution in hexane, 3.43 mmol) at -78°C in 50 mL THF. Following an addition of B(i-UPr)3 (1.1 g), a boric acid intermediate p-N-( 1-naphthyl)-N-phenylamino-biphenyl-B(OH;)Z was isolated. p-N-( 1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 (1.0 g, 2.4 mmol) was reacted with 5-bromo-8-methoxyquinoline (0.48 g, 2.0 mmol) in a mixture of solvents: ethanol (20 mL), toluene (35 mL) and water (15 mL) in the presence of Pd(OAc)2 (0.026 g), PPh3 (0.063 g), and Na2C03. Product QNPB (see structure in Scheme 3) was produced in 85% yield. Elemental analysis: calc for C38HZgN2O, C 86.36; H, 5.30; N, 5.30. Found: C 86.40; H, 5.29; N, 5.49. The molecular structure of (6) was confirmed by X-ray crystallography; the structure is pictured in Figure 20.
'H NMR for QNPB (ppm, CDCl3): 8.97 (d, 1H), 8.32 (d, 1H), 8.00 (d, 1H), 7.92 (d, 1H), 7:82 (d, 1H), 7.68 (d, 2H), 7.50 (m, 7H), 7.42 (m, 3H), 7.24 (d, 1H), 7.15 (m, SH), 7.00 (t, 1H), 4.17 (s, 3H). See Table 1 for emission and excitation ~,m~ values anal quantum efficiency of compound (6). A current density-voltage diagram and luminance-voltage diagram for compound (6) in a single layer EL device are shown in Figures 17A and 1 TB. The photoluminescence spectrum and the electroluminescence spectrum of compound (i5) in a single layer EL device are shown in Figure 18. A current density-voltage diagram and luminance-voltage diagram of compound (6) in a double layer EL device are shown in Figure 19A and 19B where (6) is the hole transport layer and Alq3 is the emitter and electron transport layer.
Example 6. Preparation of a two layer EL device. A two layer device was made using compound 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) as both a charge (electron) transport layer and an emitting layer. The configuration was: cathode, electron transport and emitting layer of compound (3) (50 nm), hole transport layer (50 nm) of NPB, anode. The emitting layer was fabricated on an ITO substrate, which was cleaned by an ultraviolet ozone cleaner immediately before use. Both the organic layers and a metal cathode of A1 were deposited by conventional vapor vacuum deposition. Prior to the deposition, all the organic materials were purified via a train sublimation method (Wagner et al., 1982).
Example 7. Preparation of a one layer EL device. A one layer device was made using compound (4) as an emitting Layer, an electron transport layer and a hole transport layer. The configuration was: cathode, film of compound (4) (SO nm), anode. The compound (4) layer was fabricated on an ITO substrate, which was cleaned by an ultraviiolet ozone cleaner immediately before use. Both the organic layer and a metal cathode of Al were deposited by conventional vapor vacuum deposition. Prior to the deposition, all the organic materials were purified via a train sublimation method (Wagner et ad., 1982). Figure 13 shows a plot of the current vs. voltage and luminance vs voltage for this single layer device containing a 60 nm thick film of (4').
Example 8. Preparation of a two layer EL device. A tvvo layer device was made using compound QNPB (6) as a hole transport layer and Alq3 as both an electron transport layer and an emitting layer. The configuration was: cathode, electron transport and emitting layer of Alq3, hole transport layer of QNPB (6), anode. The emitting layer was fabricated on an ITO substrate, which was cleaned by an ultraviolet ozone cleaner immediately before use. Both the organic layers and a metal cathode of Al were deposited by conventional vapor vacuum deposition. Prior to the deposition, all the organic materials were purified via a train sublimation method (Wagner et al., 1982). Several such two layer EL devices were prepared with varying thicknesses (30, 60, 90, 120 nm) of the QNPB (6) hole transport layer and constant thickness (40 nm) of the Alq3 electron transport and emitter layer. A plot of current density vs. voltage for these devices is shown in Figure 19A and a corresponding plot of luminance vs. voltage is shown in Figure 19B.
A cyclic voltammetry diagram starting with the oxidation of (6) in CHZC12 is shown in Figure 21.
This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transport properties of the molecule.
All scientific and patent publications cited herein are hereby incorporated in their entirety by reference.
Although this invention is described in detail with reference to preferred embodiments thereof, these embodiments are offered to illustrate but not to li~rnit the invention. It is possible to make other embodiments that employ the principles of the invention and that fall within its spirit and scope as defined by the claims appended hereto.
Ashenhurst, J.; Brancaleon, L; Hassan, A.; Liu, W.; Schmider, H.; and Wang, S.
"Blue Luminescent Organoaluminum Compounds: Alz(CH3)4(7-azain)z, Alz(CH3)z(7-azain)4, AIz(CH3)(OCH(CF3)z)s{7-azam)z, Alz(~-OCH(CF3)z(CH3){7-azain)z((OCH(CF 3)2)2, Al 0~.3-O)(CH3)(7-azain)4(OCH(CF3)z)z, and A14(~,3-O)z(7-azain)6(OCH(CF3)z)z {7-azain = Deprotonated 7-Azaindole)." Organometallics (1998) 17: 3186-3195.
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Gao, S.; Wu, Q.; Wu, G.; and Wang, S. "Highly Fluxional Blue Luminescent Aluminum Complexes: Al(CH3)(7-azain-2-Ph)z(7-azainH-2-Ph), A13(m3-O)(CH3)3(7-azain-2-Ph)4, and AI3((m3-O)(CH3)3(7-azain-2-CH3)4, 7-azain = 7-azaindole anion.."
Organometallics (1998)17:
4666-4674.
Hassan, A.; and Wang, S. "First blue luminescent diborate compound: B2(m-O)Etz(7-azain)z (7-azain = 7-azaindole anion)." Chem. Commun. (1998) 211-212.
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Leung, L.M.; Lo, W.Y.; So, S.K.; Lee, K.M.; and Choi, W.K. J. "A High-Efficiency Blue Emitter for Small Molecule-Based Organic Light-Emitting Diode. " J Am. Chem.
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Liu, S.; Wu, Q.; Schmider, H.L.; Aziz, H.; Hu, N.; Popovic, Z.; and Wang, S.
"Syntheses, Structures, and Electroluminescence of New BIue/Green Luminescent Chelate Compounds:
Zn(2-py-in)Z(THF), BPh2(2-py-in), Be(2-py-in)2, and BPh2(2-py-aza), 2-py-in =
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Tetrahedron Letters (2001) 42(19): 3355-3357.
Yang, W.; Chen, L.; and Wang, S. "Syntheses, Structures, and Luminescence of Novel Lanthanide Complexes of Tripyridylamine, N,N,N;N'-Tetra(2-pyridyl)-1,4-phenylenediamine, and N,N,N;N'-Tetra(2-pyridyl)-biphenyl-4,4'-diamine." Inorganic Chemistry (2001) 40: 507-515.
_., . ._. _,..,.".... ......_...» , ... ..,~ _.,..~", ,y",~., rv.,...
fi'T4~raw,=::vT"~i~-~.;wtrs,<c:.:;rr... ...wm. . ,.,_.,K~,,,~;",,yyF.~:~"R.~-;-,...."~;.s:"womw:a...w.,a._.enwop,w~a~.a.».~.e..»,..-.,.~.- -___.._-_._.._
The invention also provides a method of producing photoluminescence comprising the steps of providing a photoluminescent compound of the invention having a formula as set out above; and irradiating said photoluminescent compound with radiation of a wavelength suitable for exciting the compound to photoluminescence.
The invention further provides a method of producing electroluminescence comprising the steps of providing an electroluminescent compound of the invention having a fomrmla as set out above; and applying a voltage across said electroluminescent compound.
The invention further provides an electroluminescent device for use with an applied voltage, comprising: a first electrode, an emitter (e.g., phosphor) which is an electroluminescent compound of the invention, and a second, transparent electrode, wherein a voltage is applied between the two electrodes to produce an electric field across the emitter.
'The emitter consequently eleetroluminesces. In some embodiments of the invention, the device includes one or more charge transport layers interposed between the emitter and one or both of the electrodes.
For example, spacing of a preferred embodiment of the device, called for the purposes of the present specification a "three layer EL device", is: first electrode, first charge transport layer, emitter, second charge transport layer, and second, transparent electrode.
In certain embodiments of the invention, the device includes one or more compounds of the invention acting as one or more charge transport layers and~'or emitters) interposed 'between the electrodes.
In one embodiment of the invention, called for the purposes of the present specification a "two layer EL device", the spacing is: first electrode, charge transport layer, emitter/second charge transport layer, and second electrode. A working example of a two layer EL device is described in Example 6, refernng to Figure 8. Here, compound. 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) acted as both an emitter and a charge (electron) transport layer.
In another embodiment of the invention, called for the purposes of the present specification a "one layer EL device", the spacing is: first electrode, first charge transport layer/emitter/second charge transport layer, second electrode. A working example of a one layer EL device is described in Example 7, and luminance and current produced are shown graphically ..,,.r .., . y" 5, n x.. ...... r.u.r..y_.,~ ' r~IR,rT,aF'z;:c . ,..,. ..,o..
rx:zwm. e........ . _.....~,...... ~ . . .....
. ~ki~ r'~~4GAP6~r~~"~W ~ASSeer.~.~" c.. ~ ~7....-~..~,».,-.,.,.~......»..".a.,..":,....w,r... ...r...r....,.~._...-..-_ _ , .
_..__.._.....r..,w~.n..~~.w...~,.,..
in Figure 16. Similarly, the luminance and current density for a single layer EL device of compound (6) are shown graphically in Figures 17A and 17B.
An advantage of preferred compounds of the invention is that they are highly soluble in common organic solvents such as toluene, diethyl ether, tetrahydrofuran (THF), and dichloromethane. This permits the compounds to be blended easily and conveniently with organic polymers. The role of the organic polymer in such a mixture is at least two-fold: First, a polymer can provide protection for the compound from air degradation. Second, a polymer host matrix permits the use of a spin-coating or dip-coating process as an alternative way to make films. Although spin-coating and dip-coating processes may not produce as high quality films as those produced by chemical vapor deposition or vacuum deposition, they are often much faster and more economical.
Accordingly, the invention further provides methods of applying compounds as described above to a surface. These methods include solvent cast from solution, electrochemical deposition, vacuum vapor deposition, chemical vapor deposition, spin coating and dip coating.
The compounds may be applied alone or with a carrier. In some embodiments of the invention, they are applied in a composition including an organic polymer. Such compositions are also encompassed by the invention.
As an example of this application, compounds of the invention are expected to form a clear transparent solution with the weakly luminescent polymer poly(N
vinylcarbazole) (PVK) in CHZC12/C6HSC1. This can be converted to a transparent film by evaporating the toluene solvent via either a dip-coating or spin-coating process. Films obtained. in this way are stable. (Jertain polymers such as, for example, PVK, are expected to further enhance the luminescence of an emitter in the film.
The invention provides a method of producing electroluminescence comprising the steps of providing an electroluminescent compound of the invention having the general formula (lA), (1B) or (1C) as set out above; and applying a voltage across said electroluminescent compound so that the compound electroluminesces.
According to the invention, electroluminescent devices for use with an applied voltage are provided. In general, such a device has a first electrode, an emitter which is an electroluminescent compound of the invention, and a second, transparent electrode, wherein a voltage is applied between the two electrodes to produce an electric field across the emitter of sufficient strength to cause the emitter to electroluminesce. Preferably, the first electrode is of a metal, such as, for example, aluminum, which reflects light emitted by the compound; whereas the second, transparent electrode permits passage of emitted light therethrough. The transparent electrode is preferably of indium tin oxide (ITO) glass or an equivalent known in the art. Here, the first electrode is the cathode and the second electrode is the anode.
Referring to Figure 1, a preferred embodiment of an electroluminescent device of the invention is shown. The emitter is interposed between an electron transport layer (e.g., tris-(8-hydroxyquinoline)aluminum (Alq3) or 2-(biphenyl-4-yl)-5-(4-tent-butyl phenyl)-1,3,4-oxadiazole (PBD)) adjacent the first metal electrode and a hole transport layer (e.g., N,N'-di-1-naphthyl-N,N'-diphenylbenzidiine (NPB)) adjacent the second, transparent electrode. The choice; of the materials employed as charge transport layers will depend uporA the specific properties of the particular emitter employed. The hole transport layer or the electron transport layer may also function as a supporting layer. The device is connected to a voltage source such that an electric field of sufficient strength is applied across the emitter. Light, :preferably blue light, consequently emitted from the compound of the invention passes through the transparent electrode. Some emitters may additionally function as an electron transport material and/or as a hole transport material in the device. Although some of the compounds of the invention may act in all three capacities, the best efficiency may be obtained by limiting the compound's role to one or two. Furthermore, a compound of the invention may act as a charge transport layer fir another emitter which may or may not also be a compound of the invention.
In some embodiments of the invention, the device includes one or more charge transport layers interposed between the emitter and one or both of the electrodes. Such charge transport layers) are employed in prior art systems with inorganic salt emitters to reduce the voltage drop across the emitter. In a first example of such a device, layers are arranged in a sandwich in the following order: first electrode, charge transport layer, emitter, second charge transport layer, and second, transparent electrode. In a preferred embodiment of this type, a substrate of glass, quartz or the like is employed. A reflective metal layer (corresponding to the first electrode) is deposited on one side of the substrate, and an insulating charge transport layer is deposited on the other side. The emitter layer which is a compound of the invention is deposited on the charge transport layer, preferably by vacuum vapor deposition, though other methods may be equally effective. A transparent conducting electrode (e.g., ITO) is then deposited on the emitter layer.
An effective voltage is applied to produce electroluminescence of the emitter.
In a second example of an EL device of the invention, a second charge transport layer is employed, and the sandwich layers are arranged in the following order: first electrode, first charge transport layer, emitter, second charge transport layer and second, transparent electrode.
Electroluminescent devices of the invention may include one or more of the blue-emitting compounds described herein. In some embodiments of the invention, an electroluminescent .___ . _ .w._ ~., _ _.,.,~~~,._ ,. ~. .~.. __..__ . . . , ,.,<
device such as a flat panel display device may include not only a blue-emitting phosphor as described herein, but may be a multiple-color display device including one or more other phosphors. The other phosphors may emit in other light ranges, e.g., red, green, andlor be "stacked" relative to each other. Convenient materials, structures and uses of electroluminescent display devices are described in Rack et al., 1996.
For photoluminescence, the compounds absorb energy from ultraviolet radiation and emit visible light near the ultraviolet end of the visible spectrum e.g., in the blue region. For electroluminescence, the absorbed energy is from an applied electric field. It is expected that the luminescence of compounds of the unvention can be readily quenched by the addition of acid or metal cations such as Zn2+, Cuz+, Ni~+ Cd2+, Hgz+, Ag+ and H+ (Pang et al., 2001, Yang et al., 2001 ).
The invention further provides methods employing compounds of the invention to harvest photons, and corresponding devices for such use. Spectroscopic studies have demonstrated that compounds of the invention have high efficiency to harvest photons and produce highly polarized electronic transitions. In general, when such compounds are excited by light, a charge separation occurs within the molecule; a first portion of the molecule has a negative charge and a second portion has a positive charge. Thus the first portion acts as an electron donor and the second portion as an electron acceptor. If recombination of the charge separation occurs, a photon is produced and luminescence is observed. In photovoltaic devices, recombination of the charge separation does not occur; instead the charges move toward an anode and a cathode to produce a potential difference, from which current can be produced.
Molecules with the ability to separate charges upon light initiation are useful for applications such as photocopiers, photovoltaic devices and photoreceptors.
Organic photoconductors provided by the present invention are expected to be useful in such applications, due to their stability and ability to be spread into thin films. Related methods are encompassed by the invention.
Organic semiconducting materials can be used in the manufacture of photovoltaic cells that harvest light by photoinduced charge separation. To realize an efficient photovoltaic device, a large interfacial area at which effective dissociation of excitons occurs must be created; thus an electron donor material is mixed with an electron acceptor material. (Here, an exciton is a mobile combination of an electron and a hole in an excited crystal, e.g., a semiconductor.) Organic luminescent compounds as semiconductors are advantageous due to their long lifetime, efficiency, low operating voltage and low cost.
Photocopiers use a light-initiated charge separation to attract positively-charged molecules of toner powder onto a drum that is negatively charged.
The invention further provides methods employing compounds of the invention to detect metal ions. The change in the luminescence upon coordination of metal ions may be useful for detection of gunpowder residue, bomb making activity, and/or environmental contamination such as heavy metal contamination of food or soil or water, as well as for detection of sites of meteor impact and even interplanetary exploration.
The invention further provides methods employing compounds of the invention to detect acid. This aspect of the invention is expected to be useful for a variety of applications, including, without limitation, pH sensors, as well as detection of contamination, particularly environmental contamination (e.g., acidity of lakes, soil, etc.).
The invention further provides molecular switches employing compounds as described above, and methods of use thereof.
Information processing systems of current computers are based on semiconductor logic gates or switches (Tang et al.,1987). By reducing the switching elements to a molecular level, the processing capability and memory density of computers could be increased by several orders of magnitude and the power input could be decreased significantly (Leung et ad., 2000).
Candidates for this purpose are molecules that are capable of undergoing reversible transformations in response to chemical, electrical and/or optical stimulation, and producing readily detectable optical signals in the process. For example, t:he respective neutral forms of compounds of the invention (2), (3), (4), (5) and (6), when in solution, emit blue luminescence.
The neutral forms can be easily converted to the non-luminescent protonated forms by the addition of acid. These can be switched back to the depronated forms by the addition of a base.
Three-state molecular circuits based on (2), (3) and (4) with OH-, H+and ultraviolet light as inputs and visible light as outputs have been established.
Example 1 to Example 5 below provide detailed descriptions of the syntheses of compounds (2), (3), (4), (5) and (6) respectively. As would be apparent to a person of ordinary skill in the art, other functionalities may be included in derivatives according to the invention.
Alternatively, starting materials may be modified to include, but are not limited to, funetionalities such as ether, epoxide, ester, amide or the like. Such functionalities may in some cases confer desirable physical or chemical properties, such as increased stability or luminescence.
WORKING EXAMPLES
All starting materials were purchased from Aldrich Chemical Company and used without further purification. Solvents were freshly distilled over appropriate drying reagents. All experiments were carried out under a dry nitrogen atmosphere using standard Schlenk Techniques unless otherwise stated. Thin Layer Chromatography was carried out on SiO2 (silica gel F2S4, Whatman). Flash chromatography was carried out on silica (siliica gel 60, 70-230 mesh). 'H and'3C spectra were recorded on a Broker Avance 300 spectrometer operating at 300 and 75.3 MHz respectively. Excitation and emission spectra mere recorded on a Photon.
Technologies International QuantaMaster Model 2 spectrometer. Spin coating was done on Chemat Technology spin-coater KW-4A and vacuum deposition using a modified Edwards manual diffusion pump. The EL spectra for compound (3) (see Figure 8) were taken using Ocean Optics HR2000 and all data involving current, voltage and lumiinosity using a Keithley 238 high current source measure unit. The EL spectra for compound (4) (see Figure 12) were taken using a Photo Research - 6S0 Spectra Colorimeter. Data collection for the X-ray crystal structural determinations were performed on a Broker SMART CCD 1000 X-ray diffractometer with graphite-monochromated molybdenum Ka radiation (~. = 0.710'73 !~) at 298K and the data were processed on a Pentium PC using the Broker AXS Windows NT SHELXTL software package (version 5.10). Elemental analyses were performed by Canadian Microanalytical Service Ltd., (Delta, British Columbia, Canada). Melting points were determined on a Fisher-Johns melting point apparatus. Syntheses of precursors p-{2,2'-dipyridylamino)phenylboronic acid and p-(2,2'-dipyridylamino)biphenylboronic acid were based on a modified literature method (Jia et al., 2003).
Example 1: 1-pyrenyl-2, 2 dipyridylamine (2). The mixture of 0.145 g, 1-bromopyrene (O.S mmol), 0.10 g 2,2 dipyridylamine (O.S8 mmol), 0.125 g Cu~I, 0.235 g K3P04, 0.033 mL 1,2-transdiaminocyclohexane and 1mL 1,4-dioxane was stirred at 110°C for 24 hours. After cooling to room temperature, the mixture was extracted with dichloromethane (3 x 1 SmL). The solvent was evaporated under reduced pressure. The residue was subjected to column chromatography on silica gel (CH3COOEt/Hexane, 2:1) to afford a white compound {2) in 39%
yield. The molecular structure of (2) was confirmed by X-ray crystallography, the structure is pictured in Figure 9. 'H NMR in CDZC12 at 2S°C: 8 ppm = 8.31(d, J = 8.1, 1H), 8.27(m, 3H), 8.19 (m, 3H), 8.06(m, 3H), 7.95 (d, J = 8.1, 1H), 7.56 (m, 2H), 7.08(td, d = 8.~4, 0.9, 2H), 6.94(ddd, J == 7.2, 4.8, 1H). 13C NMR in CDZCIz at 2S°C, ~ ppm: 159.08, 148.72, 139.16, 137.94, 131.81, 131.62, 131.12, 129.65, 128.91, 128.71, 128.20, 127.83, 126.94, 126.71, 126.53, 126.11, 125.94, 125.33, 123.45, 118.27, 116.57. Elemental analysis calculated. for C26H,~N3 : C, 84.1, H, 4.58, 11.32.
Found: C, 83.84, 4.72, 11.35. See Table 1 for ~.max values for the emission and excitation of (2) as well as its quantum efficiency. See Figure 2 for the photoluminescence spectra of (2) as a solid, and Figure 3 for the photoluminescence spectra of (2) as a solution.
(It is of interest that intermolecular quenching does not appear to be a factor when tlhis compound is in the solid state;
rather, it is still luminescent.) Table 1. Excitation, emission and photoluminescent quantum efficiency of compounds (2), (3), (4), (5) and (6) in CHZCIz at ambient temperature.
Compound Excitation e~",~ Emission ~.max Quantum Efficiency 2 360 nm 415 mn 70%
3 350 nm 433 ntn 72%
4 350 nm 437 nm 76%
362 nm 454 nm >40%
6 354 nm 442 nm 31%
Example 2: Synthesis of 4-(1-pyrenyl)phenyl-2.2'-dipyridylarnine (3). A
mixture of l-bromopyrene (0.5 g, 1.78 mmol), Pd(PPh3)4 (0.062 g , 0.054 mmol) and toluene(40 mL) was stirred for 10 minutes under NZ(g). A solution ofp-(2,2'-dipyridylamino)phenylboronic acid (0.57 g, 1.96 mmol) in 20 mL EtOH and a solution of NaOH (0.8 g) in 20 mL H20 were added.
The resulting mixture was heated and stirred at reflux for 24 hours and was then allowed to cool to room temperature. The water layer was separated and extracted with methylene chloride (CHzCl2) (3 x 15 mL). The combined organic layers were dried. over MgS04, and evaporated under reduced pressure. Purification of the crude product was performed by column chromatography (THF:Hexane, 3:2) and afforded (3) as a white solid in 83%
yield. The molecular structure of (3) was confirmed by X-ray crystallography, the structure is pictured in Figure 10. 1H NMR in CD2C12 at 2~°C: 8 ppm = 8.40(ddd, J = 4.8, 1.8, 0.9, 2H), 8.36(d, J = 9.3, 1H), 8.27(m, 3H), 8.11(m, SH), 7.68(m, 4H), 7.40(d, J = 8.4, 2H), 7.19(d, J =
8.1, 2H), 7.05(ddd, J = 7.2, 4.8, 0.9,2 H). 13C NMR in CDZC12 at 25C, 8 ppm: 158.91, 149.11, 145.16, 138.56, 138.17,137.80, 132.27, 132.18, 131.68, 131.27, 130.13, 129.09, 128.35, 128.12, 128.06, 127.58, 126.75, 125.88, 125.8, 125.63, 125.60, 125.42, 119.02, 118.63, 117.90.
Elemental analysis calculated for C32H21N3~1~3H2O;C, 84.77, H, 4.78, N, 9.27. Found: C, 84.89, 4.76, 9.42. See Table 1 for emission and excitation ~,m~ values and quantum efficiency of compound (3). See Figure 4 for the photoluminescence spectra of (3) as a solid, and Figure 5 for the photoluminescence spectra of (3) as a solution.
Example 3: Synthesis of 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridyYamine (4). 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine was prepared by the same procedure as that used to prepare (4) above. From 1-bromopyrene (0.2983 g, 1.045 mmol), Pd(PPh3)4 (0.036 g , 0.031 mmol), p-(2,2'-dipyridylamino)biphenylboronic acid (0.4218 g, 1.149 mmol) and NaOH(0.5 g) was obtained (4) as a white solid in 71.4% yield. The molecular structure of (4) was confirmed by X-ray crystallography, the structure is pictured in Figure 11. 1H NMR in CDZC12 at 2S°C: b ppm = 8.36(ddd, J = 4.8, 1.8, 0.9, 2H), 8.32(d, J = 1.5, 1H), 8.26, (m,3H), 8.11(m, SH), 7.88(dd, J = 1.8, 6.6, 2H), 7.78(m, 4H), 7.66(m, 2H), 7.33(dt, J = 9.0, 2.4, 2H), 7.14(d, J = 8.4, 2H), 7.02(ddd, J = 7.2, 4.8, 0.9, 2H). '3C NMR in CDzCl2 at 25°C, 8 ppm 158.79, 149.07, 146.40, 140.74, 140.03, 138.12, 138.00, 132.66, 132.53, 132.18, 131.74e, 131.67, 131.31, 130.04, 129.13, 128.71, 128.30, 128.17, 128.07, 127.54, 126.77, 125.87, 125.81, 125.2, 125.40, 118.97, 117.76, 116.22, 112.06. Elemental analysis calculated for C38Hz5N3: C, 87.19, H, 4.78, N, 8.03. Found:
C, 87.56, H, 4.94, N, 8.28. See Table 1 for emission and excitation ~.max values and quantum efficiency of compound (4). See Fi~ure 6 for the luminescence spectra of (4) as a solid, and Figure 7 for the luminescence spectra of (4) as a solution. The photoluminescence spectra is overlaid with an electroluminescence spectrum in Figure 12. Luminance-voltage and current density-voltage diagrams of (4) in a 2-layer EL device are shown in Figure 13.
Figure 16 shows the luminance-voltage and current-voltage diagrams of (4) in a single layer EL
device.
Example 4. Synthesis of 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5): To a THF
(20m1) of 4-Iodo-4'-diphenylaminobiphenyl (Koene et al. 1998) (O.Sg, 1.l2mmol) was added a hexane solution of n-BuLi (0.77m1, 1.23mmo1) at -78°C. After being stirred for 1 h at this temperature, B(OMe)3 (0.2m1, 2.Smmol) was added. After the mixture was stirred for another 1 h at -~78°C, it was warmed to ambient temperature and stirred overnight. The solution was partitioned between saturated aqueous NH4Cl (30 mL) and CHZC12 (30 mL). The adueous layer was extracted further with dichloromethane (2 X 30 mL) and the combined organic layers were dried over MgS04.
The solvent was evaporated under vacuum to provide the boronic acid in 96%
yield. A mixture of 1-bromopyrene (0.258, 0.89mmo1), Pd(PPh3)4 (0.0318 , 0.027 mmol) and toluene (40 ml) was stirred for 10 min. The above boronic acid (0.368, 0.98 mmol) in 15 ml EtOH
and NazC',03(0.48 g) in 15 ml H20 were subsequently added. The mixture was stirred and refluxed for 24 h and then allowed to cool to room temperature. The water layer was separated and extracted with CHZC12 (3 x 15 ml). The combined organic layers were dried over MgS04, and the solvents were evaporated under reduced pressure. Purification of the crude product by column chromatography (CHZCI2:Hexane, 1:3) afforded (5) as colorless solid in 88% yield. 'H NMR in CD3Cl (8, ppm, 25°C): 8.29 (d, J = 6.9, 1H), 8.26(d, J = 5.7, 1H), 8.22 (t, J = 7.8, 2H), 8.02 - 8.13(m, SH), 7.80 (d, J = 8.1, 2H), 7.72 (d, J = 8.4, 2H), 7.63 (d, J = 8.4, 2H), 7.3 - 7.35(m, 4 H), 7.19 - 7.24 (m, 6H), 7.09 (t, J = 7.2, 2H). See Table 1 for emission and excitation ~,m~
values and quantum efficiency of compound (5) and Figure 14 for the photoluminescence spectra of (5) as a solid, and as a solution. Figure 15A shows a cyclic voltametry diagram starting with the reduction of (5) in a mixture of CHZCIz and CH3CN. This figure provides information about the Lowest Unoccupied Molecular Orbital (LUMO) of the molecule and indicates promising electron transport properties of the molecule. Figure 15B shows a cyclic voltametry diagram starting with the oxidation of (5) in a mixture of CHZCIz and CH3CN. This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transport properties of the molecule.
Example 5. Synthesis of 4-(1-naphthylphenylamino)-4"-{5-(8-methoxyquinolinyl))biphenyl (QNPB) (6): p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide (1.55 g, 3.12 mmol) was reacted with butyl lithium (2.14 mL of 1.0 M solution in hexane, 3.43 mmol) at -78°C in 50 mL THF. Following an addition of B(i-UPr)3 (1.1 g), a boric acid intermediate p-N-( 1-naphthyl)-N-phenylamino-biphenyl-B(OH;)Z was isolated. p-N-( 1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 (1.0 g, 2.4 mmol) was reacted with 5-bromo-8-methoxyquinoline (0.48 g, 2.0 mmol) in a mixture of solvents: ethanol (20 mL), toluene (35 mL) and water (15 mL) in the presence of Pd(OAc)2 (0.026 g), PPh3 (0.063 g), and Na2C03. Product QNPB (see structure in Scheme 3) was produced in 85% yield. Elemental analysis: calc for C38HZgN2O, C 86.36; H, 5.30; N, 5.30. Found: C 86.40; H, 5.29; N, 5.49. The molecular structure of (6) was confirmed by X-ray crystallography; the structure is pictured in Figure 20.
'H NMR for QNPB (ppm, CDCl3): 8.97 (d, 1H), 8.32 (d, 1H), 8.00 (d, 1H), 7.92 (d, 1H), 7:82 (d, 1H), 7.68 (d, 2H), 7.50 (m, 7H), 7.42 (m, 3H), 7.24 (d, 1H), 7.15 (m, SH), 7.00 (t, 1H), 4.17 (s, 3H). See Table 1 for emission and excitation ~,m~ values anal quantum efficiency of compound (6). A current density-voltage diagram and luminance-voltage diagram for compound (6) in a single layer EL device are shown in Figures 17A and 1 TB. The photoluminescence spectrum and the electroluminescence spectrum of compound (i5) in a single layer EL device are shown in Figure 18. A current density-voltage diagram and luminance-voltage diagram of compound (6) in a double layer EL device are shown in Figure 19A and 19B where (6) is the hole transport layer and Alq3 is the emitter and electron transport layer.
Example 6. Preparation of a two layer EL device. A two layer device was made using compound 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3) as both a charge (electron) transport layer and an emitting layer. The configuration was: cathode, electron transport and emitting layer of compound (3) (50 nm), hole transport layer (50 nm) of NPB, anode. The emitting layer was fabricated on an ITO substrate, which was cleaned by an ultraviolet ozone cleaner immediately before use. Both the organic layers and a metal cathode of A1 were deposited by conventional vapor vacuum deposition. Prior to the deposition, all the organic materials were purified via a train sublimation method (Wagner et al., 1982).
Example 7. Preparation of a one layer EL device. A one layer device was made using compound (4) as an emitting Layer, an electron transport layer and a hole transport layer. The configuration was: cathode, film of compound (4) (SO nm), anode. The compound (4) layer was fabricated on an ITO substrate, which was cleaned by an ultraviiolet ozone cleaner immediately before use. Both the organic layer and a metal cathode of Al were deposited by conventional vapor vacuum deposition. Prior to the deposition, all the organic materials were purified via a train sublimation method (Wagner et ad., 1982). Figure 13 shows a plot of the current vs. voltage and luminance vs voltage for this single layer device containing a 60 nm thick film of (4').
Example 8. Preparation of a two layer EL device. A tvvo layer device was made using compound QNPB (6) as a hole transport layer and Alq3 as both an electron transport layer and an emitting layer. The configuration was: cathode, electron transport and emitting layer of Alq3, hole transport layer of QNPB (6), anode. The emitting layer was fabricated on an ITO substrate, which was cleaned by an ultraviolet ozone cleaner immediately before use. Both the organic layers and a metal cathode of Al were deposited by conventional vapor vacuum deposition. Prior to the deposition, all the organic materials were purified via a train sublimation method (Wagner et al., 1982). Several such two layer EL devices were prepared with varying thicknesses (30, 60, 90, 120 nm) of the QNPB (6) hole transport layer and constant thickness (40 nm) of the Alq3 electron transport and emitter layer. A plot of current density vs. voltage for these devices is shown in Figure 19A and a corresponding plot of luminance vs. voltage is shown in Figure 19B.
A cyclic voltammetry diagram starting with the oxidation of (6) in CHZC12 is shown in Figure 21.
This figure provides information about the Highest Occupied Molecular Orbital (HOMO) of the molecule and indicates promising hole transport properties of the molecule.
All scientific and patent publications cited herein are hereby incorporated in their entirety by reference.
Although this invention is described in detail with reference to preferred embodiments thereof, these embodiments are offered to illustrate but not to li~rnit the invention. It is possible to make other embodiments that employ the principles of the invention and that fall within its spirit and scope as defined by the claims appended hereto.
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fi'T4~raw,=::vT"~i~-~.;wtrs,<c:.:;rr... ...wm. . ,.,_.,K~,,,~;",,yyF.~:~"R.~-;-,...."~;.s:"womw:a...w.,a._.enwop,w~a~.a.».~.e..»,..-.,.~.- -___.._-_._.._
Claims (51)
1. A compound having a general formula (1A):
(1A) where X5, X6 and X7 are each independently selected from the group consisting of carbon and nitrogen;
n is a number from 0-2;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl; and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
(1A) where X5, X6 and X7 are each independently selected from the group consisting of carbon and nitrogen;
n is a number from 0-2;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl; and wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
2. A compound having a general formula (1B):
where X8, X9 and X10 are each independently selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
m is a number from 0-10;
Q, S and T are the same or different and are selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
p and q are the same or different and are a number between 0-5;
r is a number between 0-4;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
where X8, X9 and X10 are each independently selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
m is a number from 0-10;
Q, S and T are the same or different and are selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
p and q are the same or different and are a number between 0-5;
r is a number between 0-4;
Z is a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
3. A compound having a general formula (1C) a (1C) where Z2, Z3 and Z4 are each independently a substituted or unsubstituted aryl moiety selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, pyridyl, bipyridyl, indyl, and quinolinyl;
m is a number from 0-10;
Q is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrile group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
r is a number between 0 and 4;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
m is a number from 0-10;
Q is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrile group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic;
r is a number between 0 and 4;
wherein a said substituent is selected from the group consisting of an aryl group, an alkoxy group, a hydroxy group, a halo group, an amino group, a nitro group, a nitrite group, -CF3 and an aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic.
4. A compound as claimed in claim 1, wherein said compound is photoluminescent or electroluminescent.
5. A compound as claimed in claim 2, wherein said compound is photoluminescent or electroluminescent.
6. A compound as claimed in claim 3, wherein said compound is photoluminescent or electroluminescent.
7. A compound as claimed in claim 1, 2 or 3 wherein said compound is a hole transporter.
8. A compound as claimed in claim 1, wherein X5, X6 and X' are each independently selected from the group consisting of a substituted carbon, an unsubstituted carbon and an unsubstituted nitrogen.
9. A compound as claimed in claim 1, wherein at least one of X5, X6 and X7 is nitrogen.
10. A compound as claimed in claim 1, wherein X5, X6 and X7 are nitrogen.
11. A method of synthesizing a compound as claimed in claim 1, comprising a step selected from the group consisting of:
1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3PO4+ 1,2-transdiaminocyclohexane + 1,4-dioxane .fwdarw.1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-bromopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid .fwdarw.4-(1-pyrenyl)phenyl-2,2'-dipyridylamine(3);
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid .fwdarw.4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4);
4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-BuLi .fwdarw.4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5); and p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi .fwdarw.p-N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + Na2CO3 .fwdarw. QNPB (6).
1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3PO4+ 1,2-transdiaminocyclohexane + 1,4-dioxane .fwdarw.1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-bromopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid .fwdarw.4-(1-pyrenyl)phenyl-2,2'-dipyridylamine(3);
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid .fwdarw.4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4);
4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-BuLi .fwdarw.4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5); and p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi .fwdarw.p-N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + Na2CO3 .fwdarw. QNPB (6).
12. A compound as claimed in claim 2, wherein X8 is selected from the group consisting of a substituted or unsubstituted carbon, an unsubstituted nitrogen and a substituted or unsubstituted silicon;
X9 and X10 are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 0 to 4.
X9 and X10 are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 0 to 4.
13. A compound as claimed in claim 2, wherein X8 is nitrogen;
X9 and X10 are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 1 to 4.
X9 and X10 are each independently selected from the group consisting of a substituted or unsubstituted carbon and an unsubstituted nitrogen; and m is a number from 1 to 4.
14. A method of synthesizing a compound as claimed in claim 2, comprising a step selected from the group consisting of 1-bromopyrenyl + 2,2'-dipyridylamine + CuI + K3PO4+ 1,2-transdiaminocyclohexane + 1,4-dioxane .fwdarw.1-pyrenyl-2,2'-dipyridylamine (2);
Pd(PPh3)4 + 1-bromopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid .fwdarw.4-(1-pyrenyl)phenyl-2,2'-dipyridylamine(3);
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid .fwdarw.4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4); and 4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-BuLi .fwdarw.4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5).
Pd(PPh3)4 + 1-bromopyrene +p-(2,2'-dipyridylamino)phenyl boronic acid .fwdarw.4-(1-pyrenyl)phenyl-2,2'-dipyridylamine(3);
Pd(PPh3)4 + 1-bromopyrene + p-(2,2'-dipyridylamino)biphenylboronic acid .fwdarw.4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine(4); and 4-iodo-4'-diphenylaminobiphenyl + B(OCH3)3 + N-BuLi .fwdarw.4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5).
15. A method of synthesizing a compound as claimed in claim 3, comprising a step selected from the group consisting of:
p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi .fwdarw.p-N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + Na2CO3 .fwdarw. QNPB (6).
p-N-(1-naphthyl)-N-phenylamino-biphenyl-iodide + B(i-OPr)3 + N-BuLi .fwdarw.p-N-(1-naphthyl)-N-phenylamino-biphenyl-B(OH)2 + 5-bromo-8-methoxyquinoline + Pd(OAc)2 + PPh3 + Na2CO3 .fwdarw. QNPB (6).
16. A photoluminescent or electroluminescent compound having a formula selected from the group consisting of 1-pyrenyl-2,2'-dipyridylamine (2), 4-(1-pyrenyl)phenyl-2,2'-dipyridylamine (3), 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (4), 4-(1-pyrenyl)biphenyl-2,2'-diphenylamine (5) and QNPB (6).
17. A composition comprising a compound as claimed in claim 1, an organic polymer and a solvent.
18. A composition comprising a compound as claimed in claim 2, an organic polymer and a solvent.
19. A composition comprising a compound as claimed in claim 3, an organic polymer and a solvent.
20. A photoluminescent product or an electroluminescent product comprising a compound as claimed in claim 1, 2, 3 or 16.
21. The product of claim 20 which is a flat panel display device.
22. The product of claim 20 which is a luminescent probe.
23. A method of producing electroluminescence, comprising the steps of:
providing an electroluminescent compound as claimed in claim 4, 5, or 6 and applying a voltage across said compound sa that said compound electroluminesces.
providing an electroluminescent compound as claimed in claim 4, 5, or 6 and applying a voltage across said compound sa that said compound electroluminesces.
24. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, an emitter which is an electroluminescent compound as claimed in claim 4, 5, or 6, and a second, transparent electrode, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
a first electrode, an emitter which is an electroluminescent compound as claimed in claim 4, 5, or 6, and a second, transparent electrode, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
25. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, an electron transport layer adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is an electroluminescent compound as claimed in claim 4, 5, or 6 interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, an electron transport layer adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is an electroluminescent compound as claimed in claim 4, 5, or 6 interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
26. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, a layer which is both an emitter and an electron transporter which is an electroluminescent compound as claimed in claim 4, 5, or 6 and which is located adjacent the first electrode, and a hole transport layer which is interposed between the emitter and electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, a layer which is both an emitter and an electron transporter which is an electroluminescent compound as claimed in claim 4, 5, or 6 and which is located adjacent the first electrode, and a hole transport layer which is interposed between the emitter and electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
27. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, a layer which is all of an emitter, an electron transporter and a hole transporter which is an electroluminescent compound as claimed in claim 4, 5, or 6 and which is interposed between the first and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, a layer which is all of an emitter, an electron transporter and a hole transporter which is an electroluminescent compound as claimed in claim 4, 5, or 6 and which is interposed between the first and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
28. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, an electron transport layer which is a compound as claimed in claim 1, 2, or 3 and which is located adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, an electron transport layer which is a compound as claimed in claim 1, 2, or 3 and which is located adjacent the first electrode, a hole transport layer adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
29. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, a hole transport layer which is a compound as claimed in claim 1, 2, or 3 and which is located adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, a hole transport layer which is a compound as claimed in claim 1, 2, or 3 and which is located adjacent the second electrode, and an emitter which is interposed between the electron transport layer and the hole transport layer, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
30. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, a layer which is both an electron transporter and an emitter which is located adjacent the first electrode, and a hole transport layer which is a compound as claimed in claim 1, 2, or 3 and which is interposed between the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, a layer which is both an electron transporter and an emitter which is located adjacent the first electrode, and a hole transport layer which is a compound as claimed in claim 1, 2, or 3 and which is interposed between the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
31. An electroluminescent device for use with an applied voltage, comprising:
a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, and a layer which is both an emitter and a hole transporter which is a compound as claimed in claim 1, 2, or 3 and which is interposed between the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
a first electrode, a second, transparent electrode, an electron transport layer which is located adjacent the first electrode, and a layer which is both an emitter and a hole transporter which is a compound as claimed in claim 1, 2, or 3 and which is interposed between the electron transport layer and the second electrode, wherein voltage is applied to the two electrodes to produce an electric field so that the emitter electroluminesces.
32. A method of detecting metal ions comprising the steps of: providing a photoluminescent compound as claimed in claim 4, 5, or 6 and detecting photoluminescence of said compound, wherein contact with a metal ion quenches said photoluminescence of said compound.
33. The method of claim 32, wherein said metal ions are selected from the group consisting of Zn2+, Cu2+, Ni2+ Cd2+, Hg2+ and Ag+.
34. A method of detecting acid comprising the steps of: providing a photoluminescent compound as claimed in claim 4, 5, or 6 and detecting photoluminescence of said compound, wherein protonation of said compound changes the state of said compound's photoluminescence.
35. A method of harvesting photons comprising the steps of: providing a compound as claimed in claim 1, and providing light such that photons strike said compound and charge separation occurs in said compound.
36. A method of harvesting photons comprising the steps of: providing a compound as claimed in claim 2, and providing light such that photons strike said compound and charge separation occurs in said compound.
37. A method of harvesting photons comprising the steps of: providing a compound as claimed in claim 3, and providing light such that photons strike said compound and charge separation occurs in said compound.
38. The method as claimed in claim 35, 36 or 37, wherein said separated charges recombine and photons are released.
39. The method as claimed in claim 35, 36 or 37, wherein said separated charges migrate to respective electrodes to produce a potential difference.
40. A method of separating charges comprising the steps of: providing a compound as claimed in claim 1 and providing light such that photons strike said compound and charge separation occurs in said compound.
41. A method of separating charges comprising the steps of: providing a compound as claimed in claim 2 and providing light such that photons strike said compound and charge separation occurs in said compound.
42. A method of separating charges comprising the steps of: providing a compound as claimed in claim 3 and providing light such that photons strike said compound and charge separation occurs in said compound.
43. The method of claim 40, 41 or 42, wherein said separated charges recombine and photons are released.
44. The method of claim 40, 41 or 42, wherein said separated charges migrate to respective electrodes to produce a potential difference.
45. A photocopier employing the method of claim 35, 36, 37, 40, 41 or 42.
46. A photovoltaic device employing the method of claim 3S, 36, 37, 40, 41 or 42.
47. A photoreceptor employing the method of claim 35, 36, 37, 40, 41 or 42.
48. A solar cell employing the method of claim 35, 36, 37, 40, 41 or 42.
49. A semiconductor employing the method of claim 35, 36, 37, 40, 41 or 42.
50. A molecular switch comprising a compound as claimed in claim 4, 5 or 6 that is capable of existing in more than one luminescent state, wherein acid, base, and/or incident light produces a change in the luminescent state of said compound.
51. A circuit comprising a molecular switch as claimed in claim 48.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2464604 CA2464604A1 (en) | 2003-04-17 | 2004-04-16 | Organic luminescent compounds and methods of making and using same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46333603P | 2003-04-17 | 2003-04-17 | |
| CA002425817A CA2425817A1 (en) | 2003-04-17 | 2003-04-17 | Organic luminescent compounds and methods of making and using same |
| US60/463,336 | 2003-04-17 | ||
| CA2,425,817 | 2003-04-17 | ||
| CA 2464604 CA2464604A1 (en) | 2003-04-17 | 2004-04-16 | Organic luminescent compounds and methods of making and using same |
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| Publication Number | Publication Date |
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| CA2464604A1 true CA2464604A1 (en) | 2004-10-17 |
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| CA 2464604 Abandoned CA2464604A1 (en) | 2003-04-17 | 2004-04-16 | Organic luminescent compounds and methods of making and using same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013039413A1 (en) | 2011-09-13 | 2013-03-21 | Instituto Superior Tecnico | Mono-and polynuclear boron iminopyprolyl complexes: methods of preparation and use as luminescent materials |
| US11046658B2 (en) | 2018-07-02 | 2021-06-29 | Incyte Corporation | Aminopyrazine derivatives as PI3K-γ inhibitors |
| US11926616B2 (en) | 2018-03-08 | 2024-03-12 | Incyte Corporation | Aminopyrazine diol compounds as PI3K-γ inhibitors |
-
2004
- 2004-04-16 CA CA 2464604 patent/CA2464604A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013039413A1 (en) | 2011-09-13 | 2013-03-21 | Instituto Superior Tecnico | Mono-and polynuclear boron iminopyprolyl complexes: methods of preparation and use as luminescent materials |
| US11926616B2 (en) | 2018-03-08 | 2024-03-12 | Incyte Corporation | Aminopyrazine diol compounds as PI3K-γ inhibitors |
| US11046658B2 (en) | 2018-07-02 | 2021-06-29 | Incyte Corporation | Aminopyrazine derivatives as PI3K-γ inhibitors |
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