阅读说明：本技术 三并咔唑衍生物、有机光电器件及显示或照明装置 (Tri-carbazole derivative, organic photoelectric device, and display or lighting device ) 是由 王鹏 王子兴 高春吉 吴利 张迪 于 2021-08-30 设计创作，主要内容包括：本发明公开了一种三并咔唑衍生物、有机光电器件及显示或照明装置,其中该三并咔唑衍生物其具有下列式(1)所示的结构：式(1)。本发明的三并咔唑衍生物用于制作有机光电器件,该器件的电流效率有了显著提升,同时其寿命也有所提升。(The invention discloses a trislocarbazole derivative, an organic photoelectric device and a display or lighting device, wherein the trislocarbazole derivative has a structure shown in a following formula (1):)

1. A tris-carbazole derivative having a structure represented by the following formula (1):

formula (1)

X₁-X₈Each independently selected from a CR or N atom, wherein R is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, cycloalkyl, heteroalkyl heterocycloalkyl, or aryl or heteroaryl;

X₁-X₈are the same or different from each other, wherein when X is₁-X₈When none is N atom, R₁、R₂And R₃Not all of which are the same or all of which are different;

L₁、L₂and L₃Each independently is a single bond or a substituted or unsubstituted aryl group;

R₁、R₂and R₃Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl or bonded to adjacent atoms to form a ring;

R₄and R₅Each independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C4-C30 heteroaryl;

wherein R is₁、R₂And R₃At least one of which is selected from the group consisting of substituted or unsubstituted groups,

wherein R is₆-R₁₀Each independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C4-C30 heteroaryl;

and when R is₁Is the above-mentioned S-44, and R₂And R₃When not S-44, L₁Is a single bond;

when R is₂Is the above-mentioned S-44, and R₁And R₃When not S-44, L₂Is a single bond;

when R is₃Is as followsS-44, and R₁And R₂When not S-44, L₃Is a single bond.

2. The tris-carbazole derivative according to claim 1, wherein the tris-carbazole derivative is any one of the following structures:

。

3. an organic opto-electrical device comprising a cathode layer, an anode layer and an organic layer,

wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, or an electron transport layer, wherein the organic layer comprises the tricarbazole derivative of claim 1 or 2.

4. The organic optoelectronic device according to claim 3, wherein the organic layer is a light emitting layer further comprising a dopant therein, wherein the mass ratio of the tris-carbazole derivative to the dopant is 1: 99-99: 1.

5. the organic optoelectronic device according to claim 3, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.

6. A display or lighting device comprising the organic optoelectronic device of claim 3.

Technical Field

The invention relates to a tri-carbazole derivative, in particular to a tri-carbazole derivative, an organic photoelectric device and a display or lighting device, and belongs to the field of organic electroluminescence.

Background

Organic optoelectronic devices (e.g., organic electroluminescent diodes, abbreviated as OLEDs) are attracting attention because they are thin and capable of emitting light with high luminance at low driving voltages and also capable of emitting light in multiple colors by selecting light-emitting materials. Since c.w.tang et al by kodak corporation revealed that organic thin film elements can emit light with high brightness, much research and advancement has been made into their applications by a large number of researchers in the OLED industry. Organic photoelectric devices are widely used in various main displays and the like, and their practical use has been advanced. Although the research on organic electroluminescence is rapidly progressing, there are still many problems to be solved, such as improvement of External Quantum Efficiency (EQE), how to design and synthesize new materials with excellent purity, high efficiency electron transport, hole blocking, and the like. For the organic electroluminescent device, the luminous quantum efficiency of the device is the comprehensive reflection of various factors and is an important index for measuring the quality of the device.

Electroluminescence can be generally classified into fluorescence and phosphorescence. In fluorescence emission, an organic molecule in a singlet excited state transits to a ground state, thereby emitting light. On the other hand, in phosphorescence, organic molecules in a triplet excited state transition to a ground state, thereby emitting light. At present, some organic electroluminescent materials have excellent performance and certain application value, but as a host material in an organic electroluminescent device, the host material has good hole transport performance except that the triplet state energy level is higher than that of a guest material, and energy reverse transfer for exciton transition release is prevented. However, materials having both a high triplet level and good hole mobility in the host material are still lacking at present. Therefore, how to design a host material with better performance is always a problem to be solved by those skilled in the art.

Disclosure of Invention

In order to overcome the defects in the prior art, the present invention provides a tris-carbazole derivative and an organic optoelectronic device including the tris-carbazole derivative, wherein the organic optoelectronic device has high luminous efficiency and a prolonged service life.

In order to realize the purpose of the invention, the technical scheme of the invention is as follows:

the present invention provides a tricarbazole derivative having a structure represented by the following formula (1):

formula (1).

Wherein X₁-X₈Each independently selected from CR or N atoms, wherein R is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or heteroaryl.

X₁-X₈Are the same or different from each other, wherein, when X is₁-X₈When none is N atom, R₁、R₂And R₃Not all of which are the same or all of which are different.

L₁、L₂And L₃Is a single bond or a substituted or unsubstituted aryl group.

R₁、R₂And R₃Each independently selected from substituted or unsubstituted C₆~C₃₀Aryl, substituted or unsubstituted C₄~C₃₀Heteroaryl, or bonded to an adjacent atom to form a ring.

R₄-R₅Each independently selected from hydrogen, substituted or unsubstituted C₁-C₁₅Alkyl, substituted or unsubstituted C₆~C₃₀Aryl or substituted or unsubstituted C₄~C₃₀A heteroaryl group.

Wherein R is₁、R₂And R₃At least one of which is selected from the following substituted or unsubstituted groups:

。

wherein R is₆-R₁₀Each independently selected from hydrogen, substituted or unsubstituted C₁-C₁₅Alkyl, substituted or unsubstituted C₆~C₃₀Aryl or substituted or unsubstituted C4-C30 heteroaryl.

And when R1 is the above-mentioned S-44 and R2 and R3 are not the above-mentioned S-44, L1 is a single bond.

When R2 is the above-mentioned S-44 and R1 and R3 are not the above-mentioned S-44, L2 is a single bond.

When R3 is the above-mentioned S-44 and R1 and R2 are not the above-mentioned S-44, L3 is a single bond.

More preferably, the tris-carbazole derivative is any one of the following structures:

。

the present invention provides an organic opto-electronic device comprising: a first electrode;

a second electrode facing the first electrode; an organic layer sandwiched between the first electrode and the second electrode; wherein the organic layer comprises the tris-carbazole derivative of the present invention.

The invention provides an organic photoelectric device, which comprises a cathode layer, an anode layer and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer;

wherein the organic layer comprises the tris-carbazole derivative of the present invention.

Preferably, the organic layer is a light-emitting layer, and the light-emitting layer further includes a dopant, wherein the mass ratio of the tris-carbazole derivative to the dopant (guest material) is 1: 99-99: 1, and the dopant is not subject to any limitation.

Preferably, the organic layer is an electron transport layer.

Preferably, the Organic optoelectronic device is an Organic photovoltaic device, an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), or an Organic Memory device (Organic Memory Element).

The invention also provides a display or lighting device comprising an organic optoelectronic device of the invention.

The main body material has hole transmission property and electron transmission property at the same time, and has the effect of gaining the performance of the device. The carbazole group has a certain triplet state energy level and has good hole transmission capability. The tricarbazole derivative has bipolar and balanced hole and electron transport properties, and therefore, can be better used as a main material to be applied to organic photoelectric elements.

The invention provides a novel tri-carbazole derivative which has a high triplet state energy level and has good hole transmission capability. The electron-deficient group is introduced to the N atom of carbazole, which can improve the electron transport capability of molecule. In addition, the introduction of aromatic groups on nitrogen atoms is also beneficial to the synthesis of molecules, and ideal compounds are easily obtained. And the carbazole ring has good planarity, and when a plurality of carbazole rings are formed into a ring, the planarity of molecules is further enhanced, so that the accumulation among molecules is facilitated, unnecessary vibration energy loss is reduced, and high-efficiency luminous performance is realized. In addition, the preparation method of the benzotriazolyl derivative is simple, raw materials are easy to obtain, and the industrial requirements can be met.

Detailed Description

The organic photoelectric device comprising the carbazole derivative of the present invention includes a substrate, a first electrode, an organic layer, a second electrode, and a capping layer. Preferably, the organic optoelectronic device comprises a substrate, a first electrode located on the substrate, an organic layer located on the first electrode, a second electrode located on the organic layer, and a covering layer located on the outer side of the second electrode, wherein the outer side of the second electrode refers to the side facing away from the first electrode.

The organic layer of the present invention is at least one of a light-emitting layer (active layer), a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. And the organic layer may be formed of a single layer structure or a stacked (multi-layer structure including a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer) structure. Wherein the hole transport layer may further include a first hole transport layer and a second hole transport layer. In the organic optoelectronic device of the present invention (e.g., an organic electroluminescent diode), any material known in the art for use in the layers may be used for the light-emitting layer, except that the layer contains the triscarbazole derivative of the present invention.

In the light-emitting element of the present invention, the substrate material can be any substrate typically used in organic light-emitting elements, such as soda glass, alkali-free glass or transparent flexible substrate, a substrate made of an opaque material such as silicon or stainless steel, or a flexible polyimide film, and different substrate materials have different properties and different application directions. The hole transport layer of the present invention can be formed by a method of stacking or mixing one or two or more kinds of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. Since the hole transport material needs to transport holes from the positive electrode efficiently between electrodes to which an electric field is applied, it is desirable that the hole transport material has high hole injection efficiency and can transport injected holes efficiently. Therefore, the hole transport material should have an appropriate ionization potential and an appropriate energy level and have a large hole mobility, and further, the material is excellent in stability and impurities that become traps are not easily generated during manufacturing and use. The substance satisfying such conditions is not particularly limited, and examples thereof include carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, phthalocyanine compounds, hexacarbonitrile hexaazatriphenylene compounds, quinacridone compounds, perylene derivatives, anthraquinone compounds, F4-TCNQ, polyaniline, polythiophene, and polyvinylcarbazole, but are not limited thereto.

The light-emitting layer material of the present invention may contain a dopant material (also referred to as a guest material) (may contain a plurality of dopant materials) in addition to the triscarbazole derivative of the present invention. In addition, the light emitting layer can be a single light emitting layer, or can be a composite light emitting layer formed by transversely or longitudinally overlapping the light emitting layers. The selection of the type of the doped material can be fluorescent material or phosphorescent material; the amount of the dopant is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, even more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass. The fluorescent doped material of the invention comprises: fused polycyclic aromatic derivatives, styrylamine derivatives, fused ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and the like, but are not limited thereto; the phosphorescent dopant material of the present invention comprises: heavy metal complexes,Phosphorescent rare earth metal complexes, etc., but are not limited thereto, and among them, heavy metal complexes, for example, iridium complexes, platinum complexes, osmium complexes, etc.; the rare earth metal complex may be, for example, a terbium complex, a europium complex, or the like, but is not limited thereto. The electron transport material of the present invention preferably has good electron mobility while having suitable HOMO and LUMO energy levels, and may be, for example, a metal complex, an oxathiazole derivative, an oxazole derivative, a triazole derivative, an azabenzene derivative, a phenanthroline derivative, a diaza-anthracene derivative, a silicon-containing heterocyclic compound, a boron-containing heterocyclic compound, a cyano compound, a quinoline derivative, a benzimidazole derivative, or the like, but is not limited thereto. The electron injecting material of the present invention preferably has an electron transporting ability while having an effect of injecting electrons from the cathode, and has an excellent thin film forming ability, and may be, for example, an alkali metal compound (e.g., lithium oxide, lithium fluoride, 8-hydroxyquinoline lithium, lithium boron oxide, cesium carbonate, 8-hydroxyquinoline cesium, potassium silicate, calcium fluoride, calcium oxide, magnesium fluoride, magnesium oxide), fluorenone, a nitrogen-containing five-membered ring derivative (e.g., an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a metal complex); anthraquinone dimethane, diphenoquinone, anthrone derivatives, and the like, but are not limited thereto, and these compounds may be used alone or in combination with other materials. The cathode material of the present invention preferably has a low work function so as to easily inject electrons into the organic layer, and may be, for example, a metal (e.g., magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, aluminum, silver, tin, lead, or an alloy thereof) or a multi-layered material (e.g., LiF/Al or LiO)₂Al) but not limited thereto.

The organic layer materials of the present invention, when they are used, may be formed into a single layer structure by film-forming alone, or may be mixed with other materials to form a single layer structure, or may be formed into a laminated structure of single layers formed alone, a laminated structure of single layers mixed into a film, a laminated structure of single layers formed alone and a laminated structure of single layers mixed into a film, but are not limited thereto. The organic photoelectric device (e.g., organic electroluminescent diode) of the present invention can be manufactured by sequentially stacking the above-described structures. As the production method, known methods such as a dry film formation method and a wet film formation method can be used, and examples of the dry film formation method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method; the wet film formation method may be, for example, various coating methods such as a spin coating method, a dipping method, a casting method, an ink jet method, but is not limited thereto. The organic photoelectric device (such as an organic electroluminescent diode) of the present invention can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps, and the like.

The Organic light emitting Element of the present invention is an Organic photovoltaic device, an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), and an Organic Memory device (Organic Memory Element), a lighting and display device. The synthesis of the tricarbazole derivative represented by the general formula (1) of the present invention can be carried out by a method known in the art, for example, a cross-coupling reaction using a transition metal such as nickel or palladium, or a C-C, C-N coupling formation reaction using a transition metal such as magnesium or zinc. The above reaction is limited to mild reaction conditions, superior selectivity of various functional groups, and the like, and Suzuki and Buchwald reactions are preferred.

Examples

The tricarbazole derivatives of the present invention are illustrated by the following examples, but are not limited to the tricarbazole derivatives and the synthetic methods illustrated by these examples.

The initial raw materials and solvents adopted in the embodiments and the comparative examples of the invention are purchased from national medicine, and part of commonly used products such as OLED intermediates are purchased from domestic OLED intermediate manufacturers and various palladium catalysts, ligands and the like are purchased from sigma-Aldrich companies.

1HNMR data were determined using a JEOL (400MHz) nuclear magnetic resonance apparatus; HPLC data were determined using a Shimadzu LC-20AD HPLC.

The substances used in the examples and comparative examples were:

(Compound 1) 14-phenyl-5, 8-bis (3-phenylquinolin-2-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 5) 5, 8-Diphenyl-14- (3-phenylquinolin-2-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 11) 14-phenyl-5, 8-bis (pyridin-4-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 19) 14- (Naphthalen-2-yl) -5, 8-bis (1-phenyl-1H-1, 2, 4-triazol-3-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 24) 2, 11-di-tert-butyl-5, 8, 14-tris (pyridin-4-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 29) 2,2', 2' - (2, 11-di-tert-butyl-5H-pyrrolo [3,2-b:4,5-b ' ] dicarbazole-5, 8, 14-triacyl) tris (benzo [ d ] oxazole).

(compound 38) 5,8, 14-tris (pyridin-4-yl) -8, 14-dihydro-5H-pyridine [2', 3': 4,5] pyrrolo [3,2-b ] pyrrolo [2', 3': 4,5] pyrrolo [2,3-h ] carbazole.

(compound 43) 2,2', 2' - (5H-pyridyl) [2', 3': 4,5] pyrrolyl [3,2-b ] pyridinyl [2', 3': 4,5] pyrrolyl [2,3-h ] carbazole-5, 8, 14-tris (benzo [ d ] oxazole).

(Compound 46) 14- (isoquinolin-3-yl) -5, 8-bis (quinolin-2-yl) -8, 14-dihydro-5H-pyridine [3', 4': 4,5] pyrrolo [3,2-b ] pyrrolo [3', 4': 4,5] pyrrolo [2,3-h ] carbazole.

(Compound 54) 5,8, 14-tris (quinolin-5-yl) -8, 14-dihydro-5H-pyridine [3,4 ]: 4,5] pyrrolo [3,2-b ] pyrrolo [3,4 ]: 4,5] pyrrolo [2,3-h ] carbazole.

(Compound 68) 5,8, 14-tris (pyridin-4-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole-2, 11-dicarbonitrile.

(Compound 88) 5,8, 14-Tris (pyrazin-2-yl) -8, 14-dihydro-5 h-pyridine [3,4 ]: 4,5] pyrrolo [3,2-b ] pyridine [3,4 ]: 4,5] pyrrolo [2,3-h ] carbazole.

(compound 93) 5,8, 14-tris (4- (pyridin-4-yl) phenyl) -8, 14-dihydro-5H-pyridine [2', 3': 4,5] pyrrolo [3,2-b ] pyrrolo [2', 3': 4,5] pyrrolo [2,3-h ] carbazole.

(Compound 145) 14- (1, 10-phenanthrolin-2-yl) -5, 8-diphenyl-8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 148) 14- (1, 10-phenanthrolin-2-yl) -2,5,8, 11-tetraphenyl-8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

(Compound 184) 14- (3- (1, 8-naphthyridin-4-yl) phenyl) -5, 8-bis (naphthalen-2-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

The synthetic route is as follows:

。

example 1

Synthesis of Compound 1

。

(1) Under argon atmosphere, 40.1 g (100mmol) of 2, 7-dibromo-9-phenyl-9H-carbazole, (36.7 g (220mmol) of 2-nitrophenyl) boronic acid, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro [ 3-phenylallyl ] palladium (II) catalyst 648 mg, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 1000ml of ethylene glycol dimethyl ether (DME) were charged into a reaction vessel, and heated and stirred at 80 ℃ overnight. Cooled to room temperature, added with 800ml of water, precipitated as a solid, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 39.3g of the compound 2, 7-bis (2-nitrophenyl) -9-phenyl-9H-carbazole, yield 81%, purity by HPLC 99.6%.

1HNMR(DMSO)：δ8.62(d，1H),8.31 (d，1H), 8.22(d，2H),8.03～8.00(m,4H) 7.91～7.89(m,3H),7.74～7.72(m,4H),7.62(m,2H), 7.58(m,1H),7.50(m,1H)

。

(2) Under argon atmosphere, 48.6 g (100mmol) of 2, 7-bis (2-nitrophenyl) -9-phenyl-9H-carbazole was added to a reaction vessel, and dissolved in 100ml of chlorobenzene, and 7.9 g of triphenylphosphine was added thereto, and the mixture was stirred at 180 ℃ overnight. Cooled to room temperature, filtered, and the filtrate was freed of the solvent under reduced pressure, and the crude product obtained was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 32.9g of the compound 14-phenyl-8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole in 78% yield and 98.6% purity by HPLC.

1HNMR(DMSO)：δ11.66(s，2H)，8.19(d，2H),7.63～7.62(m，4H),7.55(s，2H), 7.50(m,4H),7.40(s,2H),7.20(m,2H)。

(3) 26.9 g (240 mmol) of potassium tert-butoxide, 648 mg (1 mmol) of [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro [ 3-phenylallyl ] palladium (II) catalyst, 62.7g (220mmol) of 2-bromo-3-phenylquinoline, 42.2 g (100mmol) of 14-phenyl-8, 14-dihydro-5H-pyrrole [3,2-b:4,5-b' ] dicarbazole and 1000mL of ethylene glycol dimethyl ether (DME) were charged into a reaction vessel under an argon atmosphere, and stirred with heating at 80 ℃ for 15 hours. The reaction mixture was cooled to room temperature, 500ml of water was added, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 68.1 g of compound 1, 99.6% purity by HPLC, 82% yield.

1HNMR(DMSO)：δ8.55 (d，2H)，8.40(d，4H),7.94(d，2H),7.80(d，4H), 7.67(m,4H),7.62(m,2H),7.59～7.57(m,7H),7.50(m，2H), 7.47(s，4H), 7.35(m,2H),7.16(m,2H)。

Example 2

Synthesis of Compound 5

Same as example 1 except that the starting material was replaced with 2, 7-dibromo-9- (3-phenylquinolin-2-yl) -9H carbazole

1HNMR(DMSO)：δ8.62(d，2H),8.40(m，3H), 8.22(m，2H),8.03～8.00(m,4H) 7.89(m,2H),7.80(m,2H),7.74(s,2H),7.72(m,2H),7.62(m,2H), 7.59～7.57(m,2H)

The procedure was as in example 1 except that the starting material was changed to 3-nitro-7- (2-nitrophenyl) -2-phenyl-9- (3-phenylquinolin-2-yl) -9H-carbazole.

1HNMR(DMSO)：δ11.66(s，2H)，8.40(d2H),8.19(d,2H),7.80(d,2H),7.67(m,2H),7.63(d，2H),7.59～7.57(m，3H), 7.55(s,2H),7.50(m,2H),7.40(s,2H),7.20(m,2H).

The procedure was as in example 1 except that the starting material was replaced with 14- (3-phenylquinolin-2-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

1HNMR(DMSO)：δ8.55 (d，2H)，8.40(d，4H),7.94(d，2H),7.80(d，2H), 7.62(m,4H),7.59～7.57(m,5H),7.50(m，4H), 7.47(s，4H), 7.35(m,2H),7.16(m,2H)。

Example 3

Synthesis of Compound 11

Same as in example 1.

The procedure of example 1 was repeated, except that the bromide was replaced with p-bromopyridine.

1HNMR(DMSO)：δ8.56 (d，4H),8.55(d,2H),7.94(d，2H),7.62(m，2H), 7.58(m,1H),7.50(d,6H),7.47(s,4H),7.35(d,2H),7.16(d,2H)。

Example 4

Synthesis of Compound 19

The procedure was as in example 1 except that the starting material was changed to 2, 7-dibromo-9- (naphthalen-2-yl) -9H-carbazole.

1HNMR (DMSO)：δ8.62(d，1H),8.31 (d，1H), 8.22(d，2H),8.03～8.00(m,6H) 7.91～7.89(m,3H),7.74～7.72(m,4H),7.62(m,1H),7.58(m,2H),7.50(m,1H)

The procedure was as in example 1 except that the starting material was changed to 9- (naphthalen-2-yl) -2, 7-bis (2-nitrophenyl) -9H carbazole.

1HNMR (DMSO)：δ11.66(s，2H)，8.19(d，2H),8.03(d,3H),7.83(s,1H),7.63

(d,2H),7.59～7.58(m,2H),7.55(s,2H),7.50(m,2H),7.40(s,2H),7.36(m,1H),7.20(m,2H).

The procedure was as in example 1 except that the starting materials were replaced with 3-bromo-1-phenyl-1H-1, 2, 4-triazole and 14- (naphthalen-2-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

1HNMR (DMSO)：δ9.24(s,2H),8.55 (d，2H),8.03(d，3H),7.94(m，2H),7.83(s,1H),7.67

(d,4H),7.59～7.58(m,2H),7.57(m,4H),7.52(m,2H),7.47(s,4H),7.35(d,2H),7.16(d,2H)。

Example 5

Synthesis of Compound 24

。

The procedure was as in example 1 except that the starting materials were replaced with 2, 7-dibromo-9- (pyridin-4-yl) -9H-carbazole and (5- (tert-butyl) -2-nitrophenyl) boronic acid.

1HNMR(DMSO)：δ8.62(d，2H),8.56 (d，2H), 8.28(d，2H),8.22(d,2H),8.19

(s,2H),7.74(s,2H),7.67(m,2H),7.50(m,2H),1.43(s,18H).

The procedure was as in example 1 except that the starting material was changed to 2, 7-bis (5- (tert-butyl) -2-nitrophenyl) -9- (pyridin-4-yl) -9H-carbazole.

1HNMR (DMSO)：δ11.66(s，2H)，8.56(d,2H),8.36(s,2H),7.62(d，2H),7.55(s,2H),

7.50(m,4H),7.40(s,2H),1.43(s,18H).

The procedure was as in example 1 except that the starting materials were replaced with p-bromopyridine and 2, 11-di-tert-butyl-14- (pyridin-4-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

1HNMR (DMSO)：δ8.95(s,2H),8.56(d，6H),7.86(d，2H),7.50(m，6H),7.47(s,6H),

7.11(d,2H),1.43(s.18H).

Example 6

Synthesis of Compound 29

The procedure was as in example 1 except that the starting materials were replaced with 2- (2, 7-dibromo-9H-carbazol-9-yl) benzo [ d ] oxazole and (5- (tert-butyl) -2-nitrophenyl) boronic acid.

1HNMR (DMSO)：δ8.62(d，2H),8.28(d，2H),8.22(d,2H),8.19(s,2H),7.74(s,2H),7.72

(m,2H),7.67(m,2H),7.39(m,2H),1.43(s,18H).

The procedure was as in example 1 except that the starting material was changed to 2- (2, 7-bis (5- (tert-butyl) -2-nitrophenyl) -9H-carbazol-9-yl) benzo [ d ] oxazole.

1HNMR (DMSO)：δ11.66(s，2H),8.36(s,2H),7.72(m，2H),7.62(m,2H),7.55(s,2H),

7.50(d,2H),7.40(s,2H),7.39(m,2H),1.43(s,18H).

The procedure was as in example 1 except that the starting material was changed to 2-bromobenzo [ d ] oxazole, 2- (2, 11-di-tert-butyl-5, 8-dihydro-14H-pyrrolo [3,2-b:4,5-b' ] dicarbazolyl-14-yl) benzo [ d ] oxazole.

1HNMR (DMSO)：δ8.95(s,2H),8.36(d，6H),7.86(d，2H),7.72(m,6H), 7.47(s,6H),7.39

(m,6H),7.11(d,2H),1.43(s.18H).

Example 7

Synthesis of Compound 38

The procedure was as in example 1 except that the starting materials were replaced with 2, 7-dibromo-9- (pyridin-4-yl) -9H-carbazole and (3-nitropyridin-2-yl) boronic acid.

1HNMR (DMSO)：δ8.76(d，2H),8.62 (m，4H), 8.56(d，2H),8.30 (d,2H), 8.13(s,2H),

7.50(d,2H),7.27(m,2H)

The procedure was as in example 1 except that the starting material was changed to 2, 7-bis (3-nitropyridin-2-yl) -9- (pyridin-4-yl) -9H carbazole.

1HNMR(DMSO)：δ11.66(s，2H)，9.34(s，2H),8.56(m,2H),8.43(m,2H),7.55(s,2H), 7.50

(d,2H),7.46(d,2H),7.40(s,2H).

Except that the starting materials were replaced with p-bromopyridine and 14- (pyridin-4-yl) -8, 14-dihydro-5H-pyridine [3', 4': 4': 4,5] pyrrolo [3,2-b ] pyridine [3', 4': the procedure of example 1 was repeated except for using 4,5] pyrrolo [2,3-h ] carbazole.

1HNMR (DMSO)：δ8.56 (d，6H),8.43(m,3H),7.97(d，2H),7.55(s，2H),7.50(m,6H),

7.40(s,2H),7.22(m,2H)

Example 8

Synthesis of Compound 43

The procedure was as in example 1 except that the starting material was changed to 2- (2, 7-dibromo-9H-carbazol-9-yl) benzo [ d ] oxazole (3-nitropyridin-2-yl) boronic acid.

1HNMR (DMSO)：δ8.76(d，2H),8.62(m，2H),8.30(m,4H),8.13(s,2H),7.72(m,2H),7.39

(m,2H),7.27(m,2H).

The procedure was as in example 1 except that the starting material was changed to 2- (2, 7-bis (3-nitropyridin-2-yl) -9H-carbazol-9-yl) benzo [ d ] oxazole.

1HNMR (DMSO)：δ11.66(s，2H),9.34(s,2H),8.43(m，2H),7.72(m,2H),7.55(s,2H),7.46

(m,2H),7.40(s,2H),7.39(m,2H).

The procedure was as in example 1 except that the starting material was changed to 2-bromobenzo [ d ] oxazole, 2- (5, 8-dihydro-14H-pyrido [3', 4': 4,5] pyrrolo [3,2-b ] pyrido [3', 4': 4,5] pyrrolo [2,3-H ] carbazol-14-yl) benzo [ d ] oxazole.

1HNMR (DMSO)：δ8.43(m,2H),7.97(d，2H),7.72(m，6H),7.55(s,2H), 7.40(s,2H),7.39

(m,6H),7.22(m,2H).

Example 9

Synthesis of Compound 46

The procedure was repeated as in example 1 except for changing the starting material to 45.2 g (100mmol) of 2, 7-dibromo-9- (isoquinolin-3-yl) -9H-carbazole, (4-nitropyridin-3-yl) boronic acid.

1HNMR (DMSO)：δ9.50(s，2H),9.46(s，1H),8.62(d,2H),8.29(d,2H),8.22(m,2H),8.05

(d,2H),7.98(d,1H),7.74(s,2H),7.68(m,1H),7.64(m,1H),7.62(s,1H).

The procedure was as in example 1 except that the starting material was changed to 9- (isoquinolin-3-yl) -2, 7-bis (4-nitropyridin-3-yl) -9H-carbazole.

1HNMR (DMSO)：δ11.66(s，2H),9.46(s,1H),9.34(s,2H),8.43(m，2H),7.98(d,

1H),7.68(m,1H),7.64(d,1H),7.62(s,1H),7.57(m,1H),7.55(s,2H),7.46(d,2H),7.40(s,2H).

Except that the starting materials were changed to 2-bromoquinoline and 14- (isoquinolin-3-yl) -8, 14-dihydro-5H-pyridine [3', 4': 4,5] pyrrolo [3,2-b ] pyrrolo [3', 4': the procedure of example 1 was repeated except for using 4,5] pyrrolo [2,3-h ] carbazole.

1HNMR(DMSO)：δ9.46(s,1H),9.34(s，2H),8.43(d,2H),8.35(d,2H),8.03(d,2H),8.00(d,2H),

7.98(d,1H),7.96(d,2H),7.83(m,2H),7.68(m,1H),7.64(d,1H),7.62(s,1H),7.57(m,1H),7.53(m,2H),7.51(d,2H),7.47(s,4H).

Example 10

Synthesis of Compound 54

The procedure was as in example 1 except that the starting materials were replaced with 2, 7-dibromo-9- (quinolin-5-yl) -9H-carbazole and (4-nitropyridin-3-yl) boronic acid.

1HNMR (DMSO)：δ9.50(s，2H),8.95(d，1H),8.62(d,2H),8.46(d,1H),8.29(d,2H),8.22

(m,2H),8.12(d,1H),8.05(d,2H),8.00(m,1H),7.92(d,1H),7.74(s,2H),7.63(m,1H).

The procedure was as in example 1 except that the starting material was changed to 2, 7-bis (4-nitropyridin-3-yl) -9- (quinolin-5-yl) -9H carbazole.

1HNMR (DMSO)：δ11.66(s，2H),9.34(s,2H),8.95(d，1H),8.46(d,1H),8.43(d,2H),8.12

(d,1H),8.00(m,1H),7.92(d,1H),7.63(m,1H),7.55(s,2H),7.46(d,2H),7.40(s,2H).

Except that the starting materials were changed to 5-bromoquinoline and 14- (quinolin-5-yl) -8, 14-dihydro-5H-pyridine [3', 4': 4,5] pyrrolo [3,2-b ] pyrrolo [3', 4': the procedure of example 1 was repeated except for using 4,5] pyrrolo [2,3-h ] carbazole.

1HNMR(DMSO)：δ9.34(s，2H),8.95(d，3H),8.46(d,3H),8.35(d,2H),8.12(d,2H), 8.00

(m,3H),7.92(d,3H),7.63(m,3H),7.51(d,2H),7.47(s,4H)。

Example 11

Synthesis of Compound 68

The procedure was as in example 1 except that the starting materials were replaced with 2, 7-dibromo-9- (pyridin-4-yl) -9H-carbazole and (5-cyano-2-nitrophenyl) boronic acid.

1HNMR (DMSO)：δ8.62(s，2H),8.56 (d，2H), 8.54(d，2H),8.22(d,2H), 8.11(s,2H),7.96

(d,2H),7.74(s,2H),7.50(d,2H).

The procedure was as in example 1 except that the starting material was changed to 3,3' - (9- (pyridin-4-yl) -9H-carbazole-2, 7-diacyl) bis (4-nitrobenzonitrile).

1HNMR (DMSO)：δ11.66(s，2H),8.56(m,2H),7.80(s,2H),7.76(d,2H), 7.50(d,2H),7.55

(s,2H),7.50(d,2H),7.40(s,2H),7.33(d,2H).

The procedure was as in example 1 except for replacing the starting material with 34.8g (220mmol) of 4-bromopyridine, 14- (pyridin-4-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole-2, 11-dicarbonitrile.

1HNMR (DMSO)：δ8.56 (d,6H),8.12(d,2H),7.80(s,2H),7.50(d,6H),7.47(s,4H),7.33(d,2H).

Example 12

Synthesis of Compound 88

The procedure was repeated as in example 1 except for changing the starting material to 40.3 g (100mmol) of 2, 7-dibromo-9- (pyrazin-2-yl) -9H-carbazole, (4-nitropyridin-3-yl) boronic acid.

1HNMR (DMSO)：δ9.50(s,2H),8.83 (m，1H), 8.82(s，1H),8.76(d,1H), 8.62(d,2H),8.29

(d,2H),8.22(d,2H),8.05(d,2H),7.74(s,2H).

The procedure was as in example 1 except that the starting material was changed to 2, 7-bis (4-nitropyridin-3-yl) -9- (pyrazin-2-yl) -9H carbazole.

1HNMR (DMSO)：δ11.66(s，2H),9.34(s,2H), 8.83 (m，1H), 8.82(s，1H),8.76(d,

1H), 8.43(d,2H),7.55(s,2H),7.46(d,2H),7.40(s,2H).

The procedure was as in example 1 except that the starting material was changed to 35.0g (220mmol) of 2-bromopyrazine, 14- (pyridin-4-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

1HNMR (DMSO)：δ9.34 (s，2H), 8.83 (m，3H), 8.82(s，3H),8.76(d,3H), 8.35(d,2H),

7.51(d,2H),7.47(s,4H).

Example 13

Synthesis of Compound 93

The procedure was as in example 1 except for replacing the starting material with 47.8 g (100mmol) of 2, 7-dibromo-9- (4- (pyridin-4-yl) phenyl) -9H-carbazole (3-nitropyridin-2-yl) boronic acid.

1HNMR (DMSO)：δ8.76(d,2H),8.71 (d，2H), 8.62(s，4H),8.30(d,2H), 8.13(s,2H),8.00

(d,2H),7.92(d,2H),7.91(d,2H),7.27(d,2H).

The procedure was as in example 1 except that the starting material was changed to 2, 7-bis (3-nitropyridin-2-yl) -9- (4- (pyridin-4-yl) phenyl) -9H carbazole.

1HNMR(DMSO)：δ11.66(s，2H),9.34(s,2H), 8.71 (d，2H), 8.43(d，2H), 8.00(d,2H),7.92(d,2H),7.91(d,2H),7.55(s,2H),7.46(d,2H),7.40(s,2H).

Except that the starting material was changed to 4- (4-bromophenyl) pyridine 51.5g (220mmol), 14- (4- (pyridin-4-yl) phenyl) -8, 14-dihydro-5H-pyridine [3', 4': 4,5] pyrrolo [3,2-b ] pyrrolo [3', 4': the procedure of example 1 was repeated except for using 4,5] pyrrolo [2,3-h ] carbazole.

1HNMR(DMSO)：δ8.71 (d，6H), 8.43 (d，2H),8.00(d,6H),7.97(d,2H),7.92(d,6H),7.91(d,6H),7.55(s,2H),7.46(d,2H),7.40(s,2H),7.22(d,2H)。

Example 14

Synthesis of Compound 145

The procedure was as in example 1 except that the starting material was changed to 2- (2, 7-dibromo-9H-carbazol-9-yl) -1, 10-phenanthroline.

1HNMR (DMSO)：δ8.80 (d，1H), 8.62 (d，2H), 8.45(d,2H),8.22(d,1H),8.14(d,1H),8.03

(d,3H),8.00(d,2H),7.89(d,2H), 7.46(d,2H),7.56(m,1H)，7.47(s,4H).

The procedure was as in example 1 except that the starting material was changed to 2- (2, 7-bis (2-nitrophenyl) -9H-carbazol-9-yl) -1, 10-phenanthroline.

1HNMR (DMSO)：δ11.66 (s，2H), 8.80 (d，1H), 8.45(d,2H),8.22(d,1H),8.19(d,

2H),8.14(d,1H),7.89(d,2H),7.63(d,2H),7.55(m,3H),7.50(m,2H),7.40(s,4H),7.20(m,2H).

、

The procedure was as in example 1 except that the starting materials were replaced with bromobenzene and 14- (1, 10-phenanthrolin-2-yl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole.

1HNMR (DMSO)：δ8.80 (d，1H), 8.55(d,2H),8.45(d,2H),8.03(d,1H),7.94(d,2H),7.89

(d,1H),7.62(m,4H),7.58(m,2H),7.56(m,1H),7.50(m,4H),7.47(s,4H),7.35(m,2H),7.16(m,2H).

Example 15

Synthesis of Compound 148

The procedure was as in example 1 except that the starting materials were replaced with 2- (2, 7-dibromo-9H-carbazol-9-yl) -1, 10-phenanthroline and (4-nitro- [1,1' -biphenyl ] -3-yl) boronic acid.

1HNMR (DMSO):δ8.80(d,1H),8.45(d,2H),8.32(d,2H),8.14(d,1H),8.03(d,1H),7.99(d,2H),

7.89(s,2H),7.77(d,2H),7.75(d,4H),7.56(m,1H),7.55(s,2H),7.49(m,4H),7.41(m,2H),7.40(s,2H),

7.34(d,2H).

The procedure of example 1 was repeated, except that the starting material was changed to 2- (2, 7-bis (4-nitro- [1,1' -biphenyl ] -3-yl) -9H-carbazol-9-yl) -1, 10-phenanthroline.

1HNMR (DMSO)：δ11.66(s,2H),8.80(d,1H),8.45(d,2H),8.14(d,1H),8.03(d,1H),7.99(d,2H),

7.89(s,2H),7.77(d,2H),7.75(d,4H),7.56(m,1H),7.55(s,2H),7.49(m,4H),7.41(m,2H),7.40(s,2H).

The procedure was as in example 1 except that the starting materials were replaced with 14- (1, 10-phenanthrolin-2-yl) -2, 11-diphenyl-8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole and 2-bromobenzene.

1HNMR (DMSO)：δ8.80(d,1H),8.45 (d,2H), 8.30(d,2H),8.14(d,3H),8.03(d,1H),7.89(d,3H),

7.75(d,4H),7.62(m,4H),7.58(m,2H),7.56(m,1H),7.50(d,4H),7.49(m,4H),7.47(s,4H),7.41(m,2H)。

Example 16

Synthesis of Compound 184

The procedure was as in example 1 except that the starting material was changed to 9- (3- (1, 8-naphthyridin-4-yl) phenyl) -2, 7-dibromo-9H-carbazole.

1HNMR (DMSO)：δ8.89(d,1H),8.70(d,1H),8.62(d,2H),8.39(d,1H),8.22(m,2H),8.03(d,2H),

8.00(d,2H),7.89(m,2H),7.79(d,1H),7.74(s,2H),7.72(m,2H),7.68(m,1H),7.60(d,1H),7.47(d,1H),

7.41(m,2H).

The procedure was as in example 1 except that the starting material was changed to 9- (3- (1, 8-naphthyridin-4-yl) phenyl) -2, 7-bis (2-nitrophenyl) -9H carbazole.

1HNMR (DMSO)：δ11.66(s,2H),8.89(d,1H),8.70 (d,1H), 8.39(d,1H),8.21(s,1H),8.19

(d,2H),7.79(d,1H),7.68(m,1H),7.63(d,2H),7.60(d,1H),7.55(s,2H),7.50(m,2H),7.47(d,1H),

7.41(m,1H),7.40(s,2H),7.20(m,2H).

The procedure was as in example 1 except that the starting materials were replaced with 14- (3- (1, 8-naphthyridin-4-yl) phenyl) -8, 14-dihydro-5H-pyrrolo [3,2-b:4,5-b' ] dicarbazole and 2-bromonaphthalene.

1HNMR(DMSO)：δ8.89(d,1H),8.70 (d,1H), 8.39(d,1H),8.21(s,1H),8.19(d,2H),8.03(m,6H),7.83(s,2H),7.79(d,2H),7.68(m,1H),7.59(m,2H),7.58(m,4H),7.50(m,2H),7.47(m,5H),7.41(m,1H),7.36(d,2H),7.20(m,2H).

Device embodiments

Evaluation of luminescent Material devices

The compounds of the respective organic layers used in the device examples and comparative examples are as follows:

。

example 17

The basic structure model of the organic photoelectric device is as follows:

ITO/HAT-CN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/EML (compound of the present invention): RD (Ir complex) = 94: 6 (40nm)/ETL (30nm)/LiF (1nm)/Al (80 nm).

The manufacturing method of the organic photoelectric device comprises the following steps:

(1) a transparent anodic Indium Tin Oxide (ITO)20 (10. omega./sq) glass substrate was subjected to ultrasonic cleaning with acetone, ethanol and distilled water in this order, and then treated with ozone plasma for 15 minutes.

(2) After an ITO substrate is arranged on a substrate fixer of vacuum vapor deposition equipment, the system pressure is controlled to be 10^-6Then HAT-CN with a thickness of 10nm, TAPC with a thickness of 40nm and TCTA with a thickness of 10nm were sequentially deposited on the ITO substrate.

(3) And (2) evaporating a light-emitting layer (EML) with the thickness of 40nm on the TCTA, wherein the mass ratio of the compound 1 to RD is 94: 6.

(4) an Electron Transport Layer (ETL) material was deposited on the light-emitting layer to a thickness of 30 nm.

(5) LiF with the thickness of 1nm is evaporated on the electron transport layer to be used as an electron injection layer.

(6) And finally, evaporating and plating Al with the thickness of 80nm on the electron injection layer to be used as a cathode, and packaging the device by using a glass packaging cover.

The device test results are shown in table 1.

Example 18

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 5. The device test results are shown in table 1.

Example 19

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 11. The device test results are shown in table 1.

Example 20

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 19. The device test results are shown in table 1.

Example 21

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 24. The device test results are shown in table 1.

Example 22

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 29. The device test results are shown in table 1.

Example 23

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 38. The device test results are shown in table 1.

Example 24

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 43. The device test results are shown in table 1.

Example 25

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 46. The device test results are shown in table 1.

Example 26

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 54. The device test results are shown in table 1.

Example 27

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 68. The device test results are shown in table 1.

Example 28

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 88. The device test results are shown in table 1.

Example 29

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 93. The device test results are shown in table 1.

Example 30

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 145. The device test results are shown in table 1.

Example 31

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 148. The device test results are shown in table 1.

Example 32

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound 184. The device test results are shown in table 1.

Comparative example 1

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound RH-01. The device test results are shown in table 1.

Comparative example 2

The device in this example was fabricated as in example 17 except that the host material of the light emitting layer (EML) was compound RH-02. The device test results are shown in table 1.

Table 1 shows the results of the performance tests of the devices of examples 17-32 and comparative examples 1-2

TABLE 1

。

The device structures in the above examples and comparative examples were all the same except that the light emitting layer was different, and the current efficiency of the devices comprising the tricarbazole derivative of the present invention was remarkably improved and the lifetime thereof was also improved with reference to the device performances of RH-01 and RH-02. In conclusion, the novel carbazole derivative has a great application value in organic photoelectric devices.

The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.