TW201006862A - Phenyl-phenanthrene derivatives, polymers, copolymers and light-emitting material compositions containing the phenyl-phenanthrene derivative - Google Patents

Abstract

A phenyl-phenanthrene derivative having formula (I): in which, each of R1, R2, R3 and R4, independently, is a substituent with a long chain alkyl or alkoxyl. The phenyl-phenanthrene derivative can be copolymerized with other hole-transporting or electron-transporting conjugated molecules to form a copolymer. A light emitting material with R, G, B and full colors can be obtained by the copolymer or blending a phenyl-phenanthrene polymer or the copolymer with other light emitting materials.

Description

201006862 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel phenanthrene derivative, and a luminescent material containing the phenanthrene derivative polymer. [Prior Art] At present, polymer electroluminescent diode (PLED) components have gradually developed into one of the future light sources due to their simple structure and component process, and easy fabrication of large-area and flexible components. The color stability and component life of PLEDs depend on the polymer materials used, and molecular aggregation is the main cause of PLED color instability. At the same time, polymer materials need to have good solubility due to the requirements of component process. A novel molecular structure is disclosed in U.S. Patent No. 6,967,255, which is shown below:

It can be applied to the field of organic optoelectronic materials and is the patent of the inventor of this case. This case is an extension of the patent. Further, a phenanthrene-based conjugated polymer is disclosed in Taiwan Patent Publication No. 200531593, and its structure is as follows: 7 201006862

It can be applied to the field of organic photoelectric materials, and is also the patent of the inventor of the present invention. U.S. Patent No. 6,268,072 discloses an electroluminescent polymer having a molecular structure as follows:

It is a copolymer of adamantane, phenylene and phenylanthracene. U.S. Patent No. 2007/0191583 A1 discloses a phenanthrene electroluminescent polymer having a molecular structure as follows:

Since the molecular structure has no steric hindrance, the molecules are liable to be stacked, which in turn affects the color stability of the light-emitting element. U.S. Patent No. 6,887,972 discloses a pyrene-based copolymerized electroluminescent high molecule whose molecular structure is as follows: 8 201006862

Similarly, the molecular structure has no steric hindrance, and the molecules are liable to cause stacking and affect the light color stability of the light-emitting element. A copolymerized compound having a cyclic molecule is disclosed in European Patent No. 1,074,600, the molecular structure of which is as follows:

The proportion of individual molecules copolymerized shall be in accordance with the formula indicated in the patent. Similarly, the molecular structure has no steric hindrance, and the molecules are liable to cause stacking and affect the light color stability of the light-emitting element. U.S. Patent Publication No. 2007/0081921 A1 discloses a copolymerized compound having a steric steric barrier formed by a benzene ring and a triple bond in a main chain, the molecular structure of which is as follows:

According to the molecular structure disclosed in this patent, the core molecule having a molecular steric hindrance is a large hard molecule, and the three sides of the molecule are connected by a triple bond, and the solubility is poor. And because it is a triple bond to the benzene ring molecule as the main chain, illumination 9 201006862 is not stable, and the wavelength of the electroluminescence will be delayed due to the long electron resonance, so that the wavelength of the emission cannot reach the dark blue field (4〇〇~43 0 nm ). However, if the phenanthrene is the main molecule and the benzene ring molecules are bonded by three bonds on both sides, there is a problem that the photoelectric efficiency is not good. Therefore, there is a need for a novel electroluminescent polymer structure to overcome the above problems. SUMMARY OF THE INVENTION The present invention provides a novel phenanthrene derivative having a structure as shown by the following formula (1):

The center of the formula (1), R2, R3 and 114 are each independently a linear or branched Cm alkyl group; a linear or branched (^_22 alkoxy group; ortho, meta or para (othro-, Metaalkyl, para-) alkylphenyl or alkylbenzyl, wherein the alkyl group contains a linear or branched c63() alkane φ group, ortho, meta or pair Alkoxyphenyl or alkoxybenzyl, wherein the alkoxy group comprises a linear or branched C6_3 decyloxy group; 2,3-, 2,4-, 2 , 5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkylbenzyl, wherein the alkyl group comprises a linear or branched C6_3 〇alkyl; 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dual-oxyl stupid ((^11〇^;^)11611 And 4) or dialkoxybenzyl, wherein the alkoxy group comprises a linear or branched C6_3 decyloxy group; or an alkyl aromatic heterocyclic group, wherein the alkyl group comprises a linear chain or a branch The chain is C6_3 decyl, and any of &, R2, R3 and R4 contains a hetero 10 201006862 atom. Further, the present invention further provides a phenanthrene derivative polymer, as shown in the formula (II):

Wherein Ri, R 2, R 3 and Κ 4 are as described above, and m is the number of repeating units. The present invention further provides a phenanthrene derivative copolymer as shown in formula (III)

Αγ1^Αγ2)—(αγ3)- nxv 7q Formula (III) wherein R1, R_2, R3 and R4 are as defined above; ΑΓι, ΑΓ2 and ΑΓ3 are molecules having an electrophilic or electrophilic group, each of which is independent From:

11 201006862

a group consisting of; and wherein R5, R6, uldent 7 and r8 are each independently selected from hydrogen; linear or branched (^-22 alkyl; linear or branched Cm2 alkoxy; ortho position Or an octo-, meta-, or para-alkylphenyl or alkylbenzyl group, wherein the alkyl group contains a linear or branched alkyl group; a 'alkoxyphenyl' or alkoxyxybenzyl, wherein the alkoxy group comprises a linear or branched C6_3() alkoxy group; 3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkylbenzyl, wherein the alkane The group comprises a linear or branched C63 alkyl group; a 2,3-, 2,4-, 2,5-, 2,6-, 3,4 or 3,5-bisalkoxyphenyl group ( Dialkoxyphenyl) or diaik〇xybenzyl, wherein the alkoxy group comprises a linear or branched fluorenyl-dealkyloxy group; and an alkylaromatic heterocyclic ring group in which the alkyl group comprises a straight a group consisting of a chain or a branched chain (: 6.3 〇 alkyl group, m, n, p, q of the formula (III) is the number of repeating units, and The number of ρ and q includes 0. Further, the present invention provides a luminescent material composition comprising: a phenanthrene benzene derivative polymer or a phenanthrene benzene derivative copolymer as described above, and a luminescent material. The objects, features, and advantages can be more clearly understood. The following is a detailed description of the following drawings: [Embodiment] 201006862 The phenanthrene derivative of the present invention is a phenanthrene-derived molecule having a unique molecular steric hindrance The highly soluble benzene-derived molecules are co-synthesized to form a conjugated molecule with a high energy gap (AEg = 3.1 V) and high photochromic stability, as shown by the following formula (I):

The phenanthrene derivative of the present invention contains a phenanthrene-derived molecule having a molecular steric barrier, thereby effectively preventing aggregation between molecules and increasing the stability of the color and thermal properties of the electroluminescent light. In addition, since the benzene-derived molecule has a long-chain substituent, the solubility of the phenanthrene derivative can be increased, and the benzene-derived molecule also contributes to the improvement of the photoelectric efficiency. The phenanthrene derivative of the formula (I) can be polymerized into a phenanthrene derivative polymer as shown in the following formula (II):

In addition, the phenanthrene derivative of the formula (I) is used as a core molecule, and copolymerized with other electrophilic or electrophilic conjugated molecules to obtain a copolymer having an energy gap between 1.8 and 3.0 eV. For the purpose of producing various light colors, the phenanthrene derivative copolymer is represented by the following formula (III):

Formula (III) 13 201006862 The R!, R2, R3 and R4 in the formula (1), the formula (II) and the formula (in) are each independently a Cl-22 group of a straight bond or a bond; a straight bond or a bond a Cl-22 alkoxy group, an ortho, meta or para (othro-, meta-, para-) alkylphenyl or alkylbenzyl, wherein the alkyl group comprises a straight A chain or branched C6-3G alkyl group; an ortho, meta or para alkoxyphenyl or alkoxybenzyl, wherein the alkoxy group comprises a straight chain or a branched chain. C6_3G alkoxy; 2,3-, 2,4-, 2,5-, 2,6... ▲ 3,4- or 3,5-bisalkylphenyl ((^11^1?1^1) ^1) or dialyl lbenzyl, wherein the alkyl group comprises a linear or branched C6_3 alkyl group; 2,3-, 2,4-, 2,5-, 2,6- , 3,4- or 3,5-dially oxylkoxyphenyl or dialoloxybenzyl, wherein the alkoxy group comprises a linear or branched C6.3G alkoxy group Or an alkyl aromatic heterocyclic group wherein the alkyl group contains a linear or branched C6_3 alkyl group, and any of &, R2, R3 and may be a hetero atom. The above Ri, R2, R3 and R4 have a substituent of a long-chain alkyl ru or alkoxy group, which can increase the solubility of the phenanthrene derivative polymer or copolymer. Aiv Ar2 and Αγ3 in the formula (III) are An electrophilic or electrophilic molecule-based molecule is independently selected from:

14 201006862

a group consisting of φ; wherein Rs, Re, R7 and Rs are each independently selected from nitrogen; linear or branched (^.22 alkyl; linear or branched <^_22 alkoxy An ortho, meta or para (othro-, meta-, para-) alkylphenyl or an alkylbenzyl group in which the stimuli comprise a linear or branched C6- 3 〇 alkyl; alkoxypheny 1 or alkoxybenzy 1 in the ortho, meta or para position, wherein the alkoxy group comprises a linear or branched C6-3G Alkoxy; 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dichophenyl fluorenyl (out &11^7^^1^71), wherein the alkyl group comprises a linear or branched (: 6_3 () alkyl; 2, 3-, 2, 4-, 2, 5-, 2, 6-, 3,4- or 3,5-dialioxyphenyl or dialoloxybenzyl, wherein the alkoxy group comprises a linear or branched (6_3 ( Alkoxy; and alkyl aromatic heterocyclic group wherein the alkyl group comprises a group consisting of a linear or branched C6_3() alkyl group. m, n, p, q of formula (III) are repeating units Number And wherein the number of p and q includes 0', that is, the conjugated molecule of formula (I) can be copolymerized with one or more aromatic co-molecules, thereby adjusting the energy gap of the phenanthrene derivative copolymer. The molecular weight of the phenanthrene derivative copolymer of the invention is up to 1 million in the case of being soluble. The preferred molecular weight is between about 100,000 and 800,000, more preferably between 200,000 and 600,000. Good Photoelectric Efficacy. In one embodiment, the phenanthrene-derived co-molecular molecule in the phenanthrene derivative of the present invention can be prepared by the following scheme:

The compound I phenanthrene-derived conjugated molecule has a polycyclic stereo structure, which is called ❹ 9,10; 9,10-di(cyclopentanthene)-9,10-dihydrophenanthrene (9,10; 9,10-bis) (cyclopenta)-9,10-dihydrophenanthrene)) ° The benzene-derived conjugated molecule of the phenanthrene derivative of the present invention has one or more alkyl chains or alkoxy chains, which have high solubility properties and can be purchased directly. Sigma-Aldrich Co. or self-synthesis, for example, the following benzene-derived molecules purchased from Sigma-Aldrich Co.: 16 201006862

CAS : 1646-53-3 CAS : 556-96-7

CAS : 2655-84-7

CAS : 131738-73-3

CAS : 583-68-6

Or by the following process:

Br

Br-R K2C03

Compound II The above compound I diboron bis(cyclopentane) dihydrophenanthrene and compound II brominated alkoxybenzene (or brominated alkylbenzene) can be obtained by Suzuki coupling reaction (Suzuki Coupling Reaction). The high energy gap phenanthrene derivative compound III is further subjected to bromination and catalysis to obtain compound IV and compound V. As shown in the following reaction formula:

+ Br

OR 17 201006862

Pd(dppf)Cl2, CH2CI2 K3PO4, two a 垣.13⁄4 heating

Compound III

PdCPf)h3)4, n%co3 (峋toluene)

Compound IV

Compound V Next, the compound IV obtained from the phenanthrene derivative compound III and the compound V are polymerized by a Suzuki coupling reaction to obtain a high energy gap phenanthrene derivative polymer of the present invention, such as the following reaction formula. Show:

Wherein R1 to R4 are as defined above, and m is the number of repeating units, and the high energy gap phenanthrene derivative polymer emits blue light. The above phenanthroline-derived compound V can be copolymerized with other conjugated molecules of dibromo-electrophilic or pro- 18 201006862 holes to obtain red, green, blue and white light.

+ nBr-Arl-Br + PBr.Ai2-Br+ qBr-Ai3-Br

Satay A inch where = Γ 1, ΑΓ 2 and ΑΓ 3 As defined above, m, n, p, q are the number of repeated early 兀. ❹ The above phenanthrene polymer or copolymer can be used alone in photovoltaic elements, or with other luminescent materials, such as luminescent dyes, organic electroluminescent materials, inorganic electroluminescent materials, organic photoexcited recording materials or inorganic light. The excitation light material is doped to form a composition for use in a photovoltaic element, and the composition can emit red, green, blue, and white light full color light color. The photoelectric element is, for example, an organic electro-optic element, a pyroelectric element, a photosensor, an organic memory element, and a light-emitting body. The ratio of each component contained in the composition is not particularly limited, and the corresponding illuminating energy level can be adjusted according to the desired luminescence. The group Ϊ = = 5 〇 to " fused phenanthrene derivative polymer of the present invention j to 1 is a mixture of luminescent materials. The phenanthrene derivative polymer of the present invention or a total of 5000 is preferably more than 2 〇 〇〇〇, more preferably, a knife, a stalk, a soil of 4 〇, or more. The phenanthrene derivative polymer, copolymer or composition containing the same according to the present invention 19 201006862 can be dissolved in a single solvent or a cosolvent which is generally non-polar or low-polar, for example, (1) an aromatic hydrocarbon: Toluene, xylene, ethyl phenyl, diethyl benzene, dibutyl benzene, cymene, propyl benzene, mesitylene, trimethyl benzene (trimethylbenzene), tetralin, tetramethylbenzene or dodecylbenzene; (2) benzene derivatives containing dentate: such as chlorobenzene, dichlorobenzene or trigasbenzene; 3) Alkoxy-containing benzene derivatives: such as anisole (anis〇ie) or phenethyl ether (phenetole); (4) heterocyclic derivatives containing a nitrogen atom: such as pyridine, methyl 11-pyridine , hexahydropyridine, methyl hexapyridine, dimethyl hexahydropyridine, ethylmethyl hexahydro 0 sigma, 0 pyrrolidine, methyl σ 嘻 嘻, or η 咯 (pyrrole (5) furan derivatives: such as tetrahydrofuran (THF), mercaptotetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, tetradecyltetrahydrofuran, or Tetrahydropyran; (6) a cyclic aliphatic saturated network: such as cyclohexanone; or a combination of the foregoing cosolvents. Since the phenanthrene derivative polymer, copolymer or group φ composition thereof of the present invention has a solubility in a general non-polar or low-polar single solvent or co-solvent of about 0.1% by weight to 10% by weight, It can be applied to liquid process 'for example, inkjet printing, spin coating, die coating, screen printing or printing to manufacture photovoltaic elements, and the process is convenient. In one embodiment, the phenanthrene derivative polymer, copolymer or composition containing the composition of the present invention can be formed into a film on a substrate having a transparent electrode by a liquid process, and then the metal cathode is evaporated. It can be fabricated into an organic electroluminescent device or a photovoltaic element. Please refer to FIG. 4, which is a schematic cross-sectional view of an organic electroluminescent device, wherein the substrate 10 is a transparent or opaque glass 20 201006862 glass or plastic substrate having a transparent electrode 2 on the substrate 10, such as ITO, IZO or PEDOT. (Poly(ethylenedioxytliiophene)), a hole transport layer 30' may be provided on the transparent electrode 20, for example, PEDOT. Then, the present invention is coated on the hole transport layer 3 The phenanthrene derivative polymer, the copolymer or the solution containing the composition thereof 'forms the light-emitting layer 40, and then vapor-deposits the metal cathode 5 on the light-emitting layer 40 to form an organic electroluminescence element. ❹ The phenanthrene derivative polymer, the copolymer or the μ-containing product thereof of the invention can also be combined with other metal thin films or dielectric layers to be fabricated into various organic electrons, such as organic thin film memory, capacitors, and the like. Biochemical sensor, material wafer, thin film transistor (TFT), organic laser element, etc. The following describes in detail the phenanthrene of the formula (1), formula (II) and formula (III) according to the present invention, The synthesis steps of the polymer and the copolymer are Related Test result: • At χ Synthesis of Compound [Example 1] (9,10: 9'1 (K bis (cyclopentane) -9,10-dihydro-phenanthrene: 9,1〇 9'1Q

First, a reactant 1 was prepared, which has the following reaction formula:

201006862 Mix 2 grams of NaOH with 200 ml of sterol and heat to 60 °C. After the NaOH was completely dissolved, 3 g of phenanthrene-9,10·dione and 4 g of diethyl l,3-acetonedicarboxylate (95% by ACROS) were added to maintain 60°. C. After 36 hours of reaction, a 10% aqueous solution of HCl was added to neutralize the precipitate for filtration. The precipitate was collected and dissolved in acetic acid, and then 300 ml of a 10% aqueous HCl solution was added, and the reaction was heated for 18 hours. The acetic acid and water were removed, neutralized with an aqueous solution of sodium hydrogencarbonate, and the mixture was separated by filtration. Next, 9,10:9,10-di(cyclopentane)-9,10-dihydrophenanthrene is synthesized, and the reaction formula is as follows:

3 g of the reactant 1 was mixed with 150 ml of ethylene glycol, and 5 g of NzHU (manufactured by Lancaster Co., Ltd., 98%) was added and stirred for 10 minutes, and then 0.5 g of KOH was added and heated to 180. (:, reaction for 15 hours. After cooling to room temperature, it was diluted with water to give Compound 1 and purified by sublimation to give a white solid (yield: 48%). The 1H NMR (CDC13) spectral data measured by Compound 1 is as follows: (ppm) 1.43~1.47(m,2H), 1.59~1.64(m,2H), 1.96~2.03(m, 4H), 2.12~2.18(m,4H),7.19~7.28(m,4H),7.36~ 7.38 (d, 2H), 7.89 to 7.91 (d, 2H). 201006862 [Example 2] Synthesis of Compound 2: 9,10:9,10-di(cyclopentane)-2,7-diboron-9 , 10-dihydrophenanthrene (9,10:9,10-bis(cyclopenta)-2,7-diboron-9,10-dihydrophenant hrene) The synthesis reaction formula is as follows:

2 g of the compound 1 was dissolved in 20 ml of a solvent of dichloromethane (DCM), and then 20 ml of an acetic acid solvent was added thereto, and 3 g of bromine water (Br2, manufactured by Lancaster Co., Ltd.) was added dropwise thereto and stirred at normal temperature for three hours to obtain a white crystalline solid product. The yield was 75%. 6.66 g of Bis(pinacolato) diboron (manufactured by Boron Molecular) and 5 g of the above white crystal were dissolved under nitrogen. In 100 ml of toluene (TEDIA) solvent, add 4.72 g of potassium acetate (JT, Baker, 98%) and 0.1 g of dichloro [1, fluorene-bis(phenylphosphino)phenanthrene] (II) dichlorocarbamate. A catalyst (Pichloro [l, l'-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane) (catalyst manufactured by Strem Chem) was reacted at 23 201006862 at 60 ° C for 48 hours to obtain a white solid product compound. 2, the yield is 75%. The measured 1H NMR (400 MHz, CDC13) spectral data is as follows: δ (ρριη) 1.36 (s, 24H) ' 1.41 to 1.49 (m, 2H), 1.7 (m, 2H), 2.01 to 2.03 (m, 4H) ), 2.17~2.19 (m, 4H), 7.65~7.67 (d, 2H), 7.82 (s, 2H), 7.92~7.94 (d, 2H). [Example 3] Synthesis of Compound 3: Desertification-2-Butylbenzene-bromo-(2-ethylhexyloxy)-4-methylbenzene) The synthesis reaction formula is as follows:

Compound 3 17.5 g of desertified methyl alcohol (2-1?1*〇111〇-4-11^1; 11}^1^11〇1,169, Alfa Aesar, 98%) in a three-neck reactor, 250 ml of acetone (Jet Baker) was added, and the mixture was stirred under nitrogen and heated to reflux. Add 26 g Κ20Ό3 ( 2 eq'SHOWA) with 0.4 g 18-crown-6 (18-crown-6, 0.015 eq., Lancaster, 99%), add 23 g of desertification 2 after 10 minutes, Ethylhexyl (1.2 eq. Aldrich, 96%) After standing for 28 hr, it was allowed to stand for cooling, and the mash was filtered, and most of the solvent was removed by a rotary evaporator (rota·vapor). The ions were extracted twice with absolute ethanol (EA, Mallinckrodt Co.), NaOH (aq, Aldrich) and deionized water, and then added to MgS04 (Aldrich), 24 201006862. The filtrate was filtered and removed by a rotary evaporator. The vacuum distillation apparatus is used to remove the remaining 2-ethylhexyl bromide, and the remaining solution is purified by short column chromatography to obtain a product of residual colorless liquid, which is compound 3, and the storage rate is about 60. %. The measured 1H NMR (400 MHz, CDC13) spectral data is as follows: δ(ρριη) 7·38 (d, 1H), 7.06 (dd, 1H), 6·80 (d, 1H), 3.90 (d, 2H) , J = 5.7 Hz), 2.30 (S, 3H), 1.80 (m, 1H), 1.55 (m, 4H), 1.36 (m, 4H>, 0.96 (m, 6H). φ [Example 4] Synthesis of compound 4: 9,10:9,10-bis(cyclopentane)-2,7-bis(bromo-(2-ethyl-hexaneoxy-4-mercaptophenyl))-9,10-dihydrophenanthrene ( 9,1 〇: 9,10-bis(cyclopenta)-2,7-bis(bromo-(2-ethylhexylo xy)-4-methylbenzene))-9,10-dihydrophenanthrene) The synthesis reaction formula is as follows:

12.68 g of compound 2 (1 eq) and 15 g of compound 3 were dissolved in 250 ml of TEDIA solvent under nitrogen, and 127 ml of carbon 25 201006862 sodium (SHOWA, 2M) aqueous solution, 2.0 g (STREM, 95.9 %) was added. Pd(Pph3)4 catalyst, refluxed at 50 ° C for 4 hours to obtain a white solid intermediate 9,10:9,10-bis(cyclopentane)-2,7-bis (2· Ethyl-hexaneoxy-4-methylbenzene-9,10-bis(cyclopenta)-2,7-bis(2-ethylhexyloxy)-4-m ethylbenzene , 9,10- dihydrophenanthrene). Then, 5.36 g of the intermediate product was dissolved in 55 ml of di-methane (DCM, ECHO hplc) dissolved φ agent, and then 55 ml of acetic acid solvent was added, and 8 g of bromine water (Br2, manufactured by Lancaster) was added dropwise at 0 ° C. After stirring for 6 hours, a white solid product was obtained, and the collected solid was rinsed with decyl alcohol and purified by recrystallization from isopropyl alcohol (IPA, Aldrich) to afford compound 4 as a white solid. The 4 NMR (400 MHz, CDC13) spectral data measured for Compound 4 are as follows: δ (ppm) 0.89 to 0.96 (m, 12H), 1.31 to 1.34 (m, 12H), 1.47 to 1.52 (m, 10H), 1.61 1.67 (m, 2H), 1.70 to 1.82 (m, 2H), 2.02 to 2.13 (m, 6H), 2.18 to 2.25 (m, 4H), 3.91 to 3.94 (t, J = 6, 4H), 6.99 ( s, 2H), 7.26 (s, 2H), 7.83 (d, J = 8, 2H), 7.47 (d, J = 8, 2H), 7.98 (s, 2H). [Example 5] Synthesis of Compound 5: 26 201006862

5 bis (4,4,5,5-tetramethyl-1,3,2 diboron) (Bis (pinacolato) diboron) (manufactured by Boron Molecular) and 5 g of compound 4 under nitrogen Dissolved in 1 〇〇 ml of toluene (TEDIA) solvent, adding 4 g of potassium acetate (JT, Baker, 98%) and 0.1 g of dichloro[1, fluorene-bis(phenylphosphino)phenanthrene]palladium(II) A chloromethane adduct (Dichloro[l,l'-bis(diphenylphosphino)ferrocene] palladium (II) divalent adduct) (manufactured by Strem Chem) was subjected to a reaction at 60 ° C for 72 hours to obtain a white solid product. The collected solid was washed with decyl alcohol, and then purified by recrystallization from isopropyl alcohol (IPA, Aldrich) to afford Compound 5 as a white solid. The measured 1H NMR (400 MHz, CDC13) spectral data is as follows: δ Η = 0.90 to 0.96 (m, 4H), 1.36 (s, 24H), 1.47 to 1.55 (m, 8H), 1. 66 to 1.72 (m, 4H), 2.19~2.21 (m, 4H), 2.10~2.12 (m, 4H), 2.41 (s, 6H), 3.83~3.86 (t, J=7.97, 2H), 3.73~3.90 (t, J=7.81) , 2H), 6.85 (s, 2H), 7.01 (s, 2H), 7.34 (d, J = 8.1, 2H), 7.60 (d, J = 8.7, 2H), 8.04 (s, 2H). 27 201006862 [Example 6] Synthetic monomer Arl: 2,7-dibromo 9,9' bis(dimercaptotetrabutoxyphenyl) fluorene 2,7-Dibromo-(9,9'-Bis(3) , 4-di(2-methyl-butoxyphenyl)fluore ne, the preparation process is as follows:

Br

Add 76 g Cr〇3 (760 mmol, Aldrich) and 400 citric acid (ACROS) to the reaction flask, then mix 80 g of the two deserts ($mmol, Aldrich) with 300 ml of dichloropyrene (Aldrich). Adding to the reaction flask, stirring in an ice bath for 1 hour, adding water at room temperature to stop the reaction, stopping the reaction, filtering to obtain a solid, washing off the residual stomach with water _ _ 201006862 acid, and finally vacuuming to obtain a yellow solid Bromone (2,7-Dibromo-fluoren-9-one). 0.9 g of dibromide (1.33 mmol), 0.9 g of catechin (8 mmole, catechol, TCI), 0.75 g of methanesulfonic acid (8 mmol, merck) dissolved in 5 ml of carbon tetrachloride (Aldrich) The mixture was stirred at 100 ° C for 24 hours. After cooling to room temperature, 50 ml of aqueous sodium hydrogencarbonate (NaHCO 3 (aq), Me ck) was added to stop the reaction, and extracted with ethyl acetate (EtOAc, Aldrich). Drying, concentration and purification by column to give a dark pink solid (2,7-dibromo-9, 9-bis-(benzene-l, 2 diol)- fluorene). This dark red solid (2.0 g, 3.70 mmol), K2C03 (3.1 g, 22.2 mmol, ACROS), Toluene-4-sulfonic acid 2-methyl-butyl ester (C5HnOTs) , 4.5 g, 18.5 mmol, made with C5HnOH and TsCl) dissolved in dimethyl decylamine (DMF, 20 mL, 10 mL / 1 g SM, ACROS), placed in an oil bath at l〇〇-l20 °C Stir in the pot for 18 hours, and then cool to room temperature. Add water (50 ml) to stop the reaction. Extract with acetoxyacetate (0 〇, 5〇1111, 0108). The column was purified to give a brown liquid which was washed with ethanol several times to give a brown solid. Measured (400 MHz, CDC13): δ (ppm) 7.529 C d, 2H, 2.〇Hz), 7.453 (s, 2H), 7.415 (d, 2H, 2.0Hz), 6.707 (d, 2H, 2.2 Hz), 6.666 (d, 2H, 8.4 Hz), 6.529 (q, 2H), 3.682 (m, 8H), 1.799 (m, 4H), 1.233 (m, 8H), 1.21 (m, 12H). 29 201006862 [Example 7] Synthesis of monoterpenes Ar2: 3,6-dibromo 9-(4-tertiary butylbenzene)carbazole 3,6-Dibromo_9-(4-tert-butyl-phenyl)-carbazole, The preparation process is as follows:

Pat〇Ac]ca_ moxibustion drink-B^P, o-di-benzene

Az2

A sample prepared by placing 2 g of Carbazole (Aldrich), 0.1343 g of Palladium (II) propionate, Pd(0Ac) 2, Aldrich, and 2.529 g of tributyl butyl (Aldrich) was placed in a three-necked flask. Under nitrogen, 2.55g of evolved tertiary butylbenzene (l-bromo-4-tert-butylbenzene, Aldrich), 0.134g of tributylphosphine (t-Bu)3P, Aldrich and 75 ml of oxygen scavenging The xylene (o-xylene, Across) was injected into a three-necked flask to raise the temperature, and the reaction was carried out at 125 ° C overnight. After filtration, the precipitate was washed with THF, and the solid portion of the flask was dissolved by adding ethyl acetate (EA), and the precipitate was washed with n-Hexane, and recrystallized with EA to obtain 9 -(4-tertiary butylbenzene) oxazole white solid. 2.5 g of tertiary butyl benzoxazole, 2.973 g of N-bromosuccinimid (NBS, Fluka) and 40 ml of dimethylformamide (Dmethyl formaide, DMF, TEDIA) were placed in a single-necked flask. Medium temperature reaction overnight. After completion of the reaction, the mixture was stirred with water and filtered, and the filtrate was washed with water and then filtered. The solid obtained was washed with n-hexane and dried to obtain a white solid monomer Ar2. 4 NMR (400 MHz, CDC13): δ (ppm) 7.27 (d, J 30 201006862 = 2.4, 2H ), 7.42 ( d, J = 2.0, 2H ), 7.50 (d, J = 6.8, 2H) ), 7.62 (d, J = 2.0, 2H), 8.199 (s, 2H), 1.415 (s, 9H). [Example 8] Synthetic monomer Ar3: 4,7-Dibromo-benzothiadiazole, the preparation procedure is as follows:

Weigh 13.6 g of benzothiadiazole (Aldrich) and 100 ml of Dichloromethane (CH2Cl2, ECOHhplc) and dissolve it. Add 60 ml of HOAc (Merck) at room temperature, and add 50 ml of HO Ac to the feeding tube. With 40 ml of water (Βγ2, Merck), slowly drip into the stirring solution. The reaction was carried out at room temperature overnight. After completion of the reaction, the mixture was filtered, and the obtained solid was washed with diethyl ether and evaporated to dryness, and the solid was recrystallized from isopropyl alcohol (IPA, ACROS) to obtain white acicular crystals of monomer Ar3. 1H NMR (400 MHz, CDC13): δ (ppm) 7.724 (s, 2Η) [Example 9] Synthesis of monomer Ar4: 4,7-di-(5-bromo-thiophen-2-yl) ;-Benzene [1,2,5]thiadiazole (4,7-Bis-(5-bromo-thiophen-2-yl)-benzo[l,2,5]thiadiazole) 201006862, the preparation process is as follows :

Mol. Wt: 294 Mol. Wt: 300 2 "Sn(Bu>3 + Br

Mol. Wt.: 373

, s, Ar4

Br2 丨... — » HOAc/CH2C12 1 gram of dibromobenzodiazepine (3.4 mmole) 4.7-dibromo-2,l,3-benzothiadiazole (Aldricli), 3.06 g of tributyltin (8.2 mmole) 2- (tributylstannyl)thiophene (Aldrich) with 0.0477 g (0.068 mmole) of Pd(PPh3)2Cl2 (STREM) dissolved in 25 ml of THF solution, heated to reflux for three hours, the reaction was stopped by cooling, and φ THF was drained. Purification by column chromatography to obtain the intermediate product diphenobenzodiazepine

4.7- dithien-2-yl>2,l,3-benzothiadiazole 0.71 g, yield 69% 〇 Weigh 3 g 4,7-dithien-2,yl-2,l,3-benzothiadiazole with 30 ml CH2C12 (Aldrich) Stir and dissolve, add 30ml HOAc (ACROS) and mix at room temperature, then slowly add 20ml HO Ac and 4ml Br2 ( Merck ) mixture to 'at room temperature for 18 hours, rinse the precipitate with water, then dichloride Methane reprecipitation gave the monomer Ar4 in a dark red solid. 1H NMR (400 MHz, CDCI3) measured: δ (ppm) 7.787 (d, 4H, 4.0 Hz), 7.140 (d, 2H, 4 Hz). 32 201006862 Other bis-bromo conjugated monomers are listed below and can be purchased directly from Aldrich Co., TCI, Acros., Lancaster Co., Alfa Aesar Co., etc.

CAS : 264615-47-6

CAS : 149703-84-4 CAS : 4805-22-5

Ar5

CAS : 81090-53-1

RCL S10, 947-9/Aldrich [Example 10] Polymer I-bisphenylphenanthrene-derived conjugated polymer polymerization:

N2, toluene phase conversion agent

Pd<Ppb^4 N%C03 33 201006862

0.8 g of compound 4 and 1 g of compound 5 were dissolved in 200 ml of toluene under nitrogen, using Pd(PPh3)4 (Aldrich) as a catalyst and trioctylsulfonium azide (Aliquat 336, Aldrich) as a phase transition. Na2C03 (Merck) as a base and a reducing agent, subjected to a Suzuki coupling reaction 'reflow in benzene at 120 ° C for 96 hours. After the reaction is completed, the temperature is lowered to room temperature, and the reaction solution is slowly added to 300 ml. Extract twice in ionic water to collect the upper layer solution after separation. Then collect the solution slowly, and slowly drop it into 700 ml of sterol to precipitate. The precipitate is collected by filtration. After drying, white microfibrous polymer I is obtained. . The measured gpc: Mw = 22K dalton, PDI=2.4; UV absorption front (uV_Vis, film) is about 345 nm; the photoexcitation light (PL) peak of the solution of polymer I dissolved in toluene is 416 nm, which is formed. The photoexcitation light (PL) peak of the film is 438 mn, wherein the liquid solution is close to the PL spectrum of the solid film, indicating that no molecular stacking occurs when the film is formed. UV-Vis absorption spectrum and Pl luminescence spectrum as the first! The figure shows. [Example 11] Copolymer I-redness double phenanthroline-derived copolymer polymerization:

34 201006862 n2' toluene lion changer Ρ "Ρ 4 Ν%0〇3 MeQH 12〇t, 96 hours

2 g of compound 5 (〇.5 eq) and 0.5 g of monomer Ar3 ❹ (〇. 38 eq) '0.0.04 g of monomer Ar4 (0.02 eq) and 0.15 g of monomer Ar5 (0·1 eq) under nitrogen It is dissolved in 200 ml of toluene, using Pd(PPh3)4 (Aldrich) as a catalyst, and Aliquat 336, Aldrich is used as a phase conversion agent 'Na2C03 (Merck) as a reducing agent. The Suzuki coupling reaction was carried out 'reflowing in toluene at 1203⁄4 for 96 hours, and after the reaction was completed, the temperature was lowered to room temperature'. The reaction solution was slowly added to 300 ml of deionized water for extraction twice, and after separation, the upper layer solution was collected, and the collected solution was further collected. The precipitate was slowly added dropwise to 700 ml of methanol, and the precipitate was collected by filtration. After drying, about 1 g of the dark red powder copolymer I was obtained. The measured GPC: Mw == 44K dalton, PDI=2.8; UV absorption peak (uv_vis, film) is about 31〇, 325 nm; photoluminescence (PL) peak of the copolymer I dissolved in toluene solution The photoexcitation (PL) peak of the film formed at 539 nm ' is 621 nm. The uV-Vis absorption spectrum and the PL luminescence spectrum are shown in Fig. 2. [Example 12] Copolymer II, III, IV-R R. Photobisphenylphenanthrene-derived copolymer poly 35 201006862

The copolymers II, III and IV also adopt the Suzuki coupling polymerization method, and the polymerization steps are the same as those of the examples 10 and 11, except that the conjugated monomers used are different, thereby achieving the purpose of different light colors, the copolymer II, III and IV were dissolved in 10 cc of toluene at 1% by weight, and then spin-coated on clean glass at 4000 rpm to test the PL spectroscopy spectrum of the film type. The copolymerization ratio, UV absorption peak and PL luminescence color are listed in Table 1 below: Table 1. Polymerization ratio of copolymer I, II, III, IV, UV absorption peak and PL luminescence color copolymer copolymer UV-Vis absorption Spectral (nm) Photoexcitation Spectroscopy (nm) Molecular Weight (Mw) / K II (Compound 5) 0.5 - (Arl) 〇.5 341 442 5.2 III (Compound 5) 0.5 - (Ar2) 0.5 325, 348 431 12 IV ( Compound 5) 0.5 —(Ar3)〇.5 310, 355 552 34 I (Compound 5)〇·5—(Ar3) 〇_38 —(Ar4) 〇.〇2~(Ar5)〇.i 310, 325 621 44 The number outside the parentheses represents the percentage of moles of monomer feed [Example 13] PL spectrum test of polymer I doped low energy gap conjugated polymer: Poly bisphenanthrene derived conjugated polymer (polymer of the present invention) I) belongs to the blue color system, and its energy gap is about 3.1 eV, which can be doped with other organic electroluminescent materials to achieve the purpose of energy transfer and electric excitation of red, blue, green and multi-color light. 0 36 201006862

First, O.lg polymer I and 〇〇8g DB-PPV (UV-abs = 445 nm ' AEg = 2.36eV) and 〇 lg polymer i and 〇〇 8g Red C〇pF (UV-abS = 485 nm' △EgMm was dissolved in 1〇cc of benzene, and then spin-coated on clean glass at 4000 rpm. The PL spectroscopy spectrum was tested with 345 nm excitation light. For the result, please refer to Fig. 3, which is the polymer I of the present invention. The pL spectrum obtained by doping with other energy gap conjugated polymers DB-pp v and Red_c〇pF at a fixed ratio (8 wt%). Line B of Fig. 3 is a material not doped with DB-PPV, The main peak of the pL emission is at (2) nm; the line C indicates the material doped with Red-CoPF, and the main peak of the pL emission is at 641; and the line A indicates the pL spectrum of the original polymer I, as can be seen from Fig. 3, The polymer I is doped with DB-PPV or Red_c〇PF material, and the main PL light-emitting main peak of the polymer I is almost/obscured, and the energy of the photoexcited polymer I is smoothly transferred to the doped compound. DB_PPV & Red Cckpf polymers are synthesized by the inventor's laboratory (synthesis method can be referred to: Duan Qisheng... et al. published in the 91-year high score φ sub-seminar and 93-year Chinese chemistry Papers from), its chemical structure is as follows:

DB-PPV (Eg=2.36 eV) 37 201006862

Red-CoPF (Eg=1.93 eV) Although the present invention has been disclosed as a preferred embodiment, it is not intended to limit the invention, and any one skilled in the art can do it without departing from the spirit and scope of the invention. There are a few changes and modifications, and therefore the scope of the invention is defined by the scope of the appended claims.

38 201006862 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a UV-Vis liquid absorption spectrum and photoexcitation spectrum (PL) of a polymer I-bisphenylphenanthrene-derived coexisting polymer obtained according to Example 10 of the present invention. ) Figure. Fig. 2 is a view showing the ultraviolet-visible (UV-Vis) liquid absorption spectrum and the photoexcitation spectrum (PL) of the copolymer-emitting red-emitting bisphenanthrene-derived copolymer obtained in Example 11 according to the present invention. Fig. 3 is a photoluminescence spectrum (pl) spectrum of DB-PPV and Red CoPF doped with polymer μ bis phenanthrene derivative according to Example 13 of the present invention. Fig. 4 is a cross-sectional view showing the structure of an electroluminescence element fabricated in accordance with an embodiment of the present invention. [Main component symbol description] 10~substrate; Φ 2〇~transparent electrode; 30~ hole transmission layer; 40~ luminescent layer; 50~ cathode. 39

Claims (1)

201006862 X. Patent application scope: 1. A phenanthrene derivative, as shown in formula (1): Wherein R2, R3 and R4 are each independently a linear or branched Cl-22 alkyl group; a linear or branched (^-22 alkoxy group; ortho, meta or para (othro) -, meta-, para-) alkyl phenyl (aikylPhenyl) or alkyl benzyl (alkylbenzyl), wherein the alkyl group contains a linear or branched c6.3 〇 alkyl; ortho, meta Or para- or alkoxyphenyl or alkoxybenzyl, wherein the alkoxy group comprises a linear or branched C6-3G alkoxy group; 2,3-, 2,4 -, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkylbenzyl, wherein the alkyl group contains a straight chain or a branch Chain C6_3 〇alkyl; 2,3-, 2,4·, 2,5-, 2,6-, 3,4- or 3,5-diyloxyphenyl or dialkyloxy Dialoloxybenzyl, wherein the decyloxy group comprises a straight or branched chain C6-30 alkoxy group; or a arylaminoheterocyclyl group wherein the alkyl group comprises a linear or branched C6-3 a decyl group, and any of Ri, R2, R3 and R4 contains a hetero atom. 2. The phenanthrene derivative as described in claim 1 'In which the molecular structure of formula (I) are listed below: 40 201006862 3. A phenanthrene derivative polymer, as shown in formula (II): Wherein Ri, R2, R3 and R4 are as described in item 1 of the patent application, and m is the number of repeating units. 4. The phenanthrene derivative polymer as described in claim 3, wherein the molecular structure of formula (II) is as follows: 5. The phenanthrene derivative polymer according to claim 3, which is soluble in a solvent comprising aromatic hydrocarbons, halogen-containing benzene derivatives, alkoxy-containing benzenes. A derivative, a heterocyclic derivative containing a nitrogen atom, a quaternary derivative, a cyclic aliphatic saturated ketone or a combination of the foregoing, and the phenanthrene derivative polymer has a solubility of about 0.1 to 10% by weight. 6. The phenanthrene derivative polymer as described in claim 5, which is suitable for use in a liquid process including ink jet printing, spin coating, die coating, screen printing or printing . 7. A phenanthrene derivative polymer as described in claim 3, which is suitable for use in a photovoltaic element, including an organic electroluminescent device, a photovoltaic element, an organic memory element, and a photosensor. 41 201006862 8. A phenanthrene derivative copolymer, as shown in formula (III): Ar:, Ar2 and Ατ3 are molecules having an electrophilic or electrophilic group, each of which is independently selected from: a group consisting of: wherein R5, R6, R7 and R8 are each independently selected from hydrogen; a linear or branched Cl_22 alkyl group; a straight or branched Cl_22 alkoxy group; an ortho, meta or Para- (othro-, meta-, para-) alkylphenyl or alkylbenzyl, wherein the hospital base comprises a linear or branched 42 201006862 C6-3G system; Alkoxyphenyl or alkoxybenzyl in the meta, meta or para position, wherein the oxy group comprises a linear or branched (6-6 alkoxy group; 2, 3 -, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialy lbenzyl, wherein the alkyl group a linear or branched c6-3G alkyl group; 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-bisalkoxyphenyl ( Dialkoxyphenyl) or dialoloxyxy, whose alkoxy group contains a linear or branched Cwo alkoxy group; and an alkyl aryl group, the county of which contains a straight The number of q in which m, n, p, q of the group (III) composed of the 'wire' is a repeating unit includes 0. 莰And ,, P and 9.1 as specifically around 8 Application of phenanthrene Lai said molecular structure wherein a benzene derivative of formula (III) are listed below: ^ ' Where =; child: Wai ^^ η. For example, the application phase range η 顿 叙 (4) Property Copolymer, 43 201006862 The molecular structure of formula (III) is as follows: (iv) copolymer, 13) The phenanthrene derivative copolymer according to claim 8, wherein the phenanthrene derivative has less than 5 G% molar ratio of the green, and the color of the phenanthrene derivative copolymer includes red, Blue or green light, the phenanthrene derivative copolymer has an emission wavelength of about 400 to 7 〇〇 nm. 14. A phenanthrene derivative copolymer as described in claim 8 of the patent application, which is soluble in a solvent comprising an aromatic hydrocarbon, a halogen-containing bamboo organism, and an alkoxy-containing benzene. A derivative, a heterocyclic derivative containing a nitrogen atom, a sulphur derivative, a cyclic aliphatic saturated ketone or a combination thereof, and the solubility of the phenanthrene derivative copolymer is about 〇% by weight. 15. The phenanthrene derivative copolymer as described in claim 14 is suitable for use in a liquid process including ink jet printing, spin coating, die coating, screen printing or printing. . 16. A phenanthrene derivative copolymer as described in claim 8 of the patent application, 44 201006862, which is suitable for use in a photovoltaic element, a component, an organic memory component, and an organic electroluminescent device, and a photovoltaic sensor Device. 17. A luminescent material composition, a phenanthrene derivative polymer as described in the patent application scope flute or a phenanthrene derivative copolymer as disclosed in the eighth section of the invention; and Luminescent material. 18. For the clarification of the patent range flute, the luminescent material composition of # 4 πB, The §1 0/1 compound or the phenanthrene derivative copolymer accounts for about 50 to 99 Å and the luminescent material is contemplated. 19. The luminescent material composition of claim 17, wherein the luminescent material comprises a luminescent dye, an organic electroluminescent material, an inorganic electroluminescent material, an organic photoexcited material or an inorganic photoexciting material. 20. The luminescent material composition according to claim π, which is soluble in a solvent, the solvent comprising an aromatic pure money compound, a halogen-containing benzene derivative, a oxy-containing benzene derivative, a heterocyclic derivative containing a nitrogen atom, a _derivative, a cyclic aliphatic saturated ketone or a combination thereof, and the phenanthrene derivative polymer or the phenanthrene benzene derivative copolymer has a solution degree of about 0.1 to 10% by weight. 21. The luminescent material composition of claim 2, wherein the liquid process comprises ink jet printing, spin coating, die coating, screen printing or printing. Printed. 2 [For example, the luminescent material composition described in item 17 of the full-time occupation, the use of the -optic element] includes an organic electroluminescence element, a photovoltaic element, an organic memory element, and a photo sensor. The luminescent material composition according to claim 17, wherein the phenanthrene derivative polymer or the phenanthrene benzene derivative copolymer is transferred to the luminescent material, and the luminescent material composition The emitted light color includes red, blue, yellow, green or white light, and the luminescent material composition has an illuminating wavelength of between about 400 and 700 nm. 46