TWI312771B - Phenanthrene based conjugated polymer, copolymer, composition, and organic electroluminescent device and photovoltaic device comprising the same - Google Patents

Description

I312771 发明, the invention description: [Technical field of the invention] The invention relates to a novel multi-ring structure phenanthrene-based polymer which is soluble in a general solvent and prepares various types of photovoltaic elements in a liquid process, for example: two light-emitting elements Polar body, 2-sided display, solar cell, light sensor, etc. The bulk structure polymerization can electrically excite the blue light material; copolymerization or blending with other energy gap molecules can obtain an electro-active blue 'red, green full color light color material. [Prior Art] Electro-excitation polymer materials have a simple liquid process and can produce large 2-curve flat-panel displays, so there are many research and development. However, until now, the stability of Blu-ray high-knife materials still has doubts, so only a few commercial products are available. The polymer light-emitting diode (PLED) luminescent polymer material belongs to the structure: two molecules (four) ugated pGlymer), whose molecular structure is a single bond double bond interaction 2, due to its sp2 mixed orbital domain, its structure (4) Into the plane, · and carbon:: the unpaired electrons of the Shang Guang domain form η * unlocalized total vehicle key = ocallzed (3) ah double bond), the electron can use its single-button double-form transfer 'to achieve the purpose of conductance. The highest occupation of electronic occupation is divided into two domains. Hey. The P of the lowest unoccupied sub-track domain (lum) of the electrons (4) is separated by an energy gap (Eg), so the size of the energy gap determines the color of the light. 4 inch seat, and

The main material development of the former materials is mainly based on the main chain type of polymer, that is, the primary bond octagonal type cancer is connected, and the branch chain is mainly to increase the solubility. For example, the following knives · CeH13 〇1 • 1312771 Since the primary bonds are mainly conjugated cyclic molecules, it is easy to planar stacking under the attraction of the long-chain molecules of the south molecule, resulting in 7Γ-7Γ*unlocalized total The area of the vehicle is enlarged, and the red color shift of the illuminating color is generated, causing the display color to mutate. This is the phenomenon of molecular aggregation. For example, U.S. Patent No. 625,545 (issued to IBM in 2001) copolymerizes cyclohexane into polyaniline conductive polymers to prevent molecular aggregation and make metacresol ions more uniform. It is doped in polyaniline to increase its conductivity. U.S. Patent No. 6,268,702 (issued to Eastman Kodak Co., Ltd.) reveals a novel electroluminescent polymer whose composition is adamantane, phenylene, and phenylanthracene. Copolymer. WO 02/26856 (issued to CDT Co., Ltd. in 2002, etc.) discloses a polymer containing a benzene ring containing a cyclic structural monomer unit of five or more rings, a diphenyl ring The two benzene rings are twisted relative to each other by 5° to 75°, and have a blue-displacement luminescence effect. U.S. Patent No. 5,763,636 (issued to Hoechst in 1998) discloses an electroluminescent polymer having a novel structure of Spiro-PF. Patent No. 1074600 (issued to Sumitomo Corporation in 2001) discloses a copolymerized compound having a cyclic molecule whose individual molecular copolymerization ratio is to satisfy the formula indicated in the specification of the invention. 专利 Patent Publication No. 2003-55276 ( In 2003, the applicant was Sony, and revealed a phenanthrene electroluminescent material and its manufacturing method. Among them, there are phenanthrene-based electro-excited blue molecules and their co-compounds. The molecular form, synthesized with a variety of other molecules, can be used to electrically excite blue molecules. The above techniques also have a phenanthrene structure, but the benefits of preventing molecular aggregation are still not good. Therefore, a better polymer material is needed. It is applied to an electroluminescent display element such as a light-emitting diode (OLED) and an electro-laser (EL), or is a photovoltaic. 1327771 element. [Invention] The object of the present invention is to provide a novel phenanthrene. A total of a polymer with a polycyclic structure that transmits a long chain of a long-chain through a bicyclic nucleus substituent on the phenanthrene ring. The barrier property forces the main chain molecules to be unable to attract each other, making the πf unlocalized conjugated region Fixing and maintaining the stability of the luminescent color. The phenanthrene-based conjugated polymer of the present invention belongs to a blue color system, and has a band gap of about 3" to 3.2 eV, so that the mono-substrate and other energy gaps can be copolymerized. The purpose of electrically exciting red, blue, green and multi-color light colors. The polyfluorene-based polymer of the present invention may also be doped with other luminescent materials such as luminescent dyes or other organic electroluminescent materials. The composition is for the purpose of electrically exciting red, blue, green and multi-color light colors. Therefore, another object of the present invention is to provide a monomer unit (m〇n〇) comprising the phenanthrene-based conjugated polymer constituting the present invention. The copolymer of meric she), which copolymerizes with other energy gap molecules, achieves the purpose of electrically exciting red, blue, green and multi-color light colors. The luminescent color can be achieved by selecting a comonomer to form a copolymer. Still another object of the present invention is to provide a composition comprising the phenanthrene-based light-weight polymer of the present invention, which is a phenanthrene-based polymer of the present invention and other luminescent materials such as luminescent dyes or other organic or inorganic electroluminescent materials. The composition formed by doping can be selected as needed to achieve electrical excitation of red, i, green and polychromatic light + praise, 疋杈仏 a conjugated high knife copolymer containing the phenanthrene of the present invention, or The composition is an organic electroluminescent device of the light-emitting layer. A further object of the present invention is to provide an organic photovoltaic 8.1312771 (photovoltaic) device using the phenanthrene-based conjugated polymer, copolymer, or composition thereof of the present invention as an electron hole generating layer. In order to achieve the above object, a phenanthrene-based polymer of the present invention is a homopolymer composed of a monomer unit represented by the formula (I):

Wherein 'R1 and R2 are independently hydrogen; straight or branched c] _22 alkyl; straight or branched C]·22 alkoxy; ortho, meta or para a fluorenyl group, wherein the alkyl group may be a straight or branched Ci_3 fluorenyl group; an ortho, meta and para alkoxyphenyl or alkoxy fluorenyl group, wherein the alkoxy group may be straight Chain or branched Cuq alkoxy; 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkylbenzyl a group wherein the alkyl group may be a straight or branched Ci3q alkyl group; 2,3_, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-bisalkoxy a phenyl or bisalkoxybenzyl group, wherein the alkoxy group may be a linear or branched (^(10) alkoxy group; or an alkyl aromatic heterocyclic group, wherein the alkyl group may be a straight chain or a branched chain C _ 3G alkyl. To achieve the above other object, the copolymer of the present invention comprises (&) a monomer unit as defined in the above formula (1) and (8) a single selected from the group consisting of The bulk unit: a phenyl group, an anthracene phenyl group, an unsaturated heterocyclic group, and an anthracene ring unsaturated heterocyclic group. To achieve the above further object, the present invention The composition comprises (1) i to the column weight percentage of the above-mentioned phenanthrene conjugated polymer; and (9) 99 to! by weight of the organic conjugated molecular material. β is to achieve the above, the object of the present invention, including... The above-mentioned percentages include the copolymer of the unit 1312771 unit constituting the phenanthrene-based conjugated polymer of the present invention; and (Π) 99 to 丨 by weight of the organic co-molecular material. The organic electroluminescent device of the present invention comprises a transparent substrate; an anode is disposed on the transparent substrate; a hole transport layer is disposed on the anode; and the phenanthrene conjugated polymer of the present invention comprises the above Or a light-emitting layer of the copolymer or composition is located on the hole transport layer of the hole; and a cathode is disposed on the light-emitting layer. = To achieve the above-mentioned further object, the organic photovoltaic device of the present invention comprises a transparent a substrate; an anode disposed on the transparent substrate; a hole transporting layer on the anode, comprising the above-described phenanthrene-based polymer or copolymer of the present invention: or electrons of the composition a hole generating layer is disposed on the hole transport layer; and a cathode is located on the electron/hole generating layer. The invention is characterized in that the present invention can be used as a phenanthrene system of an organic electroluminescent material. Heat resistance, structural stability, and the main structure is blue light: material doping: together with the energy gap molecule copolymerization or with other luminescent dyes or other hair m, and wait for electricity to stimulate blue, red, green and multicolor The electro-optic material can have a wavelength of 4 〇〇i 7 GGnm, and its molecular double-ring structure can effectively prevent the inter-molecular aggregation and the color stability of the light. The function of the electric excitation is compared with the other, although the phenanthrene structure is the same, the special L (four) structure of the present invention is very different from the conventional technology, and the bis-benzene ring structure on the polymer main chain cannot be close to each other. Avoid the Si-phase stacking, keep the molecular society 谌 轻 light-------------------------------------------------------------------------------------------------------------------------------------------------------------------------- See i) Structure of the present invention is indeed possible to prevent aggregation of molecules. [Embodiment] 10 1312771 The phenanthrene-based conjugated polymer of the present invention has a polycyclic structure and is referred to herein as poly(9,10:9,10-fluorene (dimethylene)_9,1〇_二Hydrogen phenanthrene (1, 10:9, 10-biS(tHmethylene)-9, 10-dihydrophenanthrene)), which may have a substituent on the triamylene chain. The polymerized monomer unit 9,1〇_dihydrophenanthrene has two fused rings of two carbon-carbon bonds on the anaerobic atom of 苐9 and 10, two cyclopentane The alkyl fused rings may each have a substituent. The phenanthrene conjugated polymer of the present invention is a homopolymer composed of monomer units represented by the following formula (I):

Wherein 'R1 and R2 are independently hydrogen; a straight or branched chain of Chn; a straight or branched C?22 alkoxy; an ortho, meta or para phenyl or hydrazine a thiol group, wherein the alkyl group may be a linear or branched C^o alkyl group; an ortho, meta and para alkoxyphenyl or alkoxybenzyl group, wherein the alkoxy group may be straight Chain or branched 隹(^1-3〇 alkoxy; 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-bis-alkylbenzene Base or double alkyl thiol' wherein the alkyl group may be a linear or branched C!-30 alkyl group; 2,3-, 2,4-, 2,5-, 2,6-, 3,4 Or a 3,5-bisalkoxyphenyl or bisalkoxyindenyl group, wherein the alkoxy group may be a linear or branched alkoxy group; or an alkyl aromatic heterocyclic group, wherein the alkyl group It may be a linear or branched alkyl group. Among them, a linear or branched C6-12 alkyl group; a linear or branched c6_12 alkoxy group; an ortho, meta or para-alkyl phenyl group; Or an alkylbenzyl group, wherein the alkyl group may be a linear or branched C6.2G alkyl group; a-, meta or para-alkoxybenzene 11 1312771-based or alkoxy-based T-based The oxy group can be a straight chain or a branch C62G alkoxy, j, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkyl fluorenyl The alkyl group may be a linear or branched alkyl group; 2,3_, 2,4_, 2,5_, 2,6-, 3,4- or 3,5-bisalkoxyphenyl or dialkyloxy a benzyl group, wherein the alkoxy group may be a linear or branched (^(2) alkoxy group; or an alkyl aromatic heterocyclic group, wherein the alkyl group may be a linear or branched C62Q alkyl group. The phenanthrene-based polymer of the invention is composed of at least six monomer units, and is preferably > 40, and most preferably > 丨〇〇. The molecular weight of the phenanthrene-conjugated polymer of the present invention is Next, the better the Vietnam. The preferred weight average molecular weight is 20,000 or more, more preferably 50,000 or more, and a good photoelectric effect can be obtained. The phenanthrene conjugated polymer of the present invention can be obtained, for example, by the reaction shown below: 1 :

Compound (I)

12 1312771

Compound

N2, 120°C, 96hrs

Pd(dppf)Cl2.CH2Cl2 CH3COOTC+/ methylbenzene (in)

Compound (IV)

Reaction 2:

An example of a polymer of a monomer unit of formula (I) wherein R and R' are independently hydrogen; a linear or branched Cm2 alkyl group; a linear or branched C]-22 alkoxy group; a terphenyl, an ortho- or para- ortho-, meta-, or para-based alkylphenyl or alkylbenzyl group in which the alkyl group may be a linear or branched c6-3◦ An alkyl group; or an alkoxyphenyl group or an alkoxybenzyl group of the ortho, meta- 4-position, wherein the alkoxy group 13 1312771 is a linear or branched Cwo alkoxy group. Or a 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkylbenzyl ), wherein the alkyl group may be a linear or branched Ci_3 alkyl group; or 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- a bis-oxyalkylene group (<^&11<;〇\3^卩11611}4) or a dialkyloxybenzyl group in which the alkoxy group may be a linear or branched alkane An oxy group; or an alkyl aromatic heterocyclic group wherein the alkyl group may be a linear or branched Cu alkyl group. X can be CU, Br or I. The description is as follows: The phenanthrene-9,10-dione starting material shown in the above column is dissolved in an appropriate HBr and Ή2804, and the temperature is raised to 80 ° C, and a small amount of Br 2 is slowly added, and the reaction is carried out for 24 hours, and the precipitate is filtered. Halogenated phenanthrene-9,10-dione as shown in the compound (I). The synthesized dihalofoprene-9,10-dione and 2 equivalents of diethyl 1,3-acetonedicarboxylate are heated in a solvent in the presence of NaOH, and after the reaction is completed, HC1 was neutralized and a precipitate was obtained. The collected sediment was dissolved in acetic acid, and an aqueous solution of HC1 was added to heat the reaction. Then, it was neutralized with Na2C03, filtered and separated, and the compound (II) was obtained. Compound (II) was dissolved in acetone, K2C03, crown ether and alkyl bromide group (expressed as XR') were added and heated to reflux. After 18 hours of reaction, the solid was filtered, and a 5% aqueous solution of HCl was added, and the mixture was extracted with ethyl acetate. The organic layer was evaporated over magnesium sulfate and concentrated, and the product was separated by a column, and then ethylene glycol was added. N2H4 and KOH were heated to 180 ° C with stirring and reacted for 15 hours. It is diluted with a large amount of water to obtain a white solid, i.e., compound (III), which is soluble. The compound (III) is reacted with a diborate compound in toluene in the presence of a CH3COOK and Pd(dppf)Cl2 catalyst under nitrogen at elevated temperature to obtain a compound of the formula (IV) having a diborate. • ♦ Compound (III) having a dihalogen group and compound (IV) having a diborate 14 1312771 Pd(PPh3)4 catalyst and Aliquat@3 3 6 stabilizer are added to toluene under nitrogen and at elevated temperature. The sodium carbonate heating reaction was further carried out by adding sterol and water to reflux for 72 hours to carry out a Suzuki coupling reaction to obtain a phenanthrene-based polymer according to the present invention, that is, a polymer composed of the monomer unit of the formula (I). When the compound (III) or (IV) is copolymerized with other monomers, a novel phenanthrene-based alternating copolymer can be formed in the same manner as the above-mentioned Suzuki coupling reaction. The description is as follows: Reaction 3:

+ Br-Ar-Br

1312771, , where 'R and R are as defined in R&R in Reaction 2. ^ is a cyclic molecule of one or more kinds, for example, a phenyl group, a polycyclic phenyl group, an unsaturated unsaturated heterocyclic ring, a ring-unsaturated heterocyclic group, for example, each ring has 3 to 8 rings. The atom or a plurality of hydrogens on the ring atom may be optionally substituted by the following substituents: for example: ΗCl; linear or branched c] _22 is preferably Ci! 2 alkyl; linear or branched Preferably, the alkyl group or the ortho, meta or para-position of the alkyl group or the alkyl group, wherein the alkyl group is a linear or branched chain, is preferably a c(4) wire; The alkoxyphenyl group or the alkoxy group in the position or the para position wherein the alkoxy group is a straight bond or a branched chain Cm is preferably a 〇6_12 alkoxy group.

Therefore, the "copolymer of the present invention" is obtained by alternately copolymerizing monomer units of the following (4) and (8).

The monomer unit of (4) is a monomer unit constituting the phenanthrene-based polymer of the present invention, as shown by the above formula (I). The monomer unit of (b) is a ^onjugated m〇leeular moiety. The monomer unit (9) can be selected according to the desired emission wavelength to form a copolymer with the monomer unit of (4), and the electroluminescence wavelength of the copolymer can be adjusted, and the emission wavelength can be in the range of 400 to 7 〇〇 nm. And because the stereoscopic bicyclic implant structure unique to the copolymer molecule can effectively prevent the aggregation between molecules, the effect of color stabilization of the electroluminescence light is achieved. The monomer unit according to (b) of the present invention may be a monomer unit selected from the group consisting of a phenyl-extended polycyclic phenyl group and an unsaturated unsaturated heterocyclic group-extended polycyclic unsaturated heterocyclic group. Preferably, each ring has 3 Μ 8 rings. The ring atom may be carbon, sulfur, oxygen, hydrazine or nitrogen. The hydrogen on the ring atom may be substituted with a substituent. F; α; linear or The % of the branch is preferably ^(4). The linear or branched Cl. 22 is preferably 〇 1.12 alkoxy; ortho, meta or para phenyl or alkyl benzyl, wherein the alkyl group is A linear or branched Cu C6-]2 alkyl group ortho, meta or para alkoxy or alkoxy 2 group 16 1312771 wherein the alkoxy group is a straight or branched chain C- 22 is preferably a c6_12 alkoxy group. For example, the following are, but are not limited to:

Is a CN12 alkyl group; a linear or branched Ci. 22 is preferably a Cl丨2 alkoxy group; an ortho, meta or para-alkylphenyl or alkylbenzyl group in which the alkyl group is a straight chain Or a branched chain c _22 is preferably a C6 "> 2 alkyl group; or an ortho, meta or para alkoxy phenyl or alkoxy fluorenyl group, wherein the alkoxy group is a direct bond or a bond C] 22 is preferably C6.12 alkoxy. The novel phenanthrene-based polymer or copolymer of the present invention may be used as a composition alone or in combination with other light-emitting materials such as luminescent dyes, organic or inorganic electro-optic or photoexcitable materials for use in photovoltaic elements. The content ratio of each component contained in the composition and the kind of other luminescent materials are not particularly limited, and for example, the phenanthrene conjugated polymer or copolymer of the present invention and 99 to 1 weight percent of the luminescent material may be added to a percentage of 99% by weight. A composition is formed. According to the required illuminating wavelength, the selection and the amount of materials can be adjusted, and the corresponding illuminating energy level can be adjusted by the host-guest effect. It was found that the obtained composition had better luminous efficiency than the original luminescent material. The phenanthrene-based conjugated polymer or copolymer of the present invention has a weight average molecular weight of at least 5,000, more preferably more than 20, 〇〇〇, and most preferably 5 〇, 〇〇〇 or more, as the solubility permits. The phenanthrene-based polymer, copolymer or composition containing the same may be dissolved in a single solvent or a co-solvent such as (1) aromatic 17 1312771 hydrocarbon: e.g. Benzene, diphenylbenzene, ethylbenzene, diethylbenzene, dibutylbenzene, cymene, propylbenzene, 1,3,5-trisyl mesitylene, trimethyl Benzene (trimethylbenzene), tetralin, tetramethylbenzene, or dodecylbenzene; (2) halogen-containing benzene derivatives: such as chlorobenzene, dichlorobenzene or trichlorobenzene; 3) Alkoxy-containing benzene derivatives: such as anisole or phenetole; (4) heterocyclic derivatives containing a nitrogen atom: such as pyridine, mercaptopyridine, hexahydropyridine, hydrazine Pyridyl pyridine, dimethyl hexahydroindole, ethyl hexahydroindole, pyrrolidine, methyl ketone, or pyrrole; (5 Furan derivatives: such as tetrahydrofuran (THF), mercaptotetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, tetramethyltetrahydrofuran 11 south, Tetrahydro-thiopyran roar (tetrahydropyran); (6) a cyclic aliphatic saturated ketones: such as cyclohexanone (Cyclohexanone); cosolvent or combinations thereof and the like, the solubility range between 0.1 wt% to 10 wt%. Therefore, it can be applied to liquid process manufacturing components, and the process is convenient. The phenanthrene-based conjugated polymer, the copolymer or the composition containing the same can be used for spin coating, ink jet printing, die coating, screen printing or printing when applied to the manufacture of the organic electroluminescent device. The organic electroluminescent device or the photovoltaic element can be fabricated by forming a film on the ITO substrate and steaming the metal cathode. The organic electroluminescent device of the present invention comprises a transparent substrate such as glass or a flexible plastic (for example: PET (polyester), PC (polycarbonate), COC (cyclic olefin copolymer), PES (polyether) Maple), etc.; a transparent anode (such as indium tin oxide (ITO), extended ethylene dioxythiophene (PEDOT)); - hole transport layer, such as poly(ethylenedioxythiophene), PEDOT And polyaniline (Polyaniline); - a light-emitting layer comprising the polycyclic structure polyfluorene-based polymer, copolymer, or a composition thereof; and a cathode, such as Ca, Al, Mg, etc. electrode. It can be manufactured by a solution process method of the horn, and the light-emitting layer 18 I312771 r=including the polycyclic structure of the present invention, the phenanthrene-based copolymer, the copolymer, or the parallel printing, the inkjet printing, the die A head coating (diee (10) ing), screen printing or plate P method was formed on the ITO substrate. Plastic molding::Ming's photovoltaic device includes a transparent substrate, such as glass or flexible connecting circuit ^: Ton Buxin (7) Buqing ... puff - transparent anode for the hole and electrode, such as indium tin oxide (ITO) a hole transporting layer, such as a polyphenolic metal such as Ca, A, Mg, etc. (=y=enylene vinylene), PPV); a multi-ring structure comprising the present invention An electron/hole generating layer of a south molecule, a copolymer, or a composition thereof; and a cathode, -

The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. Synthesis of 7-dibromo-phenanthrene-9,10-dione (2,7-dibr〇m0_phenanthrene-9,i〇_di〇ne) intermediate 1

3 g of phenanthrene-9, ι〇_dione (Aldrich, 95%) was dissolved in 60 ml of HBr and 20 ml of H2S04, and the temperature was raised to 8 Torr. 〇 ' Slowly add a small amount of Br2 (ACROS), and react for 24 hours to precipitate the dihalophenanthrene-9,1〇-dione in a yield of more than 9〇0/〇. The following shows the procedure for preparing Intermediate 1:

Example 2 9,10; 9,10-bis(2-carbonyltrimethylene)-2,7-dibromo-9,10-dihydrophenanthrene (9,1 -9,10-bis (2-ox) 〇trimethylene)-2,7-dibromo-9,10-dihydrophen 19 1312771 anthrene) Synthesis of Intermediate 2 2 g of NaOH was mixed with 200 ml of methanol and heated to 6 〇t; After Na〇H was completely dissolved, 3 g of Intermediate 1 and 4 g of 1,3-acetonedicarboxylate (ACROS, 95%) were added and maintained at 6 Torr. Hey. After 36 hours of reaction, a 10% aqueous HCl solution was added to neutralize the precipitated hydrazine. The precipitate was collected and dissolved in acetic acid, and then 300 ml of a 1 〇% HCl aqueous solution was added, and the reaction was heated for 18 hours. Acetic acid and water were removed, neutralized with an aqueous solution of sodium hydrogencarbonate, and then separated by filtration to give the product of Intermediate 2, yield 17%. The following shows the process for preparing Intermediate 2:

Example 3 9,10; 9,10-bistrimethylene-2,7-dibromo-9,10-dihydrophenanthrene (9,10:9,10-bistrimethylene-2,7-dibromo-9,10 -dihydrophenanthren e) Synthesis of Intermediate 3 3 g of Intermediate 2 was mixed with 150 ml of ethylene glycol, and 2.4 g of N2H4 was added. After mixing for 1 minute, 2.6 g of KOH was added and heated to i80 ° C for 15 hours. After cooling to room temperature, a large amount of water was added to dilute, and a solid precipitated to collect a solid. The solid was dissolved in a minimum amount of dichloromethane to give a white solid 1.7 g, yield 61%. The following shows the procedure for preparing intermediate 3: Ο η

1312771 Example 4 9,10; 9,10-bistrisinoin-2,7-bis-(4,4,5,5-tetramethyl-1,3,2-dioxy-2-boronyl) -9,10-dihydrophenanthrene (9,10:9,10-bistrimethylene-2,7-bis-(4,4,5,5-tetramethyl-l,3,2-dio xaborolan-2-yl)- 9,10-dihydrophenanthrene) Intermediate 4.4 Synthesis Take 3g Intermediate 3 ' 2.82g Potassium Acetate (KOAc) ' 3.9g Bis (bisacic diboron) (Aldrich, 98%) > 0.015 g Pd(dppf)Cl2 · CH2C12 (Aldrich) was placed in a three-necked flask under nitrogen, added with 20 ml of toluene, and reacted at 60 ° C for 96 hours. After the reaction was completed, it was diluted with toluene and washed three times with water to remove color with activated carbon. Concentration in vacuo to remove toluene gave a white solid which was purified by recrystallization from IPA to yield 2.7 g of acicular crystalline intermediate 4 in a yield of 72%.

Example 5 9,10-2_carbonyltrimethylene-9,10-(l-(4-t-butylbenzyl)-2-carbonyl-trimethylene)-2,7-dibromo-9, Intermediate of 10-, 10-(2-oxotrimethylene)-9,10-(l-(4-i-butylbenzyl)-2-oxotrimethylene-2,7-dibromo-9,10-dihydrophenanthrene) Synthesis of Body 5 0.5 g of Intermediate 2 was dissolved in 100 ml of acetone, 0.62 g of K2CO3 (SHOWA) and 0.18 g of Crown-ether (18-crown-6 ether, TCI) were added, and after 10 minutes, 0.56 was added. 4-tert-butylbenzyl bromide (Aldrich '97%) 'heated to reflux. After 18 hours of reaction, the reaction solution was cooled and the solid was filtered off to remove the solvent from the mash. After 50 ml of a 5% aqueous solution of HCl and 50 ml of ethyl acetate were added, the organic layer was concentrated with water and then concentrated. The product was obtained in an amount of 0.54 g, yield 83%. 21 1312771 The following shows the process for preparing intermediate 5:

(9,10-trimethylene-9,10-(l-(4-i-butylbenzyl)-trimethylene)-2,7-dibromo-9,l-dihydrophenanthrene) Synthesis of Intermediate 6 2 g of Intermediate 5 with 100 ml of ethylene glycol was mixed, and after adding 1.21 g of N2H4 and stirring for 10 minutes, 1.31 g of K0H was added, and the mixture was heated to 180 ° C for 15 hours. After cooling to room temperature, a large amount of water was added to dilute, and a solid precipitated to collect a solid. The solid was dissolved in a minimum amount of dichloromethane, which was obtained by column chromatography to give a white solid. The following shows the process for preparing Intermediate 6:

Example 7 9,10-trimethylene-9,10-(1-(4-tert-butylfluorenyl)-trimethylene)·2,7-bis-(4,4,5,5-four 9,10-trimethyl ene-9,10-(1-(4-i-butylbenzyl)-trimethylene) -2,7-bis-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9,10-dihydrophenanthrene) Synthesis of intermediate 7 13 1312771 1.2 g of intermediate 6 0.83 g of potassium acetate (KOAc), 1.16 g of diterpenoid diboron (Aldrich, 98%), 0.007 g of Pd(dppf)Cl2 · CH2Cl2 (Aldrich) were placed in a three-necked flask under nitrogen, and 15 ml of toluene was added. The reaction was carried out at 60 ° C for 96 hours, and after completion of the reaction, it was diluted with toluene, washed with water three times, and the color was removed with activated carbon, and concentrated under vacuum to remove toluene to obtain a white solid which was purified by recrystallization from IPA to obtain 0.81 g of needles. Crystalline intermediate 7, yield 58%. The following shows the procedure for the preparation of intermediate 7:

KOAc / toluene

Pd(dppf)a2CH2GI2

EXAMPLE 8 Synthesis of 9,9-dioctyl- 2,7-dibromofluorene (9,9-dioctyl-2,7-dibromofluorene) intermediate 8

Take 10 grams of 2,7-two desert '苐(2,7-(11131'〇111〇£111〇116) (human 1<11^]1,97%) in a round bottom bottle, add 175 ml In DMSO, add 8 g of potassium t-butoxide (Lancaster, 97%), and then slowly add 19 g of octylbromide (Aldrich, 99%) to the addition funnel at 45 ° C. The reaction was carried out for 24 hours. After the reaction was completed, it was diluted with ethyl acetate and washed three times with 1 ml of water, dried and concentrated under reduced pressure to give 15 g of white solid, which was purified by recrystallization from IPA to give intermediate 8. The gram is a needle-like crystalline solid with a yield of 77%. The following shows the procedure for preparing the intermediate 8:

Example 9. Poly 9,10-triazinyl-9,10-(1-(4-t-butylbenzyl)-trimethylene)-9,10-dihydro-non 23 1312771 (poly-( 9,10-trimethylene-9,10-(1 -(4-i-butylbenzy 1)-trimethylene)- 9,10-dihydrophenanthrene)) Synthesis of Polymer I Under nitrogen, 〇·5g of intermediate 7 And 0.32 g of the intermediate 3 monomer were dissolved in 40 ml of toluene, using Pd(PPh3)4 (Aldrich) as a catalyst, Aliquat 33 6 (Aldrich) as a phase change agent, and Na2C03 as a reducing agent for Suzuki coupling. (coupling) the reaction, refluxing in toluene at 120 ° C for 96 hours, after the completion of the reaction 'cooling to room temperature', the reaction solution was slowly added to 350 ml of hexane, the precipitate was collected by filtration, and the collected precipitate was collected. 40 ml of THF was dissolved, slowly dropped into a mixed solvent of 600 ml of methanol and 100 ml of water, and the precipitate was collected by filtration, and after drying, the polymer I was obtained, which was a polycyclic structure of the present invention as shown in the formula (II). It is a conjugated polymer. The UV absorption peak was measured to be about 330 nm, and the photoexcitation light (PL) peak was 412 nm. The following shows the process for preparing Polymer I:

Example 10 Poly((9,10:9,10-bistriindolino-9,10-dihydrophenanthrene)-(3-n-hexylthiophene)) (p〇ly-((9,10;9,10) -bistrimethylene- 9,10-dihydrophenanthrene)-(3-hexylthiophene)) Synthesis of Copolymer II 0.5 g of Intermediate 4 monomer and 0.39 g of 2,5-dibromo '3-hexene 24 1312771 hydrazine under nitrogen Phenol (2,5-dibromo-3-hexylthiophene) (Aldrich, 97%) was dissolved in 33 ml of toluene with Pd(PPh3)4 (Aldrich) as catalyst, Aliquat 336 (Aldrich) as phase conversion agent, and Na2C03 as The reducing agent was tested and subjected to a Suzuki coupling reaction. The mixture was refluxed in toluene at 120 ° C for 96 hours. After the reaction was completed, the temperature was lowered to room temperature, and the reaction solution was slowly added to 350 ml of n-hexane, and the precipitate was collected by filtration. The collected precipitate was dissolved in 40 ml of THF, slowly dropped into a mixed solvent of 600 ml of methanol and 1 ml of water, and the precipitate was collected by filtration, and after drying, the copolymer II was obtained, which is the formula (III) of the present invention. The copolymerized polymer containing the phenanthrene molecular structure of the present invention is shown to have a UV absorption peak of about 358 nm, and the solution state photoexcitation light peak is 455 nm. (As shown in Figure 2), the film state photoexcitation light peak is 495 nm. The following shows the process for preparing the copolymer II:

Aliquat@336 120 °C Pd(Pph3)4 reflux 96 hr Na2C03

Example 11 Poly((9,10-triindolyl-9,10-(1-(4-t-butylbenzyl)-trientylene)-9,10-dihydrophenanthrene)-(9,9 - Dioctyl hydrazone)) (poly-(9,l 0-trimethylene-9,10-(1 -(4-i-butylbenzyl)-trimethylene)- 9,10-dihydrophenanthrene)-(9,9-dioctylfluorene) Synthesis of Copolymer III In a nitrogen gas, 5 g of compound 7 monomer and 0.32 g of compound 8 monomer 1312771 were dissolved in 33 ml of a stupid, using pd(pph3)4 (Aldrich) as a catalyst. 336 (Aldrich) is a phase conversion agent, Na2C〇3 is used as a base and a reducing agent, and a Suzuki coupling reaction is carried out, 12 曱 in toluene. Under reflux for 96 hours, after the completion of the reaction, 'cool down to> JE·', slowly add the reaction solution to 350 ml of hexane, collect the precipitate by filtration, and dissolve the collected precipitate in 40 ml of THF, slowly dropping Into a mixed solvent of 600 ml of sterol and 100 ml of water, the precipitate is collected by filtration. After drying, the copolymer is obtained as a polycyclic structure polyfluorene-conjugated conjugated molecule of the present invention as shown in formula (II). . The UV absorption peak was measured to be about 334 nm (as shown in Figure 3).

The light excitation light (PL) peak is 415 nm, and the electroluminescence (EL) peak is 435 nm. The following is a flow chart for preparing a copolymer crucible:

N2 , toluene N2 Aliquat@336 Pd(Pph3)4 "Na^CC^

Thiamine Example 12 (E)-2,3-Di(2-thienyl-2-propanth((E)-2,3-di(2-thienyl)-2-propenenitrile) monomer synthesis 4.55 g 2 - thiophene oxime (2-1;]11〇卩]16116.&1>1)〇乂&1(1611}^(16)(Bagua 1·03' 98%) and 5 g 2-thiophene 2-thiopheneacetonitrile (Acros, 94%) was placed in a round bottom flask, 50 ml of ethanol (TEDIA, 95 °/.) was added, and 2.2 g of potassium hydroxide (SHOWA) was added at room temperature. After the completion of the reaction, the mixture was filtered, and the product was washed with 150 ml of ethyl alcohol. After drying, the compound 7 was obtained in a total of 8.37 g, which was obtained as a yellow powdery solid, yield 95%. HNMR (CDCl3) The spectral data is as follows: (5 (ppm) 6.97~6·99 (m, lfJ) 7,04~7.06 (m, lH), 7.18~7.20 (m, 1H), 7.25 (d, lH), 7.40 (s) , iH), 7.41 to 7.46 (m, 1H), 7.52 to 7.53 (d, 1H) ' The following shows the preparation of (E)-2,3-di(2-(thienyl)-2-acrylonitrile (thienyl single) Process 1):

s/ ~CHO

NaOH „ NC MeOH S thienyl 1 (E)-2,3-- one (5-dimethyl-2-thiophene ((-E)-l, 2-di(5-bromo-2-thienyl)-2-propenenitrile) Monomer synthesis

Take a single-necked flask, a bottle-necked addition funnel, dissolve l〇g (46 mmol) of thienyl 1 monomer in 100 ml of dichloromethane, and add 16 17 g (1 mmol) of bromine into the reaction flask. (SHOWA, 99%) was dissolved in 50 ml of di-methane, added to the addition funnel, slowly dropped into the reaction flask, and stirred at room temperature for half an hour to form a yellow solid. The solid was filtered 'with ethanol (TEDIA, 95%) was recrystallized to obtain 13.4 g of a yellow needle crystal product, yield 78.21%. The 1H NMR (CDC13) spectral data were as follows: 5 coffee 111) 6.95~6.96 ((1,111), 7.01~1.〇3(111,211), 7.14(8, 1H), 7.21-7.22 (d, 1H) The following shows the procedure for preparing the dibromothienyl monomer 2:

Example 14 Poly(9,l〇j,10*-bistrientylene-9,10-dihydrophenanthrene)_(E)_2,3_2 27 1312771 (2 - 13⁄4 phenyl-2 - propylene (poly-(9,10-trimethyl ene-9,10-(1 -(4-i-butylbenzyl)-trimethylene)- 9,10-dihydrophenanthrene) -(E)-2,3-di(2-thienyl) )-2-propenenitrile) Synthesis of Copolymer IV 0.5 g of Intermediate 7 monomer and 0.29 g of dibromothienyl monomer 2 were dissolved in 33 ml of toluene under nitrogen, using Pd(PPh3)4 (Aldrich) as Catalyst, Aliquat 336 (Aldrich) is a phase conversion agent, Na2C03 is used as a base and a reducing agent, and subjected to a Suzuki coupling reaction. The mixture is refluxed in toluene at i2 ° C for 96 hours. After the reaction is completed, the temperature is lowered to room temperature. The reaction solution was slowly added to 3 ml of n-hexane, and the precipitate was collected by filtration. The collected precipitate was dissolved in 6 ml of THF, and slowly added dropwise to a mixed solvent of 800 ml of methanol and 160 ml of water, and the precipitate was collected by filtration. Copolymer IV is obtained after drying. The Uv absorption peak was measured to be about 488 nm (as shown in Fig. 4), and the photoexcitation (PL) peak was 554 (liquid) nm, 6 〇 8 (membrane) nm, and the electroluminescence (EL) peak was 616 nm. . The following shows the procedure for preparing the copolymer IV:

Copolymer IV Example 15 Preparation of Electrically Excited Element 28 1312771 Referring to Figure 5, the copolymer III of the former example was dissolved in an anhydrous terpene solvent under a N2 atmosphere at a concentration of 1 wt%, the molecular weight of the copolymer III. It is 20,000 and has a molecular weight distribution of 1.8. PEDOT (i.e., poly(ethylenedioxythiophene)) was spin-coated on the cleaned ITO glass 20, 10 to serve as a hole transport layer 30 having a thickness of 60 nm. The solution in which the copolymer III was dissolved was spin-coated on the PEDOT layer at 2000 rpm to form a light-emitting layer 40 having a thickness of about 50 nm, which was then sent to a vacuum chamber to evacuate to 10.6 Torr, and a thickness of 50 nm was used as a cathode. The electrode 60 is further vapor-deposited with A1 as a protective layer (not shown) to complete the fabrication of the device. Testing the photoelectric properties, as can be seen from Fig. 5, the novel polymer has a luminance of up to 300 nits (candles per square meter, cd/m2), and the method described in this embodiment is applicable to the text described herein. All of the phenanthrene polymers of the invention are copolymers and compositions thereof. Example 16 Preparation of a composition comprising a phenanthrene-based conjugated polymer of the present invention (1) An electroelastic blue blue novel polycyclic structure polyphenanthrene copolymer III of the present invention was selected as a matrix material, and the energy gap was measured by UV. At 3.2 eV, it can be doped with other low-gap organic electroluminescent materials to achieve the purpose of electrically exciting red, green and multi-color light. Table 1 is a polyphenanthrene copolymer III of the present invention and other energy gap conjugated polymers MEH-PPV and DB-PPV, each dissolved in anhydrous toluene at 0.5 wt%, and then doped at a fixed ratio, and then by way of example The process described in 12 was fabricated into a light-emitting diode element, and UV absorption spectrum and photoluminescence (PL) and electroluminescence spectrum were measured by UV-Vis and a fluorescence meter. It is known from experiments that the phenanthrene-based conjugated polymer of the present invention is doped with MEH-PPV and DB-PPV, and the luminescent color of the PL (light laser) range of 499 to 583 nm and the EL (electro-laser) range of 509 to 589 nm can be obtained. Luminous color. 29 1312771 .............................

A: polyphenanthrene derivative (copolymer ni) (Eg = 3.14 eV)

B. DB-Ρργ (Eg=2.4 eV) C : MEH-PPV (Eg=2.1 eV) --- Table 1 Composition doping ratio (% by weight) UV spectrum (nm) PL spectrum (nm) EL spectrum (nm ) A 100 332 415 435 B 100 446 520 538 C 100 492 583 5 7 5 ~ 610 A/B 95/5 334 499 509 A/C 95/5 _____334 559 589 A/B/C Si lack 85/10/5士α口Γ7 Crest 334 __4 450 559 571

'Only the dog walks on the road, but it is not used to f. Anyone who is familiar with this technique can be used as a more moving fish; from the spirit and scope of the present invention f. Therefore the present invention

The definition of the scope of patent application is as follows:, after HU, R 30 1312771 [Simplified description of the drawings] FIG. 1 is a computer simulation of a conjugated polymer monomer unit of a polycyclic structure according to an embodiment of the present invention. The molecular arrangement is a perspective view. Fig. 2 is a photoexcited light (PL) spectrum of a phenanthrene copolymer (polymer π) according to Example 1 of the present invention. Figure 3 is a phenanthrene copolymer according to Example 11 of the present invention (poly(buried)-(9,10:9,10-Wu (trimethylene)_9,1〇-dihydrophenanthrene), polymer ΙΠ Ultraviolet (UV) absorption spectrum and photo-induced (PL) spectrum in solution, and UV absorption spectrum, photo-induced (PL) spectrum, and electric (EL) spectrum of film formation. Figure 4 is a phenanthrene poly(9, ι〇:9, ΐ〇-bis-trirumethylene-9,10-dihydrophenanthrene)-pentane-2,3-di according to Example 14 of the present invention. (2-Thienyl-2-acrylonitrile) Copolymer 1乂) Ultraviolet (UV) absorption spectrum and photoexcited (PL) photo-pattern in solution, and film formation - UV absorption spectrum, light excitation (PL) Spectrograms, and electro-optic (EL) light maps. - Figure 5 is a schematic view of an organic electroluminescent device according to an embodiment of the present invention. Fig. 6 is a graph showing the current efficiency of the electroluminescent device ITO/PEDOT/polymer ΠΙ/Ca/Al obtained according to Example 11 of the present invention versus voltage and luminance versus voltage. 【 [Illustration of Symbols] 10: Transparent substrate 20: ITO electrode, anode 30: hole transport layer 40: electroluminescent layer (light emitting diode), or electron/hole generating layer (photovoltaic element) 60: Cathode 31

Claims (1)

J3 12^^106441 Patent Application Revision Amendment, Patent Application Range: 1. An electroluminescent polymer, a homopolymer consisting of monomer units as shown in formula (I): Wherein R1 and R2 are independently hydrazine; a linear or branched CU2 alkyl group; a linear or branched <^_22 alkoxy group; an ortho, meta or para-alkylphenyl or alkylbenzyl group a group wherein the alkyl group is a linear or branched Cl alkyl group; an ortho, meta and para alkoxyphenyl or alkoxyfluorenyl group, wherein the alkoxy group is linear or branched C^oalkoxy; 2.3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkyl fluorenyl, wherein The alkyl group is a linear or branched Cu alkyl group; a 2,3-, 2,4-, 2,5-, 2,6-, 3.4- or 3,5-bisalkoxyphenyl or bisane An oxybenzyl group, wherein the alkoxy group is a linear or branched C^o alkoxy group; or an alkyl aromatic heterocyclic group in which the alkyl group is a linear or branched C 1-30 alkyl group. 2. The electroluminescent polymer according to claim 1, wherein R1 and R2 are independently a C6-12 alkyl group of a nitrogen, a straight bond or a bond; and a C6-12 alkoxy group of a direct bond or a bond An ortho, meta or para-alkylphenyl or alkylbenzyl group in which the alkyl group is a linear or branched C6_2G alkyl group; an ortho, meta or para alkoxyphenyl group or Alkoxybenzyl, wherein the alkoxy group is a linear or branched C6_2Q alkoxy group; 2,3-, 2,4-, 2.5-, 2,6-, 3,4- or 3,5- a dialkylphenyl or a dialkylbenzyl group in which the alkyl group is a straight or branched chain (6-2()alkyl; 2,3-, 2,4-, 2,5-, 2,6 a -3,4- or 3,5-bisalkoxyphenyl or bisalkoxy T group, wherein the alkoxy group is a linear or branched C6-20 alkoxy group; or an alkyl aromatic heterocyclic group The alkyl group is a linear or branched C6-20 alkane 32 1312771. 3. The electroluminescent polymer according to claim 1, which is used in a photovoltaic element. The electroluminescence polymer according to 3, wherein the photoelectric element is a light emitting diode, a solar cell, an organic transistor, Photoelectric sensor 5. The electroluminescent polymer according to claim 1, which is formed into a composition with other organic conjugated molecular materials and used in a photovoltaic element. It includes the following monomer units: (a) Monomer units of formula (I): Wherein R1 and R2 are independently hydrogen; linear or branched (^-22 alkyl; linear or branched <^22 alkoxy; ortho, meta or para alkyl) a phenyl or alkylbenzyl group in which the thiol group is a straight bond or a bond of a Ci_3G alkyl group; an ortho, meta and para alkoxyphenyl group or an alkoxypurine group wherein the alkoxy group is Ci_3〇 alkoxy group of a straight bond or a branch; 2.3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkylphenyl or dialkyl T a Cwo alkyl group in which the alkyl group is a straight or branched chain; 2,3-, 2,4-, 2,5-, 2,6-, 3.4- or 3,5-bisalkoxybenzene Or a bis-alkoxybenzyl group, wherein the alkoxy group is a linear or branched C^o alkoxy group; or an alkyl aromatic heterocyclic group wherein the alkyl group is a straight or branched C 1- And (b) - a monomer unit selected from the group consisting of a phenyl group, a polyphenylene group, an unsaturated heterocyclic group, and a polycyclic unsaturated heterocyclic group. An electroluminescent polymer as described in claim 6 of the patent application, wherein (b) Each of the ring units of 33 1312771 has 3 to 8 ring atoms, which are carbon, sulfur, oxygen, helium or nitrogen. 8. The electroluminescent polymer according to claim 7, wherein each of the ring atoms independently has the following substituents: hydrogen; F; C1; a linear or branched CN22 alkyl group; a straight chain or a branched chain; (^_22 alkoxy; ortho, meta or para-alkylphenyl or alkylbenzyl, wherein the alkyl group is a straight or branched <^22 alkyl; or an ortho, Alkoxyphenyl or alkoxybenzyl as a straight or branched chain, wherein the alkoxy group is a linear or branched C 1-22 alkoxy group. 9. The electricity as described in claim 6 Excitation light polymer, wherein R1 and R2 are independently a C6-12 alkyl group of a nitrogen, a straight bond or a bond, a C6-12Hexyloxy group of a straight bond or a bond; an ortho, meta or para-alkyl group a phenyl or alkylbenzyl group wherein the alkyl group is a linear or branched C6_2G alkyl group; an ortho, meta or para alkoxyphenyl or alkoxyfluorenyl group, wherein the alkoxy group is Linear or branched C6_2G alkoxy; 2,3-, 2,4-, 2,5-, 2,6, 3,4- or 3,5-dialkylphenyl or dialkyl a benzyl group wherein the alkyl group is a linear or branched C6_2G alkyl group; 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5 - a bisalkoxyphenyl or bis alkoxy fluorenyl group, wherein the alkoxy group is a linear or branched C6-20 alkoxy group; or an alkyl aromatic heterocyclic group in which the alkyl group is a straight chain or a branched chain The C6_20 alkyl group of the chain. 10. The electroluminescent polymer according to claim 6, which is an alternating copolymer of the monomer unit of (a) and the monomer unit of (b), the illuminating wavelength can be covered 400 to 700 nm ° 11. The electroluminescent polymer according to item 8 of the patent application, wherein the monomer unit of (b) is 34 1312771 Wherein each R is independently hydrogen; F; Cl; a linear or branched CW2 alkyl group; a linear or branched C!22 alkoxy group; an ortho, meta or para-alkyl phenyl or alkane a benzyl group, wherein the alkyl group is a linear or branched Cu 2 alkyl group; or an ortho, meta or para alkoxyphenyl or alkoxybenzyl group, wherein the alkoxy group is linear or Branched Ci 22 alkoxy. 12. The electroluminescent polymer according to claim 5, wherein each r is independently hydrogen; F; Cl; a linear or branched Cl l2 alkyl; a linear or branched Ci i2 alkoxy An alkylphenyl or alkylbenzyl group in the ortho, meta or para position, wherein the alkyl group is a linear J-chain CVu alkyl group; or an ortho, meta or para alkoxybenzene group; Or an alkoxyalkyl group, wherein the alkoxy group is a linear or branched alkoxy group. 13. The electroluminescent polymer according to item 6 of the patent application, which is used for a photovoltaic element. _ 14. The electroluminescent polymer as described in claim 13 is an illuminating body, a solar cell, an organic transistor, or a photo sensor. His right towel is a full-time electric excitation polymer as described in Item 6, which is formed into a composition with a yoke molecular material for use in a photovoltaic element. 16. An electroluminescent polymer composition comprising: an optically excited metal (1-3) 99 to 1 weight percent organic conjugated molecular material as described in claim 1 of the patent application. 17. An electroluminescent excitation polymer composition comprising: a high light weight percentage, such as a medium range, "electrical excitation (1 to 1 weight percent of an organic conjugated molecular material. 18· An electromechanical excitation device comprising the following: 35 1312771 a transparent substrate; an anode on the transparent substrate; a hole transport layer on the anode; and an electrical excitation as described in claim 1 The light emitting layer of the photopolymer is located on the hole transport layer; and a cathode is located on the light emitting layer. 19. An organic photovoltaic device comprising the following: a transparent substrate; an anode disposed on the transparent substrate a hole transport layer is disposed on the anode; an electron/hole generating layer comprising the electroluminescent polymer as described in claim 1 is located on the hole transport layer; The cathode is located on the electron/hole generating layer. 20. An organic electroluminescent device comprising the following: a transparent substrate; an anode disposed on the transparent substrate; a hole transport layer The light-emitting layer is disposed on the hole transport layer, and comprises an electroluminescent polymer as described in claim 6; and a cathode is disposed on the light-emitting layer. An organic photovoltaic device comprising the following: a transparent substrate; an anode on the transparent substrate; a hole transport layer on the anode; and an electroluminescent light as described in claim 6 The electron/hole generating layer of the polymer is located on the transport layer of the hole; and a cathode is located at the electron/hole generating layer. 22. An organic electroluminescent device comprising the following: a substrate; an anode disposed on the transparent substrate; a hole transport layer disposed on the anode; a light emitting layer disposed on the hole transport layer, including as in claim 16 or 17 The electroluminescent polymer composition is described; and a cathode is disposed on the luminescent layer. 37