TW200422323A - Organic compounds having a core-shell structure - Google Patents

Abstract

The invention relates to compounds having a core-shell structure, to a process for preparing them and to their use as semiconductors in electronic components.

Description

200422323

The method contains organic matter with a core-shell structure, and the method also relates to its application as a semiconductor in electronic components. In the past 15 years, with the discovery of organic conductive compounds and compounds, the field of molecular electronics has developed rapidly. During this period 10 15 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 20 compounds with semiconducting and electro-optical properties were discovered. Generally ~ for knife electronics will not replace traditional Ishiba semiconductor components. On the contrary, people believe that molecular electronic components can open up new application areas that require large-area coatings, structural flexibility, and low-temperature and low-cost processing. At present, semi-conductive organic characters, such as the field-effect transistor (Caτ), organic Wei Diode, sensor and optoelectronic elements, have obtained a simple combination of 10 FETs into organic semiconductor integrated circuits, which is cost-effective and cost-effective. The problem of smart cards or price indicators that have not been solved so far with the help of Shi Xi technology, which lacks flexibility, finds a low-cost solution. At the same time, 〇FET can be used for large-area flexible building displays. About semiconductor semiconducting Zhao, semiconductor integrated circuits and their applications are reviewed in "Electronics", 2002, Vol. 15, the title page. A FET is a three-electrode element, in which the conductivity of a small conductive channel between two electrodes (also known as "source" and "drain") is isolated by a thin insulating layer. Each electrode (also known as the "face pole") is controlled. The most important characteristic of a field effect transistor is the movement characteristic of the charge carrier. It has an important effect on the switching speed of the transistor and the ratio of the current in the on / off state, that is, the “on / off ratio”. So far, there are two main types of organic compounds used in organic field effect tubes. These organics all contain long conjugated units, and they are divided into paper according to the molecular weight and structure. The paper size is applicable to the Chinese National Standard (UNS) A4 specification (21 × X 297) «200422323 A7 B7 5. Description of the invention (2) Conjugated polymers and conjugated oligomers. Oligomers usually have a uniform molecular structure and a molecular weight of less than 10,000 Daltons. Polymers usually contain uniform repeating units and chains of molecular weight distribution. However, there is a continuous transition between oligomers and polymers. 5 The difference between oligomers and polymers is usually reflected in the fundamental differences in the processing of these compounds. The oligomers are usually vaporized and applied to a substrate by a vapor deposition method. The term polymer usually refers to compounds that no longer evaporate, so regardless of their molecular structure, they must be applied by other methods. For polymers, it is usually necessary to dissolve them in a liquid medium, such as in an organic solvent, and then apply the corresponding method. For example, a common application method is spin coating. A particularly good method for applying the semiconductive compound is by the inkjet method. In this method, a semiconductive solution is dropped on a substrate in the form of very fine droplets, and then dried. This method allows structure to be formed during application. This method of applying the semi-conductive compound 15 has been introduced, for example, "Nature > 401, p. 685." Generally speaking, the wet chemical method is considered to be a simple method for obtaining inexpensive organic semiconductor integrated circuits. Greater potential. An important prerequisite for the production of high-quality organic semiconductor circuits is printed by the consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Ordering plays an important role in semiconductors. Non-uniform alignment of the compounds 20 and obvious grain boundaries can cause significant degradation of semiconductor characteristics. Therefore, organic semiconductor circuits produced without a particularly high-purity compound are generally unusable. For example, residual impurities can inject a charge into a semiconducting compound ("dopant,"), thereby reducing the on / off ratio, or significantly reducing its conductivity as a charge scavenger. Furthermore, the paper is applicable in this standard. afg ^ (CNS) x ^ lattice (21 (^ 297 to) 200422323 A7 B7 V. Description of the invention (3) Ground impurities can cause a reaction between a semiconductive compound and oxygen, and impurities that undergo oxidation can oxidize a semiconductive compound , Which shortens the possible storage, processing and working life. The generally required purity cannot be achieved by known polymers = 5 methods, such as washing, re-sinking and extraction. On the other hand, the two are uniform and usually Volatile oligomers can be purified relatively easily by sublimation and chromatography. Some important representatives of some semi-conductive polymers are, for example, copolymers of the following degrees, such as poly (9,9-dioctylfluorene · co- -Bisphene) ⑴ 10

(D, 2000

I I

I

Transfer to I I I I I I I I I

The charge mobility of the consumer cooperative system of the Intellectual Property Bureau of the Ministry of Economic Affairs, u.uzcnr / vs (1, 290, p. 2123), hereinafter referred to as mobility, poly (3-hexylthiophene_2) , 5_ 二 基 > (11)

This paper scale applies Chinese National Standard (〇 ^ 5) 8.4 size (210x297 mm) 200422323 A7 B7 V. Description of the invention (ο has been able to reach a mobility of 0.1cm2 / Vs ("Science", 1998, 280 volumes, Page 1741). Polyfluorene, copolymers and poly (3-hexylthiophene 2,5-diyl), like virtually all long-chain polymers, form a good film after application from solution, so Easy to process. However, high molecular weight polymers with molecular weight distribution cannot be sublimated by vacuum, they can only be purified by chromatography, and there are certain difficulties. Important representatives of oligomeric semiconductive compounds, such as oligothiophene, especially those A compound having a terminal alkyl substituent, represented by chemical formula (III), 10

η-4-6 (HI) RX = H, alkyl, alkoxy and 2,3,6,7_dibenzoanthracene (IV)

(IV) The typical mobility of dihexyltetrathiophene, -pentathiophene and -hexathiophene printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs is 15 0.05-0.1cm2 / Vs. The mesophase, especially the liquid crystal phase, plays an important role in semi-conductive organic compounds, but so far scientists have not fully understood this field. For example, the mobility of α, α'-dihexyltetrathiophene crystals is the highest reported to date (Chem. Mater., 1998, Vol. 10, 457). These crystals change from a liquid crystal phase at a temperature of 80 ° C at a denaturation of 20. Crystallized from medium (Synth · Met., 1999, 101 -6_ This paper size applies to the Chinese National Standard (CNS) A4 specification (210x297 public copy) 200422323 A7 B7 V. Description of the invention (5) volume, page 544). Particularly high mobility is obtained when using single crystals. For example, α, α'-hexathiophene single crystals have been reported to have a mobility of 1.1 cm2 / Vs (Science, 2000, 290, p. 963). If oligomers are applied in solution, the mobility is usually significantly reduced. 5 In general, the reduction in semiconducting properties of oligomeric compounds processed from solution is due to the moderate solubility of the oligomeric compounds and the weak tendency to form films. Therefore, for example, the heterogeneity is attributed to Shen Dianwu (Chem. Mater 1998, Vol. 10, 633) formed during the drying of the solution. Therefore, the excellent processing properties and the formation of semiconductive polymers have been formed into films. An attempt to combine the properties of a polymer with the properties of a semiconductive oligomer. U S-A6025462 describes a conductive polymer with a star structure consisting of a dendritic core and a conjugated side shell. However, these compounds have many advantages If these pendant groups consist of non-side substituted conjugated structures, the resulting compounds are slightly soluble or insoluble and cannot be processed. If the conjugated unit 15 is replaced with a pendant group, solubility will definitely increase, However, due to the space it occupies, the side group causes internal disorder and morphological rupture, resulting in the weakening of the semiconducting properties of these compounds. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, WO02-26859 describes the connection on the conjugated main chain Polymers with aromatic conjugation bonds. These polymers have diaryl 20-based amine pendant groups that make electron conduction possible. However, these diaryl amine pendant groups are not suitable. As a semiconductor, there is a continuing need for compounds that combine the properties of organic semiconductive oligomers and polymers. Therefore, an object of the present invention is to provide organic compounds with good semiconducting properties obtained by processing in general solvents. These organic semi-conducting standards are applicable to the Kansuka Standard (cns) a4 rule; (2ιOX 297) _ 200422323 V. Description of the invention (e) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Area coating is particularly suitable. The compound is formed of high-quality uniform thickness and morphology to suit electronic applications. 疋 It has now surprisingly been discovered that organic compounds with the required properties have been formed by multifunctional units. The core-shell structure consists of a core and a shell composed of a linear conjugated oligomeric chain with an irreversible non-common chain link at its endpoints. According to this, the present invention prepares a core and a shell composed of multifunctional units and A core-shell structured compound composed of linear co-simple oligomeric chains with flexible non-co-probable chain links at the endpoints. 10 纟 In a preferred embodiment, the compound of the present invention is An oligomer or polymer. According to the present invention, this core-shell structure is at the molecular level, that is, it relates to the structure of a molecule. For the purposes of the present invention, linear conjugated oligomeric chains The terminal link point 15 is a point in the terminal unit of a linear conjugated oligomeric chain in which no other such link exists. The compound of the present invention preferably has a core-shell structure K + L represented by the chemical formula (Z). —R) n (Z) where 20 K is a η-functional core L is a linear co-consumptive oligomeric chain R is a linear or branched QtCm-alkyl, monounsaturated or polyunsaturated Standard (CNS) A4 specification (210x297 mm) 200422323 A7 B7 V. Description of the invention (7 r ::; cr; r, C2'c ^^ 'c ^ The number η is an integer greater than or equal to 3, preferably greater than or equal to The entire 5 shells of or equal to 6 are supported by n linear conjugated chains B supported by R. For example, if n is 3 or 6, this is the structure represented by the chemical formula (M) or (Z · 6)

R

K * —L—R

R, FT l:! ≪

R I R (Z-6) 10 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 15 (Z-3) where K, L and R are as defined above. In the structure of this compound, a core composed of polyfunctional units, for example, a branched core, a linear conjugated oligomeric chain and a tough non-conjugated chain are connected together. The core composed of polyfunctional units has a dendritic structure. Or super branchy structure. Ultrabranched structures and their preparation are well known to those skilled in the art. Ultra-branched polymers or oligomers have a unique structure determined by the monomer structure used. The monomer used is ABn monomer, that is, the monomer has two different functional groups A and B. Among them, the functional group A only exists in one molecule and the other energy group B appears multiple times (n times). These two functional groups A and -9- this paper size is applicable to the ten solid standard (CNS) A4 specification (210x297 & meal). B can react with each other to form a chemical bond, that is, is polymerized. Due to the structure of the monomer, a branched polymer having a dendritic structure is polymerized, that is, an ultra-multibranched polymer. The ultra-multi-branched polymer has no regular branching points, and the end without% 'bond has no B functional group. Hyperbranched polymers, their structures, branching problems, and nomenclature have been described in LJ Mathias, TW Carothers, Adv · Dendritic Macromol. (1995), 2, 10M21 for examples of silicone-based ultra-branched polymers There are narratives and these studies are cited here. The ultra-branched structure which is preferred for the purpose of the present invention is an ultra-branched polymer. 10 However, cores composed of polyfunctional units are particularly preferred to have a tree-like structure, which is particularly suitable because of their regular composition. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for the purpose of the present invention. Each step of the number of bodies grows exponentially, and the last 15 passes to the spherical branch structure. This forms a three-dimensional macromolecule that contains branches and a structure that extends regularly from the center to the periphery. This structure is usually formed layer by layer by methods well known to those skilled in the art. The number of layers is often called the generation. The number of branches and the number of end groups per layer increase with the generation. The dendritic structure preparation and nomenclature has been well known and described by those skilled in this method.20 For example, G.R. Newkome et al.

Dendrimers and Dendrons, Wiley_VCH, Weiheim, 2001. Useful structures in nuclei consist of dendritic structures, hereinafter also referred to as tree dendritic nuclei, in principle those described in USA 6,025,462. For example, 'These are ultra-branched structures, such as polyphenylene, polyether_, -10- This paper size applies Ningguo National Standard (CNS) A4 specifications 1210 X 297 public love) 200422323 A7 B7 employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives 5. Invention Description (9) Polyester, which has been described in, for example, USA5,183,862, USA5,225,522, and USA5,270,402, such as in USA5,264,543, aromatic amidamine, such as USA5,346,984 Polyamines described in, for example, polycarbosulfan or polycarboxan as described in US 6,384,172, and polyarylene as described in 5 USA5,070,183 or USA 5,145,930, Or dendritic structures such as polyarylenes, polyarylene ethers, or polyamines of the type described in USA 4,435,548 and USA 4,507,466, and for example polyamines described in USA 4,631,337 Ethylimine. But 'other structural units can also be used to form dendritic nuclei. The function of the dendritic core is to form many different functional groups, thereby forming a matrix connected by a linear conjugated oligomeric chain to form a core-shell structure. The linear oligomeric chains are pre-determined by connecting to the substrate, and their role is therefore increased. The dendritic core has a series of functionalities—that is, connection points—suitable for connecting 15 linear oligo chains. According to the invention, the dendritic core and the core composed of an ultra-multi-dendritic structure have at least three, preferably at least six different functionalities. The preferred structure of the dendritic core is 1,3,5_phenylene units (chemical formula να) and chemical formula (Vb) to chemical formula (V_e), and there are 20 units of the same or different in the chemical formula (v_a) to (ve). Connected to each other. -11-This paper size applies to the national standard of country A (Stone Jsj 乂 4 specification (210x297 mm) ------

200422323 A7 B7 V. Description of the invention (10)

(V_a)

--¾ (V-e) The positions marked by * in the chemical formulae (V-a) to (V-e) and the formulae used below are the connection points. The units of '(V-a) to (V-e) are connected to each other or to a linear conjugated oligochain through them. Examples of dendritic nuclei composed of units of formula (V-a) are as follows:

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The quick contacts connected to the linear conjugated oligomeric chain occur at the positions marked with *. 10 The shell of the compound in the present invention is formed by a linear conjugated oligomeric chain connected to the core. Suitable linear co-oligomeric chains have in principle all chain structures of oligomers or polymers known to be conductive or semi-conductive. They are, for example -12- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 200422323 A7 B7

V. Description of the invention (11) For example, substituted or unsubstituted polyaniline, polythiophene, polyethylenedioxythiophene, polyphenylene, poly11-pyrrole, polyacetylene, polyisonaphthyl, polyphenylene Stupid, burial, these can be used as homopolymers or homo-oligomers or as copolymers or co-oligomers. Examples of these preferred as the linear conjugated oligomeric chain structure 5 are chains consisting of 2 to 10, especially 2 to 7 units represented by chemical formulae (vi-a) to (VI-e), R1

(Vl-a) (Vl-b) (V | .C)

Among them, 10 Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 15 R1, R2 and R3 may be the same or different, and they are each a hydrogen atom or a straight or branched chain CrC ^ o-alkyl or branched chain Fortunately, the same and all are hydrogen atoms. R4 may be the same or different. Each is a hydrogen atom or a straight or branched CrCw alkyl group or a branched CrCw alkyl group, preferably a hydrogen atom or C6-C12. -Branyl group 'R5 is a hydrogen atom or a fluorenyl group or an ethyl group, preferably a hydrogen atom. -13- The size of this paper applies to China National Standard (CNS) A4 (210x297 mm) 200422323 V. Description of the invention ( 12) The positions marked by * in the chemical formulae (VI_a) to (VI_e) are the connection points. The units to (V_e) are connected by this to form a linear co-light oligomeric chain, or the end of the chain is passed through the connection point. Linked to the core, a tough, non-conjugated chain. Particularly preferred is the presence of a substituted or unsubstituted 2,5-thiophene (VI_ Magic or (vi_b) unit, or a substituted or unsubstituted ι, 4-phenylene (νι⑷ The unit's linear common vehicle low poly bond. The above digits are 2,5- or Shows the position where the unit is attached. Particularly good is the presence of a substituted or unsubstituted 2, thiothiophene (VI_a) or 10 2,5- (3,4-ethylenedioxythiophene) (VI-b). May be involved The example is a compound represented by the chemical formula (2_6-1). 5 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 15

(Z-6-1) wherein R is as defined in the chemical formula (Z). P is an integer from 2 to 10, preferably from 2 to 7. The linear record of the low-order noise indicated by R in the formula 3 (Z) is maintained at the end of the non-common vehicle chain. The delicate chain refers to the U part) The molecular mobility and the result react with the solvent molecules to increase the resolvability. For the purposes of the present invention, softness refers to (internal) points. • The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (2l5TS7 ^ y 200422323 A7 B7 13) V. Description of the invention === ether group of r 嶋 oxygen atom in 2 and 0m. In particular, good 疋 has unbranched C2_C2 "alkyl or 2 <: 20-alkoxy. An example of a suitable chain is an alkane Groups such as n-hexyl, n-heptyl ^, n-octyl, n-nonyl, n-decyl and n-dodecyl, or alkoxy 10 ^, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyl 4-oxyl, n-decyloxy and n-dodecyloxy. 4-The preferred embodiment of the present invention preferably has a phenylene unit in the dendritic core with 2 to 4 thiophenes or 3,4-ethylene Oligofluorene or oligo (3,4-ethylenedioxydiphene) unsaturated chain based on dioxythiophene units as linear co-simple oligomeric chains, and C6_C12-carbon groups as flexible non-co-bonded 15 compounds. The two compounds represented by the formulas (XII) and (XIII) are described below:

Pi〇H2

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

\ J # (XII This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm)

200422323 Invention description (14)

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Consumer Affairs Agency The compounds of the present invention are conductive or semi-conductive. According to the present invention, a semiconductive compound is preferred, and a compound having a migration rate of at least 10-4 cmVvs is most preferred. The organic compound of the present invention can be easily dissolved in general solvents such as aeroform, toluene, diethyl ether, digasmethane, and tetrahydrofuran, and is therefore very suitable for processing in a solution. It is particularly surprising that the compounds of the invention have linear conjugated oligomeric chains with unsaturated thiophene or 34-ethylendiodiphene units. The chains have good solubility, and the internal sequence -

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 200422323 Not broken by large side keys. Therefore, the organic compound of the present invention has good semiconducting properties and very good film forming characteristics. They are therefore very suitable for large-area coatings. Furthermore, the organic compound of the present invention has very good thermal stability and good anti-aging properties. 5 In principle, the compounds of the present invention can be prepared by two different routes, that is, the methods of preparation for convergence and divergence. I. In a convergent preparation method, the linear conjugated oligomeric chain is retained by the non-common flexible chain prepared in the first step. In the case of a dendritic nucleus, it is connected to a structural unit called a single branch, that is, a structural unit containing a dendritic structure-part and a unit that can be connected to form a dendritic structure. Many single branches are connected to form the final structure in the last step of the preparation. In the divergent preparation method, dendritic nuclei or nuclei containing ultra-multi-dendritic structures are prepared in the first step. The linear shared car oligomeric chain maintained by the non-shared car soft chain can be connected to the core in the next step. As for the properties of the compounds of the present invention, the preparation method described is in principle inconclusive. Many variations can occur in the described preparation methods. Therefore, for example, it is possible to change the order of the individual preparation steps and, for example, to link the non-conjugated flexible chain and the linear conjugated oligomeric chain as the last step of the preparation. 20 However, depending on the structure to be produced, for example, it is effective to link non-conjugated flexible chains and linear conjugated oligomeric chains in the preparation, because the flexible chains increase the solubility of the structural unit, so there are Contribute to the preparation of this composition. In principle, those who are proficient in this method are familiar with a series of chemical reactions. -17- This paper size applies the Zhongguanjia Standard (CNS) A4 specification (21G X 297 public love)

200422323 A7 B7 V. Description of the invention (16), for forming a core composed of polyfunctional units 'connecting it with a linear co-light oligomeric chain' and a series of non-conjugated flexible bonds to these chemical reaction. Therefore, the present invention also provides a method for preparing the compound of the present invention, which is characterized by being prepared by an organometallic reaction. For organometallic reactions, it is necessary to introduce a suitable functional group to a dendritic or ultra-multi-dendritic core 'and the linear co-oligomeric chains and flexible non-conjugated bonds are connected to these in order. For example, these functional groups are halogen, such as gas, bromine, iodine, preferably 10 bromine, organotin groups such as trifluorenyltin or triethyltin, organosilicon groups such as trifluorenylsilyl, or A methylsilyl group, or an organic boron group such as boric acid. An organometallic reaction that is particularly suitable for coupling a single component of a compound of the present invention is the use of a palladium catalyst with two bromo groups via a Grignard reagent, for example, 15,1-bis (diphenylphosphino) ferrocene digas palladium ), Kumada coupling was performed, and Suzuki coupling was carried out using a silkening agent with a moth-containing group under basic conditions. Those skilled in the art are familiar with the steps for performing this coupling reaction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The towels between the two preparations and the final compounds should preferably be purified. This can be done by 6 known methods: steaming, sublimation, recrystallization, extraction, re-sinking, washing or chromatography. Intermediates and final compounds are best purified by distillation, sublimation and chromatography, as these guarantee the highest purity. Compared with known semi-conductive polymers, this has the advantage that the present invention can prepare high-purity compounds by simple traditional purification methods, so -18- this paper is sized to the relevant standard (CNS) A4 specification U1G χ 297 male ______ 200422323

Make them suitable for application in semiconductor technology. The compounds of the present invention can form a mesophase (mesogenic state), that is, a physical state between a solid and a liquid. This also relates to the liquid crystal phase and helps to predetermine the compounds of the invention. The compounds of the present invention form a liquid crystal phase at temperatures ranging from 5 to 300 ° C, particularly preferably from 跗 ^ to ⑽⑽ ^. The compounds of the present invention can be dissolved in at least 0%, preferably at least 1%, and particularly preferably at least 5% of common solvents, such as aeroform, methylbenzyl, benzene, ethyl scale, digas, or tetrahydro Squeak. The compound of the present invention can form 10 layers of high-quality thin films of uniform thickness and morphology, and is therefore suitable for electronic applications. Finally, the invention also provides compounds of the invention as semiconductors in electronic components such as field-effect tubes, light-emitting components such as organic light-emitting diodes or photovoltaic cells, lasers, and sensors. For these purposes, the compound of the present invention is preferably used in the form of a film. … Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In order for them to function effectively as semiconductors, the compounds of the present invention have sufficient mobility, such as at least 10-4 cm2 / Vs. For applications, the compounds of the present invention are applied to suitable substrates, such as silicon wafers, polymer films, glass wafers provided in power or electronics. In principle, it can be applied by all 20 application methods. The compounds of the present invention are preferably applied in the liquid phase, i.e., the solution, after which the solvent is vaporized. Application in solution is performed by known methods, such as spraying, dipping, printing and doctoring. Application is preferably performed by spin coating and ink jet methods. The layer of the compound of the present invention can be further processed after application. Example -19- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 200422323 A7 B7 V. Description of the invention (ι〇, such as By heat treatment, such as by liquid crystal phase inversion, or structured, such as by misfired rice cooking. Furthermore, the present invention provides an electronic component comprising a compound of the present invention as a semiconductor. 5 Example 5-Decyl-2,2 ： 5, 2, 2, and triple thiophene (8, 1 ^ 8, 1993, p. 1099; Chem. Mater., 1993, Vol. 5, 430) (3,5-diphenylphenyl) trimethylsilyl Calcination (J. Organomet · Chem "1983, Vol. 215, p. 149) has been prepared by known procedures used in the present invention. Example 1: (Intermediates containing linear conjugated oligomeric and end chains). ΥΠ) 15 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (5Π-decyl-2,2 ': 5', 2 " Trithiophene-5-yl) Preparation of Deserted Magnesium (VII): Butyl (1.6 Mn n-BuLi was dissolved in 8.8 m (14.0 mmol hexane), and was added dropwise to 5-decyl · 2,2,: 2,2 "trithia through a syringe. (6.60 g, 14.4 mm) in anhydrous THF (100 mL), and stirred under N 2 at 2 ° C. After the 20% addition was completed, the solution was heated to room temperature (23.0, and stirred for one more). Hours. Then cooled to 2 ° C, immediately added MgBr2-Et20 (3.67, 14.2 mmol). The reaction mixture was warmed to room temperature again and stirred for another hour. (5 " _decyl_2,2,: 5 ,, 2 ,, = 嗟 phenyl) > The odorized town was not separated, instead the solution obtained was directly used to enter -20- This paper size applies to China's national standard (cns) A4 specification (〇χ 297 public love) 200422323 A7 B7 V. Description of the invention (19) One-step reaction Example 2: (Preparation of single branch intermediate containing silane functional group)

(VIII) 4 10 15 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [3,5-Double 5 " -decyl · 2,2 ': 5', 2 " Trithiophene-5-yl) phenyl] ( Preparation of trimethyl) silane (VIII) · Freshly prepared solution of 5-decyl_2,2, · 5,2 "diphenphene (14.0 mmol) in anhydrous THF (Example 1) at room temperature (3,5-monobenzyl) difluorenylsilane (L54g, 5mm) and Pd (dppoc1 2 (70mg, 0.1mmol) (dppf = diphenylphosphine) dissolved in 50ml of anhydrous THF After completion of the addition, the solution was stirred for another two hours. The completion of the reaction was monitored by TLC. Then the reaction mixture was poured into 300 ml of cold anhydrous ether, and then 200 ml containing 20 ml of 1 M (1 mole) HC1 was added. The ice phase. The ether phase containing the yellow precipitate (the desired product) was separated, and each was washed three times with 100 ml of ice water. The ether phase was filtered through a glass sieve, and the separated products were each washed three times with 50 ml of cold anhydrous ether. Drying under reduced pressure. This gave 3.36 g of a dark yellow crystalline crude product. After purification by column chromatography (eluent ·· n-hexane / aqueous 4 ·· 1) at a temperature of 40 ° C, 1- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (2i0x297 mm) 200422323 A7 _ B7 V. Description of the invention (20) Recrystallization from hexane to finally obtain 2.64g of pale yellow crystals. Yield: 57%. Melting point: 120 ° C. NMRGOO MHz, CDC13, TMS / ppm): 0.353 (s, 9H), 0.884 (t, 6H, J = 6.9), 1.20-1.45 (overlapping peak, 28H), L688 (m, 4H, J = 7.3, M = 5), 2.798 (t, 4H, J = 7.6), 5 6.692 (d, 2H, J = 3.9), 6.696 (d, 2H, J = 3.9), 7.021 (d, 2H, J = 3.9), 7.109 (d, 2ft3.9), 7.156 (d, 2H, 3.4) ^ 7.287 (d, 2H, 3.9), 7.623 (d, 2H, J = 2.0), 7.763 ( UH, J = L7). Example 3: (Preparation of boron-functional group single branch oligosome) 10

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2- [3,5-Bis (5, decyl-2,2 ': 5', 2 " Triphenylphene_5_yl) phenyl] _4,4,5 Preparation of 5,5-tetramethyl-1,3,2-dioxane sintering (DC): A 100 ml three-necked round bottom flask was connected to a reflux condenser 'septum and a protective gas inlet, and the flask was filled with N2. Add 15 compound (VIII) (2.31 g, 2.5 mmol) and 40 ml of anhydrous tetrakis. Next, a 5 ml, 1 MBBr3 solution of tetragasmethane was added with a disposable polypropylene syringe through a septum, and the reaction mixture was refluxed for 40 hours. Then the reaction is mixed-22- This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) 200422323 A7 B7 V. Description of the invention (21) The product is cooled to room temperature and transferred to a 500ml cone containing 250ml lMNaOH solution through a syringe Shaped bottle. 200 ml of water was added and the mixture was stirred vigorously. The aqueous phase was decanted and the remaining wet salt was suspended in a mixture of ether (200 ml), THF (100 ml) and 2M HCl (300 ml). The mixture was stirred vigorously for 3 hours until two phases formed. The ether phase was separated, the aqueous phase was washed with diethyl ether, the mixed ether phases were each washed three times with 100 ml of water, dried over Na2S04 'and the solvent was removed with a rotary evaporator. This gave 4 g of a wet brown solid lysine derivative, and pinacol (330 mg, 2.75 mmol) and 100 ml of anhydrous toluene were added. The mixture was refluxed overnight using a Dean Stark device (water separator). After cooling and removing toluene on a rotary evaporator, 3 g of a crude product was obtained as a brown solid. After purification by column chromatography (eluent: toluene), 2.64 g of dark yellow crystals were obtained. Yield · 61%. 4 NMR (400 MHz, CDC13, TMS / ppm): 0.884 (tj 6H5J = 6.9) 51 20- 1.45 (overlapping peak, 28H), L388 (s, 12H), 1.688 (m, 4H, M = 5, J = 7e5), 15 2.798 (t, 4H, JN7.6), 6.692 (d, 2H, J = 3.4), 6.995 (d, 2H, 1 = 3.4), 7.071 (d, 2H, J = 3.9), 7.104 ( d, 2H, 3.9), 7.l48 (d52H53.9), 7.334 (d, 2H, 3.4), 7.868 (t, lH, J = 1.7), 7.935 (d, 2H, J = 2.0) Intellectual Property Bureau, Ministry of Economic Affairs Printed by Employee Consumption Cooperative Example 4: (Preparation of Silane-functional Group Single Branch Intermediate) -23- tm gg? (CNS) A4 ^ r (210 x 297 ^) 200422323 A7 ____B7 V. Description of the Invention (22)

Trisyl [3,3 ", 5,5 "_tetra (5,, · decyl_2,2 ,: 5,, 2 " triple thienyl-5-yl) 1,1 :: 3, Γ-triple Preparation of phenyl-5'-yl] oxetane (X): 100ml three-necked flask connected to a magnetic stirrer, reflux condenser, protective gas inlet and septum under N2 5 (3,5-dibromobenzene) Base) trisylsilane (215g, 0.7mmol). Then add Pd (PPh3) 4 (170mg, 1.5xl (T4mol) to the glove box. The glass device is installed and removed from the glovebox. Then compound (IX) is prepared (1.47g, 1.5mmol) dissolved in 30ml of toluene and NafO3 (2Maq · (aqueous phase), 10ml) The solution printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and then deoxygenated by N2. The solution Add to a reaction vessel, and reflux the reaction mixture for 36 hours at A. Then, cool the reaction mixture to room temperature and pour into a flask containing 100 ml of water and 300 ml of CH2Cl2. Wash with 100 ml CH2Cl2. Wash the mixed CH2C12 phase with water, dry and evaporate on MgSCU. The product is purified by recrystallization from a 4: 1 n-hexane / aerobic mixture to obtain 15 to 3% pure product in the form of a brown solid. Yield: 59%. Solvent-24 · This paper is suitable for 1 size (21Gx297, 200422323, A7, B7) 5. Description of the invention (23) Point: 158 ° C. GPC ( Polystyrene standard) MP = 1540. 4 NMR (400 MHz, CDC13, TMS / ppm): 0.421 (s, 9H), 0.882 (t '12H, J = 7.1), 1.20-1.45 (overlapping peak, 56H ), 1.684 (m, 8H, M = 5 j = 7.6), 2.792 (t, 8H, J = 7.6), 6.684 (d, 4H, J = 3.9), 5 6.992 (d, 4H, J = 3.4), 7 · 012 ((1, 4Η, 3 · 9), 7.117 (d, 4H, 3.9) '7.179 (d, 4H, 3.4) 7.369 (d, 4H, 3.4), 7.753 (d, 4H, J = 1.5), 7.802 (d, 2H, J = 1.5), 7.816 (t, 2H, J = 1.5), 7.865 (t, 1H, J = 1.7) · Example 5 (Preparation of boron-functional single branched intermediate) 10

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4,4,5,5-Tetramethyl-2_ [3,3 ", 5,5 " -tetra (5 ,,-decyl-2,2,: 5, , 2,, Triphenylphen-5-yl) -1,1,: 3,, Γ-terphenyl-5, -yl] -1,3,2-dioxorane (XI): Preparation of compounds (X) (610mg, 0.33mmol), 2ml 1M Βγ3 dissolved in 15 solution in tetrachloroarsine and pinacol (44mg, 0.37mmol) through the implementation of -25- This paper size applies Chinese National Standard (CNS) A4 specifications (210x297 mm) 200422323 A7 B7 V. Description of the invention (24) Prepared by the process described in Example 3. The washing procedure described in Example 3 and drying under reduced pressure gave 650 mg of a crude product as a brown solid. After purification by column chromatography (eluent: toluene), 310 mg of yellowish brown crystals were obtained. Yield: 49%. 4 NMR (400 MHz, CDC13, TMS / ppm): 0.882 (t, 12H, J = 7.1), 1.20-1.45 (overlapping peak, 56H), 1.683 (m, 8H, M = 5, J = 7.6) 5 2.790 (t, 8H, J = 7.6), 6.682 (d, 4H, J = 3.4), 6.987 (d, 4H, J = 3.4), 7.001 (d, 4H, 3.9), 7.112 (d, 4H, 3.9), 7.175 (d, 4H, 3.9), 7.374 (d, 4H, 3.9), 7.785 (d, 4H, J = 2.0), 7.799 (t52H? J = 1.7), 7.988 (t, lH5J = 1.7), 8.123 (d52H , J = 1.5) 〇10 Example 6 (Example of preparing compounds according to the present invention) Order

200422323 A7 B7 V. Description of the invention (25) 1,3,5-tris [3,5-bis (5 " -decyl · 2,2 :: 5,, 2 " triplethiophen-5-yl) phenyl] Preparation of benzene (XII): Compound (IX) (450 mg, 4 · 6χ10 · 4πιο1), 1,3,5-tribromobenzene (40mg, I · 27χ10 · 4ιηο1), and Pd (PPh3) 4 (17mg, 1 5χ1 (T 5mol) was prepared by the procedure described in Example 4. After refluxing under nitrogen for 16 hours, the yellow solid Shen Dianwu was the main product. The reaction mixture was cooled to room temperature and poured into 100 ml of water and 400. ml CHzCl2. The organic phase containing yellow Shen Dianwu was washed three times with 100 ml of water each, and the residues (products) on the g3 glass screening program were washed three times with 20 ml each. It was dried under vacuum overnight to obtain 330 10 ratio: 99%. Melting point · 202. (3. g pure Tsuza per hour Example 7 · (Preparation of the compound according to the present invention)

200422323 A7 B7 V. Description of the invention (26), 1,3,5-tri [3,3 ", 5,5 " vertical tetra (5 " -decyl-2,2,: 5,2 " Trithiophene- 5-yl) Fine 1, Γ ·· 3,, Γ, -terphenyl-5, -yl] benzene (χΙΠ) Preparation: Using compound (XI) (250mg, 1.3x10 · 4πιο1), 1, 3, 5-Tribromobenzene (12 mg, 3 · 8χ1 (Γ 5 mol) and Pd (PPh3) 4 (10 mg, 8.7 > < 10 · 6ιηο1) were prepared by the procedure described in Example 4 under nitrogen. Under nitrogen After refluxing for 24 hours, the compound was isolated using the procedure described in Example 4. After column chromatography (eluent: toluene) of 275 mg of a brown solid crude product was purified, 210 mg of a glassy brown solid was obtained. Yield: 76 %. GPC (Polyethylene Standard): MP = 6900, DPI = 1.02 〇 This paper is printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, and the paper size is applicable to China National Standard (CNS) A4 (210 X297 mm)

Claims (1)

200422323 A8 B8 C8 __D8_ 6. Application scope 1. A compound characterized by having a core composed of a multifunctional unit and a shell composed of linear co-oligomeric chains with flexible non-co-chain links at the endpoints Core-shell structure. 2. The compound according to item 1 of the scope of patent application, characterized in that it has a core-shell structure K + L-R) n (Z) represented by the chemical formula (Z), where K is an η-functional core, 10 L is a linear co-oligomeric chain, R is a linear or branched C2-C2 (r alkyl, monounsaturated or polyunsaturated C2-C20-alkenyl, C2-C2 (r alkoxy, C2- C2 (raralkyl, C2-C2 (r oligoether group, or C2-C2 (r polyether group, η is an integer greater than or equal to 3. 15) Compounds according to item 1 or 2 of the scope of patent application , Characterized in that the core contains a dendritic structure. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4. The compound according to item 3 of the scope of patent application, characterized in that the structure of the dendritic core is 1, 3, 5- Phenyl unit. 5. The compound according to item 1 or 2 of the scope of patent application is characterized in that the 20 core contains a highly branched structure. 6. The compound according to item 5 of the patent scope is characterized in that the core contains a highly branched structure. The polymer is a highly branched structure. 7. The compound according to at least one of the claims 1 to 6, -29-λ. a inKiQ \ AiliaJA. ^ 9ΐΠν 907 / X ^ ^ Q742 ^ B 200422323 VI. Application scope of patents A8 B8 C8 D8 5 10 15 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 It is characterized in that the shell contains a substituted or not A substituted 2,5-thiophene, or a substituted or unsubstituted M-phenylene unit is used as a linear co-oligomeric chain. 8. A compound according to at least one of items i to 7 of the scope of patent application, characterized by a shell It is a unit containing unsubstituted 2, fluorenethiophene or 2,5_ (3,4-ethylethyloxythiophene) as a linear conjugated oligomeric chain. 9. According to claims 1 to 8 of the scope of patent application, at least one The compound of the present invention is characterized in that the linearly covalent oligomeric chain is a bond having a chain length of 2 to 7 units. 10. The compound according to at least one of the items in the scope of application for patents Nos. Each of the polychains is terminated by the same or different, branched or unbranched alkyl or alkoxy groups at the end of the chain. 11. The compound according to item 10 of the scope of patent application, which is characterized by alkyl or alkoxy groups Is unbranched C2_C2G_alkyl or C2_C2G_alkoxy 12. Compounds according to item 10 or u of the scope of the patent application, characterized in that the alkyl or alkoxy group is n-hexyl, n-decyl and n-dodecyl. 13. According to the scope of patent applications 1 to 12 The compound of at least one of the characteristics is characterized in that it forms a mesophase in the temperature range of 50. (: -300. (: The temperature range. 14. The compound according to at least one of the claims 1 to 13 in the patent application range, characterized in that It is semi-conductive. 15. The compound according to at least one of items 1 to 14 of the scope of patent application, characterized in that it has a flowability of at least 10-4 cm2 / Vs. K · A preparation according to at least one of the items 1 to 15 of the scope of the applied patent -30-φ Pu Guo Tuo standard car for Taiji Jufufu iCNS) A4 specification (210 X 297 mm) i Order 200422323 The method of compounds is characterized by preparing an oligomer or polymer by an organometallic reaction. Π. The method according to item 16 of the patent application, whose job is to prepare oligomers or polymers by Kumada coupling reaction. 5 18. The method according to item 16 of the patent application is characterized in that an oligomer or polymer is prepared by a Suzuki coupling reaction. 19. An application of a compound according to at least one of items i to 15 of the scope of patent application, characterized in that it is used as a semiconductor in electronic components. 20. According to the scope of the patent application, the application of the 19-shaped compound is characterized as a semiconductor in a field effect tube, a light emitting element such as an organic light emitting diode or a photovoltaic cell, a laser, and a sensor. 21. Application of a compound according to item 19 or 20 of the scope of application for a patent, characterized in that the application form is a thin film applied in a solution. 22 · An electronic component comprising, as a semiconductor, a compound according to at least one of items 15 to 15 of the scope of patent application. The paper size printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210x297). (1) The designated representative in this case is:% Μ (None) (II). Simple description of component representative symbols: None Κ ~ Κ—R) n (Z) Page 2-1