COMPOUND WITH BRANCHING ALKYL CHAINS, METHOD FOR PREPARING THE SAME, AND USE THEREOF IN PHOTOELECTRIC DEVICE

Abstract

The invention discloses a compound having branching alkyl chains, the method for preparing the same and use thereof in photoelectric devices. By applying the branching alkyl chains as the solubilizing group to the preparation of organic conjugated molecules (for example, organic conjugated polymers), the number of methylenes between the resultant alkyl side chains and the backbone, i.e., m>1, which can effectively reduce the effect of the alkyl chains on the backbone - stacking, thereby ensuring the solubility of the organic conjugated molecule while greatly increasing the mobility of their carriers. It is suitable for an organic semiconductor material in photoelectric devices such as organic solar cells, organic light emitting diodes and organic field effect transistors, etc.

Claims

1. A Formula (I) compound: ##STR00077## in the structure of Formula (I), m is an integer from 3 to 18; R is a halogen atom, hydroxyl, amino, trifluoromethanesulfonate group, p-toluenesulfonate group, azide group, cyano, alkenyl, alkynyl or alkoxy; R.sup.3 and R.sup.4 are the same or different, independently selected from alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl and alkynyl; R.sup.5 is hydrogen, hydroxyl, alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl or alkynyl.

2. The Formula (I) compound according to claim 1, wherein m is an integer from 3 to 4.

3. The Formula (I) compound according to claim 1, wherein the compound is selected from one of the following compounds: ##STR00078##

4. The method for preparation the Formula (I) compound according to claim 1 comprising the following steps: 1) Starting from the diol as shown in Formula (a), protection by a protecting group is conducted to obtain the diol with one terminus protected as shown in Formula (b); ##STR00079## 2) The diol with one terminus protected is oxidized to obtain the carboxylic acid as shown in Formula (c); ##STR00080## 3) The carboxylic acid as shown in Formula (c) is subject to functional group transformation and nucleophilic substitution to introduce the R.sup.3 and R.sup.4 groups; ##STR00081## 4) R.sup.5 is introduced; ##STR00082## 5) The protecting group is eliminated to generate the corresponding alcohol; ##STR00083## 6) When the R in Formula (I) is not hydroxyl, a substitution is conducted on the hydroxyl in the Formula (k) compound to convert it to other functional group, obtaining the Formula (1) compound with R being the corresponding functional group, wherein m1 is an integer of from 3 to 18 or from 3 to 4; R.sup.3 and R.sup.4 are the same or different, independently selected from alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl and alkynyl; R.sup.5 is hydrogen, hydroxyl, alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl or alkynyl.

5. The method of preparation according to claim 4, wherein the step 3) is conducted with the following method 3a) or 3b): 3a) The carboxylic acid is reacted with an alcohol and converted into an ester, followed by a nucleophilic substitution to introduce the R.sup.3 and R.sup.4 groups: ##STR00084## wherein R.sup.1 is alkyl; 3b) The carboxylic acid is converted to an acyl halide, then the nucleophilic substitution is conducted to introduce the R.sup.3 and R.sup.4 groups: ##STR00085## wherein X is halogen, wherein m1 is an integer of from 3 to 18 or from 3 to 4; R.sup.3 and R.sup.4 are the same or different, independently selected from alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl and alkynyl.

6. The method of preparation according to claim 4, wherein the step 4) is conducted with the following method 4a), 4b) or 4c): 4a) When R.sup.5 is alkoxy, a strong alkaline is reacted with the alcohol hydroxyl of the Formula (e) compound to generate an oxygen anion, which is subsequently subject to a nucleophilic substutition by R.sup.5X to obtain the compound of Formula (g): ##STR00086## wherein OR.sup.5 is R.sup.5; X is a halogen atom, trifluoromethanesulfonate group or p-toluenesulfonate group; and R.sup.5 is alkyl; 4b) When R.sup.5 is alkyl, halogen substituted alkoxy, alkenyl or alkynyl, the Formula (e) compound is reacted with trifluoromethanesulfonyl chloride to generate trifluoromethanesulfonate group, and then a nucleophilic substitution is conducted to obtain the Formula (i) compound: ##STR00087## 4c) When R.sup.5 is hydrogen atom, the oxygen atom is removed under the conditions of triethylsilane and trifluoroacetic acid to form the Formula (j) compound, ##STR00088## wherein m1 is an integer of from 3 to 18 or from 3 to 4; R.sup.3 and R.sup.4 are the same or different, independently selected from alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl and alkynyl.

7. The method of preparation according to claim 4, wherein the step 6) is conducted using one of the following method 6a)6f) depending on different substituents of R: 6a) When R is halogen, one of the following reactions is conducted to obtain the corresponding Formula (I) compound: ##STR00089## 6b) When R is trifluoromethanesulfonate group or p-toluenesulfonate group, an alkaline is reacted with the alcohol hydroxyl to generate an oxygen anion, which is subsequently subject to a nucleophilic substutition by MsCl or TsCl to obtain the corresponding Formula (1) compound; ##STR00090## 6c) When R is an azide group, the Formula (I) compound with R being an azide group is obtained by a nucleophilic substitution between sodium azide and halogen, trifluoromethanesulfonate group or p-toluenesulfonate group: ##STR00091## In the aforementioned reaction, X represents a halogen atom, trifluoromethanesulfonate group or p-toluenesulfonate group; 6d) When R is cyano, the Formula (I) compound with R being a cyano is obtained by a nucleophilic substitution between a cyanide and halogen, trifluoromethanesulfonate group or p-toluenesulfonate group: ##STR00092## In the aforementioned reaction, X represents a halogen atom, trifluoromethanesulfonate group or p-toluenesulfonate group; 6e) When R is amino, the Formula (I) compound with R being an amino is obtained by that the azide group or cyano is reduced to amino, or a Gabriel amine synthesis: ##STR00093## In the aforementioned reaction, X represents a halogen atom, trifluoromethanesulfonate group or p-toluenesulfonate group; 6f) When R is an alkenyl or alkynyl, the Formula (1) compound with R being alkenyl or alkynyl is obtained by a nucleophilic substitution of the Formula (I) compound with R being a halogen atom by a nucleophilic agent containing the alkenyl or alkynyl, wherein m1 is an integer of from 3 to 18 or from 3 to 4; R.sup.3 and R.sup.4 are the same or different, independently selected from alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl and alkynyl; R.sup.5 is hydrogen, hydroxyl, alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl or alkynyl.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0105] FIG. 1 shows the effect of the position of the solubilizing group (such as the alkyl chain) on the - stacking of the organic conjugated polymers.

[0106] FIG. 2 shows the structural diagram of the organic conjugated polymer having the branching alkyl chains according to an embodiment of the invention.

DETAILED DESCRIPTION

[0107] The invention is further described in details by way of examples in relation to figures. However, they are by no means limiting the scope of the invention.

[0108] Example 1 to Example 3 are Method for Synthesizing Alcohols Protected by Benzyloxy

EXAMPLE 1

[0109] ##STR00045##

[0110] Scheme for synthesizing Compound 1: 1,3-propanediol (60 g, 0.79 mol) was added into a 500 ml round bottom flask, then solid KOH (17.7 g, 0.32 mol) was added to remove the trace moisture in the 1,3-propanediol. Under agitation at 90 C., benzyl chloride (39.8 g, 0.32 mol) was added into the 1,3-propanediol using a dropping funnel. Then temperature was increased to 130 C. for a 2 h reaction. The reaction was stopped and cooled to the room temperature. After extraction of the organic phase using water/diethyl ether separation, the solvent was removed by reduced pressure rotatory evaporation, followed by reduced pressure distillation. 39.8 g colorless oily product Compound 1 was obtained with a yield of 77%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 7.36-7.28 (m, 5H), 4.51 (s, 2H), 3.79-3.75 (m, 2H), 3.66-3.64 (t, J=5.5 Hz, 2H), 2.44 (br, s, 1H), 1.88-1.83 (m, 2H).

EXAMPLE 2

[0111] ##STR00046##

[0112] Scheme for synthesizing Compound 2: At 0 C., 1,4-butanediol (40 g, 0.44 mol) was added into 200 ml dry THF. Sodium hydride (5.3 g, 0.22 mol) was added in batches within 30 min. The temperature returned to the room temperature for a 2 h reaction. Benzyl bromide (38 g, 0.22 mol) was dissolved in 20 ml THF, which was dropped into the aforementioned system at 0 C. followed by reflux for 4 h. After the complete of the reaction, the reaction was quenched with cold water. The organic phase was extracted with diethyl ether. After drying the organic phase with anhydrous sodium sulfate, it was filtered, then subject to reduced pressure rotatory evaporation to remove the solvent, followed by reduced pressure, distillation to obtain 28.1 g of colorless oily liquid 2 with a yield of 71%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 7.36-7.26 (m, 5H), 4.52 (s, 2H), 3.65-3.61 (m, 2H), 3.53-3.50 (t, J=5.3 Hz, 2H), 2.36 (br, s, 1H), 1.73-1.65 (m, 4H).

EXAMPLE 3

[0113] ##STR00047##

[0114] Scheme for synthesizing Compound 3: At 0 C., 1,5-pentanediol (40 g, 0.39 mol) was added into 200 ml dry THF. Sodium hydride (4.6 g, 0.19 mol) was added in batches within 30 min. The temperature returned to the room temperature for a 2 h reaction. Benzyl bromide (33 g, 0.19 mol) was dissolved in 20 ml THF, which was dropped into the aforementioned system at 0 C. followed by reflux for 4 h. After the complete of the reaction, the reaction was quenched with cold water. The organic phase was extracted with diethyl ether. After drying the organic phase with anhydrous sodium sulfate, it was filtered, then subject to rotatory evaporation to remove the solvent, followed by reduced pressure distillation to obtain 23.1 g of colorless oily liquid 3 with a yield of 62%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 7.36-7.26 (m, 5H), 4.50 (s, 2H), 3.64-3.61 (t, J=6.5 Hz, 2H), 3.50-3.64 (t, J=6.5 Hz, 2H), 1.68-1.54 (m, 4H), 1.49-1.43 (m, 2H).

[0115] Example 4 to Example 6 are the Jones Oxidation and Protection by Esterification of the Alcohols Protected by Benzyloxy

EXAMPLE 4

[0116] ##STR00048##

[0117] Scheme for synthesizing Compound 4: Compound 1 (10 g, 60.2 mmol) was dissolved into 200 ml acetone. At 0 C., Jones reagent (26.72 g chromium trioxide : 23 ml concentrated sulfuric acid, diluted with water to 100 ml) was added dropwise until the orange red color was sustained without turning green. The temperature returned to the room temperature followed by agitation for 2 h. The resultant mixture was vacuum suck filtrated and loaded onto a column which was eluted with acetone. After acetone was removed by vacuum rotatory evaporation, the organic phases were extracted with ethyl acetate for three times. The organic phases were combined and washed once with saturated saline. After dried with anhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentrated H.sub.2SO.sub.4 were added for 12 h reflux reaction. After most solvent was removed by rotatory evaporation, water/ethyl acetate phase separation was conducted. The organic phase was washed with sodium bicarbonate solution, water, and saturated saline respectively, and then dried with anhydrous sodium sulfate. After the solvent was removed by rotatory evaporation, reduced pressure distillation was conducted to obtain 9.7 g colorless oily liquid 4 with a yield of 77%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 7.36-7.28 (m, 5H), 4.54 (s, 2H), 4.17-4.13 (q, J=7.0 Hz, 2H), 3.77-3.74 (t, J=6.2 Hz, 2H), 2.63-2.60 (t, J=6.2 Hz, 2H), 1.28-1.24 (t, J=7.1 Hz, 3H).

EXAMPLE 5

[0118] ##STR00049##

[0119] Scheme for synthesizing Compound 5: Compound 2 (26.6 g) was dissolved into 200 ml acetone. At 0 C., Jones reagent was added dropwise until the orange red color was sustained without turning green. The temperature returned to the room temperature followed by agitation for 2 h. The resultant mixture was vacuum suck filtrated and loaded onto a column which was eluted with acetone. After acetone was removed by vacuum rotatory evaporation, the organic phases were extracted with ethyl acetate for three times. The organic phases were combined and washed once with saturated saline. After dried with anhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentrated H.sub.2SO.sub.4 were added for 12 h reflux reaction. After most solvent was removed by rotatory evaporation, water/ethyl acetate phase separation was conducted. The organic phase was washed with sodium bicarbonate solution, water, and saturated saline respectively, and then dried with anhydrous sodium sulfate. After the solvent was removed by rotatory evaporation, reduced pressure distillation was conducted to obtain 24.2 g colorless oily liquid 5 with a yield of 70%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 7.36-7.27 (m, 5H), 4.49 (s, 2H), 4.14-4.08 (q, J=7.1 Hz, 2H), 3.52-3.49 (t, J=6.1 Hz, 2H), 2.44-2.40 (t, J=7.3 Hz, 2H), 1.97-1.91 (m, 2H), 1.26-1.22 (t, J=7.1 Hz, 3H).

EXAMPLE 6

[0120] ##STR00050##

[0121] Scheme for synthesizing Compound 6: Compound 3 (23.1 g) was dissolved into 200 ml acetone. At 0 C., Jones reagent was added dropwise until the orange red color was sustained without turning green. The temperature returned to the room temperature followed by agitation for 2 h. The resultant mixture was vacuum suck filtrated and loaded onto a column which was eluted with acetone. After acetone was removed by vacuum rotatory evaporation, the organic phases were extracted with ethyl acetate for three times. The organic phases were combined and washed once with saturated saline. After dried with anhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentrated H.sub.2SO.sub.4 were added for 12 h reflux reaction. After most solvent was removed by rotatory evaporation, water/ethyl acetate phase separation was conducted. The organic phase was washed with sodium bicarbonate solution, water, and saturated saline respectively, and then dried with anhydrous sodium sulfate. After the solvent was removed by rotatory evaporation, reduced pressure distillation was conducted to obtain a colorless oily liquid 6 with a yield of 62%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm): 7.36-7.28 (m, 5H), 4.50 (s, 2H), 4.15-4.09 (q, J=6.8 Hz, 2H), 3.50-3.47 (t, J=5.8 Hz, 2H), 2.34-2.30 (t, J=7.0 Hz, 2H), 1.73-1.65 (m, 4H), 1.27-1.23 (t, J=6.9 Hz, 3H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm): 173.50, 138.48, 128.28, 127.52, 127.44, 72.82, 69.78, 60.14, 34.00, 29.11, 21.72, 14.19. ESI-HRMS: Calcd. for [M+H].sup.+: 237.14852. Found: 237.14859. Calcd. for [M+Na].sup.+: 259.13047. Found: 259.13068.

[0122] Example 7 to Example 9 are Reactions Between Esters and Grignard Reagents:

EXAMPLE 7

[0123] ##STR00051##

[0124] Scheme for synthesizing Compound 7: Dry magnesium powders (2.88 g, 120 mmol) and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromodecane (26.5 g, 120 mmol) in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 4 was added dropwise into the system. After 5 h reflux, it was quenched with H.sub.2SO.sub.4 (2 M) under ice bath, and then extracted with diethyl ether (350 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na.sub.2SO.sub.4 and rotatory evaporation, it was loaded onto the silica gel column for separation. Compound 7 (12.4 g) was obtained with a yield of 60%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm): 7.35-7.26 (m, 5H), 4.51 (s, 2H), 3.69-3.66 (t, J=6.0 Hz, 2H), 2.98 (s, 1H), 1.79-1.76 (t, J=6.0 Hz, 2H), 1.49-1.37 (m, 4H), 1.33-1.15 (m, 32H), 0.90-0.86 (t, J=6.4 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 137.80, 128.36, 127.67, 74.06, 73.34, 67.25, 39.14, 37.73, 31.89, 30.27, 29.62, 29.60, 29.32, 23.65, 22.65, 14.07. ESI-HRMS: Calcd. for [MOH].sup.: 429.40909. Found: 429.40925; Calcd. for [M+Na].sup.+: 469.40160. Found: 469.40182. Elemental Anal: Calcd. for C.sub.30H.sub.54O.sub.2: C, 80.65; H, 12.18. Found: C, 80.61; H, 12.16.

EXAMPLE 8

[0125] ##STR00052##

[0126] Scheme for synthesizing Compound 8: Dry magnesium powders and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromodecane in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 5 was added dropwise into the system. After 5 h reflux, it was quenched with H.sub.2SO.sub.4 (2 M) under ice bath, and then extracted with diethyl ether (350 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na.sub.2SO.sub.4 and rotatory evaporation, it was loaded onto the silica gel column for separation. Compound 8 was obtained with a yield of 47%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm): 7.36-7.25 (m, 5H), 4.51 (s, 2H), 3.50-3.47 (t, J=6.3 Hz, 2H), 1.68-1.62 (m, 2H), 1.52-1.48 (m, 2H), 1.43-1.38 (m, 4H), 1.32-1.26 (m, 32H), 0.90-0.86 (t, J=6.4 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 138.36, 128.26, 127.51, 127.43, 73.84, 72.83, 70.93, 39.20, 36.05, 31.87, 30.25, 29.61, 29.59, 29.30, 23.87, 23.50, 22.63, 14.05. ESI-HRMS: Calcd. for [MOH].sup.+: 443.42474. Found: 443.42496; Calcd. for [M+Na].sup.+: 483.41725. Found: 483.41761.

EXAMPLE 9

[0127] ##STR00053##

[0128] Scheme for synthesizing Compound 9: Dry magnesium powders and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromodecane in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 6 was added dropwise into the system. After 5 h reflux, it was quenched with H.sub.2SO.sub.4 (2 M) under ice bath, and then extracted with diethyl ether (350 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na.sub.2SO.sub.4 and rotatory evaporation, it was loaded onto the silica gel column for separation. Compound 9 was obtained with a yield of 58%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 7.35-7.25 (m, 5H), 4.50 (s, 2H), 3.50-3.47 (t, J=6.0 Hz, 2H), 1.63-1.57 (m, 2H), 1.40-1.20 (m, 40H), 1.12 (s, 1H), 0.90-0.86 (t, J=6.4 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 138.61, 128.30, 127.60, 127.45, 74.35, 72.88, 70.27, 39.23, 39.04, 31.90, 30.28, 30.26, 29.65, 29.63, 29.61, 29.33, 23.47, 22.67, 20.14, 14.09. ESI-HRMS: Calcd. for [MOH].sup.+: 457.44094. Found: 457.44063; Calcd. for [M+Na].sup.+: 497.43290. Found: 457.43363.

[0129] Example 10 to Example 12 are Deoxygenation and Palladium Carbon Catalyzed Hydrogenation:

EXAMPLE 10

[0130] ##STR00054##

[0131] Scheme for synthesizing Compound 10: Compound 7 (12.4 g, 27.8 mmol) was dissolved into 100 ml dry dichloromethane, to which Et.sub.3SiH (3.54 g, 30.5 mmol) and TFA (15.85 g, 139 mmol) were added. After 12 h reaction under the room temperature, Na.sub.2CO.sub.3 (10 g) was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichlorometane, then a rotatory evaporuation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C (0.50 g) catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24 h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A colorless oily liquid 10 was obtained with a yield of 38%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.68-3.64 (t, J=7.0 Hz, 2H), 1.55-1.50 (q, J=6.8 Hz, 2H), 1.41 (br, s, 1H), 1.32-1.25 (m, 36H), 0.90-0.86 (t, J=6.7 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 61.31, 37.01, 34.27, 33.75, 31.92, 30.07, 29.69, 29.65, 29.35, 26.57, 22.69, 14.10. ESI-HRMS: Calcd. for [M+Na].sup.+: 363.35974. Found: 363.35895.

EXAMPLE 11

[0132] ##STR00055##

[0133] Scheme for synthesizing Compound 11: Compound 8 was dissolved into 100 ml dry dichloromethane, to which Et.sub.3SiH and TFA were added. After 12 h reaction under the room temperature, Na.sub.2CO.sub.3 was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichlorometane, then a rotatory evaporuation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24 h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A colorless oily liquid 11 was obtained with a yield of 67%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.64-3.61 (t, J=6.6 Hz, 2H), 1.58-1.50 (m, 2H), 1.34-1.24 (m, 39H), 0.90-0.86 (t, J=6.7 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 63.48, 37.25, 33.61, 31.92, 30.13, 29.97, 29.71, 29.66, 29.59, 29.35, 26.67, 22.68, 14.07. ESI-HRMS: Calcd. for [M+Na].sup.+: 377.37539. Found: 377.37555.

EXAMPLE 12

[0134] ##STR00056##

[0135] Scheme for synthesizing Compound 12: Compound 9 was dissolved into 100 ml dry dichloromethane, to which Et.sub.3SiH and TFA were added. After 12 h reaction under the room temperature, Na.sub.2CO.sub.3 was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichlorometane, then a rotatory evaporuation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24 h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A colorless oily liquid 12 was obtained with a yield of 60%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.66-3.63 (t, J=6.6 Hz, 2H), 1.58-1.51 (m, 2H), 1.34-1.23 (m, 41H), 0.90-0.86 (t, J=6.7 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 63.10, 37.42, 33.63, 33.53, 33.30, 31.93, 30.14, 29.72, 29.66, 29.36, 26.71, 22.90, 22.69, 14.10. ESI-HRMS: Calcd. for [M+Na].sup.+: 391.39104. Found: 391.39139.

[0136] Example 13 to Example 15 are Reactions in Which Hydroxyl is Converted to Iodide:

Example 13

[0137] ##STR00057##

[0138] Scheme for synthesizing Compound 13: Compound 10 (3.6 g, 10.6 mmol) was dissolved into dichloromethane, to which imidazole (0.93 g, 13.7 mmol) and triphenylphosphine (3.59 g 13.7 mmol) were added. Under ice bath, 12 (3.48 g, 13.7 mmol) was added. After reacting under agitation at the room temperature for 4 h, Na.sub.2SO.sub.3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column to obtain a colorless oily liquid Compound 13 with a yield of 95%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.21-3.17 (t, J=7.6 Hz, 2H), 1.83-1.77 (q, J=7.2 Hz, 2H), 1.40 (s, 1H), 1.33-1.24 (m, 37H), 0.90-0.86 (t, J=6.7 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm): 38.64, 38.28, 32.88, 31.93, 30.03, 29.69, 29.65, 29.36, 26.41, 22.70, 14.12, 5.15. EI-MS: Calcd. for [MI].sup.+: 323. Found: m/z=323. Elemental Anal: Calcd. for C.sub.23H.sub.47I: C, 61.32; H, 10.62. Found: C, 61.56; H, 10.60.

EXAMPLE 14

[0139] ##STR00058##

[0140] Scheme for synthesizing Compound 14: Compound 11 was dissolved into dichloromethane, to which imidazole and triphenylphosphine were added. Under ice bath, 12 was added. After reacting under agitation at the room temperature for 4 h, Na.sub.2SO.sub.3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column to obtain a colorless oily liquid Compound 14 with a yield of 75%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.19-3.15 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 36.75, 34.60, 33.60, 31.93, 30.97, 30.08, 29.70, 29.66, 29.37, 26.66, 22.70, 14.11, 7.62. EI-MS: Calcd. for [M].sup.+: 464. Found: m/z=464. Calcd. for [MI].sup.+: 337. Found: m/z=337. Elemental Anal: Calcd. for C.sub.24H.sub.49I: C, 62.05; H, 10.63. Found: C, 62.35; H, 10.54.

EXAMPLE 15

[0141] ##STR00059##

[0142] Scheme for synthesizing Compound 15: Compound 12 was dissolved into dichloromethane, to which imidazole and triphenylphosphine were added. Under ice bath, I.sub.2 was added. After reacting under agitation at the room temperature for 4 h, Na.sub.2SO.sub.3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column to obtain a colorless oily liquid Compound 15 with a yield of 94%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.21-3.18 (t, J=7.0 Hz, 2H), 1.87-1.77 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 41H), 0.90-0.86 (t, J=6.8 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm): 37.25, 34.01, 33.59, 32.52, 31.94, 30.13, 29.71, 29.67, 29.37, 27.65, 26.67, 22.70, 14.12, 7.25. EI-MS: Calcd. for [MI].sup.+: 351. Found: m/z=351. Elemental Anal: Calcd. for C.sub.25H.sub.51I: C, 62.74; H, 10.74. Found: C. 62.87; H, 10.70.

EXAMPLE 16

[0143] ##STR00060##

[0144] Scheme for Synthesizing Compound 16: Dry magnesium powders (3.0 g, 124 mmol) and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromotetradecane (34.3 g, 124 mmol) in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the ether solution of Compound 5 (11 g, 49.5 mmol) was added dropwise into the system. After 5 h reflux, it was quenched with H.sub.2SO.sub.4 (2 M) under ice bath, and then extracted with diethyl ether (350 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na.sub.2SO.sub.4 and rotatory evaporation, it was loaded onto the silica gel column for separation. 22.3 g of Compound 16 was obtained with a yield of 79%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm): 7.36-7.25 (m, 5H), 4.51 (s, 2H), 3.50-3.47 (t, J=6.3 Hz, 2H), 2.98 (s, 1H), 1.69-1.62 (m, 2H), 1.52-1.49 (m, 2H), 1.43-1.39 (m, 4H), 1.32-1.26 (m, 48H), 0.90-0.86 (t, J=6.7 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 138.40, 128.33, 127.58, 127.51, 73.95, 72.90, 70.99, 39.24, 36.11, 31.92, 30.29, 29.70, 29.68, 29.65, 29.36, 23.92, 23.54, 22.68, 14.11. ESI-HRMS: Calcd. for [MOH].sup.+: 555.54994. Found: 555.55003.

EXAMPLE 17

[0145] ##STR00061##

[0146] Scheme for Synthesizing Compound 17: Dry magnesium powders (2.72 g, 113 mmol) and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromooctadecane (37.6 g, 113 mmol) in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 5 (10 g, 45 mmol) was added dropwise into the system. After 5 h reflux, it was quenched with H.sub.2SO.sub.4 (2 M) under ice bath, and then extracted with diethyl ether (350 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na.sub.2SO.sub.4 and rotatory evaporation, it was loaded onto the silica gel column for separation. 22.9 g of Compound 17 was obtained with a yield of 74%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm): 7.34-7.26 (m, 5H), 4.51 (s, 2H), 3.50-3.47 (t, J=6.3 Hz, 2H), 1.66-1.63 (m, 2H), 1.52-1.48 (m, 2H), 1.43-1.39 (m, 4H), 1.32-1.21 (m, 64H), 0.90-0.86 (t, J=6.7 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 138.39, 128.32, 127.56, 127.49, 73.92, 72.89, 70.98, 39.24, 36.11, 31.92, 30.29, 29.70, 29.69, 29.66, 29.36, 23.92, 23.54, 22.68, 14.10. ESI-HRMS: Calcd. for [MOH].sup.+: 667.67514. Found: 667.67503.

EXAMPLE 18

[0147] ##STR00062##

[0148] Scheme for Synthesizing Compound 18: Compound 16 (22 g, 38.4 mmol) was dissolved into 250 ml dry dichloromethane, to which Et.sub.3SiH (5.3 g, 46.1 mmol) and TFA (21.9 g, 192 mmol) were added. After 12 h reaction under the room temperature, Na.sub.2CO.sub.3 (10 g) was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichlorometane, then a rotatory evaporuation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of AcOEt/MeOH (300 mL/200 mL), to which 5% Pd/C (1 g) catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24 h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A white solid 18 was obtained with a yield of 68%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.64-3.61 (t, J=6.8 Hz, 2H), 1.58-1.50 (m, 2H), 1.32-1.23 (m, 55H), 0.90-0.86 (t, J=6.6 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) 63.57, 37.24, 33.61, 31.93, 30.13, 29.99, 29.71, 29.67, 29.57, 29.37, 26.67, 22.69, 14.10.

EXAMPLE 19

[0149] ##STR00063##

[0150] Scheme for Synthesizing Compound 19: Compound 17 (22.9 g, 33.4 mmol) was dissolved into 250 ml dry dichloromethane, to which Et.sub.3SiH (4.66 g, 40.08 mmol) and TFA (19 g, 167 mmol) were added. After 12 h reaction under the room temperature, Na.sub.2CO.sub.3 (10 g) was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichlorometane, then a rotatory evaporuation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of AcOEt/MeOH (300 mL/200 mL), to which 5% Pd/C (1 g) catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24 h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. 12.9 g of white solid 19 was obtained with a yield of 67%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.63-3.60 (t, J=6.6 Hz, 2H), 1.57-1.51 (m, 2H), 1.32-1.24 (m, 71H), 0.90-0.86 (t, J=6.8 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 63.52, 37.26, 33.62, 31.95, 30.16, 29.99, 29.74, 29.69, 29.59, 29.39, 26.69, 22.70, 14.10.

EXAMPLE 20

[0151] ##STR00064##

[0152] Scheme for synthesizing Compound 20: Compound 18 (8.92 g, 19.1 mmol) was dissolved into dichloromethane, to which imidazole (1.56 g, 22.9 mmol) and triphenylphosphine (6.0 g, 22.9 mmol) were added. Under ice bath, I.sub.2 (5.82 g, 22.9 mmol) was added. After reacting under agitation at the room temperature for 4 h, Na.sub.2SO.sub.3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column to obtain 10.8 g of colorless oily liquid Compound 20 with a yield of 98%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.19-3.15 (t, J=7.0 Hz, 2H), 1.83-1.76 (m, 2H), 1.32-1.22 (m, 55H), 0.90-0.86 (t, J=6.6 Hz, 6H). EI-MS: Calcd. for [M].sup.+: 576. Found: m/z=576.

EXAMPLE 21

[0153] ##STR00065##

[0154] Scheme for synthesizing Compound 21: Compound 19 (11.27 g, 19.46 mmol) was dissolved into dichloromethane, to which imidazole (1.59 g, 23.4 mmol) and triphenylphosphine (6.14 g, 23.4 mmol) were added. Under ice bath, 12 (5.93 g, 23.4 mmol) was added. After reacting under agitation at the room temperature for 4 h, Na.sub.2SO.sub.3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column to obtain 13.17 g of colorless oily liquid Compound 21 with a yield of 98%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) 5: 3.18-3.15 (t, J=7.0 Hz, 2H), 1.83-1.76 (p, J=7.1 Hz, 2H), 1.33-1.22 (m, 71H), 0.90-0.86 (t, J=6.6 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm) : 36.75, 34.60, 33.61, 31.96, 30.97, 30.10, 29.74, 29.72, 29.70, 29.40, 26.67, 22.72, 14.13, 7.55. EI-MS: Calcd. for [M].sup.+: 688. Found: m/z=688.

EXAMPLE 22

[0155] ##STR00066##

[0156] Scheme for synthesizing Compound 22: Compound 14 (1.0 g, 2.15 mmol) was dissolved into 100 ml DMF. At the room temperature, sodium azide (0.7 g, 10.5 mmol) was added in batches. After reaction under agitation at 85 C. for 4 h, DMF was removed by vacuum distillation. Extraction was conducted with petroleum ether. The organic phase was washed with saturated saline once and dried with anhydrous Na.sub.2SO.sub.4. The solvent was removed by vacuum to obtain the product 22 (0.81 g) with a yield of 100%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.26-3.22 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). EI-MS: Calcd. for [M].sup.+: 379. Found: m/z=379.

EXAMPLE 23

[0157] ##STR00067##

[0158] Scheme for synthesizing Compound 23: Compound 22 (0.81 g, 2.15 mmol) was dissolved in 100 ml petroleum ether. Pd/C (0.1 g) was added. At the room temperature, hydrogenation was conducted for 12 h, followed by filtration with kieselguhr and column separation to obtain 0.6 g of colorless oily liquid Compound 23 with a yield of 80%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 3.26-3.22 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). EI-MS: Calcd. for [M].sup.+: 354. Found: m/z=354.

[0159] Example 24 to Example 28 are Reactions for Preparing the Monomers for Polymerization:

EXAMPLE 24

[0160] ##STR00068##

[0161] Synthesis of Monomer M2: 6,6-dibromoisoindigo (1.70 g, 4.04 mmol) and potassium carbonate (1.68 g, 12.1 mmol) were dissolved in DMF (100 mL). Compound 13 (4.19 g, 9.31 mmol) was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100 C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After solvation into CHCl.sub.3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain 3.79 g of dark red solid M2 with a yield of 88%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 9.09-9.07 (d, J=8.6 Hz, 2H), 7.17-7.15 (dd, J.sub.1=8.6 Hz, J.sub.2=1.6 Hz, 2H), 6.89-6.88 (d, J=1.6 Hz, 2H), 3.74-3.70 (t, J=7.4 Hz 4H), 1.71-1.56 (q, J=6.3 Hz, 4H), 1.42-1.26 (m, 74H), 0.90-0.86 (t, J=6.8 Hz, 4H)..sup.13C NMR (CDCl.sub.3, 100 MHz, ppm): 167.49, 145.68, 132.55, 131.22, 126.66, 125.05, 120.44, 111.18, 55 38.39, 35.61, 33.44, 31.93, 30.96, 30.04, 29.70, 29.69, 29.66, 29.36, 26.62, 22.70, 14.12. Elemental Anal: Calcd. for C.sub.62H.sub.100Br.sub.2N.sub.2O.sub.2: C, 69.90; H, 9.46; N, 2.63. Found: C, 69.78; H, 9.46; N, 2.62. ESI-HRMS: Calcd. for [M+H].sup.+: 1063.62243. Found: 1063.62480.

EXAMPLE 25

[0162] ##STR00069##

[0163] Synthesis of Monomer M3: 6,6-dibromoisoindigo and potassium carbonate were dissolved in DMF (100 mL). Compound 14 was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100 C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl.sub.3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain a dark red solid M3 with a yield of 71%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.16 (dd, J.sub.1=8.6 Hz, J.sub.2=1.6 Hz, 2H), 6.93-6.92 (d, J=1.6 Hz, 2H), 3.73-3.69 (t, J=7.4 Hz, 4H), 1.68-1.64 (m, 4H), 1.34-1.22 (m, 78H), 0.89-0.86 (t, J=6.6 Hz, 12H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm): 167.68, 145.76, 132.60, 131.21, 126.72, 125.10, 120.41, 111.28, 40.61, 37.10, 33.52, 31.93, 30.81, 30.09, 29.69, 29.65, 29.36, 26.67, 24.47, 22.69, 14.12. Elemental Anal: Calcd. for C.sub.64H.sub.104Br.sub.2N.sub.2O.sub.2: C, 70.31; H, 9.59; N, 2.56. Found: C, 70.50; H, 9.62; N, 2.53. ESI-HRMS: Calcd. for [M+H].sup.+: 1091.65373. Found: 1093.65487.

EXAMPLE 26

[0164] ##STR00070##

[0165] Synthesis of Monomer M4: 6,6-dibromoisoindigo and potassium carbonate were dissolved in DMF (100 mL). Compound 15 was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100 C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl.sub.3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain a dark red solid M4 with a yield of 83%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 9.10-9.07 (d, J=8.6 Hz, 2H), 7.17-7.14 (dd, J.sub.1=8.6 Hz, J.sub.2=1.6 Hz, 2H), 6.92-6.91 (d, J=1.6 Hz, 2H), 3.74-3.70 (t, J=7.4 Hz, 4H), 1.67-1.62 (m, 4H), 1.36-1.22 (m, 82H), 0.89-0.86 (t, J=6.8 Hz, 12H). .sup.13C NMR (CDCl.sub.3, 100 MHz, ppm): 167.67, 145.76, 132.59, 131.23, 126.71, 125.10, 120.41, 111.26, 40.27, 37.39, 33.61, 33.36, 31.93, 30.13, 29.72, 29.66, 29.37, 27.78, 26.71, 24.22, 22.70, 14.12. Elemental Anal: Calcd. for C.sub.66H.sub.108Br.sub.2N.sub.2O.sub.2: C, 70.69; H, 9.71; N, 2.50. Found: C, 70.79; 11, 9.55; N, 2.49. ESI-HRMS: Calcd. for [M+Na].sup.+: 1141.66698. Found: 1141.66836.

EXAMPLE 27

[0166] ##STR00071##

[0167] Synthesis of Monomer M5: 6,6-dibromoisoindigo (2 g, 4.76 mmol) and potassium carbonate (1.97 g, 14.28 mmol) were dissolved in DMF (100 mL). Compound 20 (6.0 g, 10.4 mmol) was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100 C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl.sub.3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain 6.0 g of dark red solid M5 with a yield of 95%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.15 (dd, J.sub.1=8.6 Hz, J.sub.2=1.81 Hz, 2H), 6.93-6.92 (d, J=1.8 Hz, 2H), 3.73-3.69 (t, J=7.5 Hz, 4H), 1.67-1.64 (m, 4H), 1.34-1.22 (m, 114H), 0.89-0.86 (t, J=6.6 Hz, 12H).

EXAMPLE 28

[0168] ##STR00072##

[0169] Synthesis of Monomer M6: 6,6-dibromoisoindigo (1.5 g, 3.57 mmol) and potassium carbonate (1.48 g, 10.71 mmol) were dissolved in DMF (100 mL). Compound 21 (5.41 g, 7.86 mmol) was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100 C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl.sub.3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na.sub.2SO.sub.4. After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain 4.95 g of dark red solid M6 with a yield of 90%. .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) .sup.1H NMR (CDCl.sub.3, 400 MHz, ppm) : 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.15 (dd, J.sub.1=8.6 Hz, J.sub.2=1.8 Hz, 2H), 6.93-6.92 (d, J=1.8 Hz, 2H), 3.73-3.69 (t, J=7.5 Hz, 4H), 1.67-1.64 (m, 4H), 1.34-1.22 (m, 142H), 0.89-0.86 (t, J=6.6 Hz, 12H).

[0170] Example 29 to Example 31 are Polymerization for the Polymers:

EXAMPLE 29

[0171] ##STR00073##

[0172] Synthesis of Polymer P2: Under nitrogen protection, M2 (0.235 mmol), 5,5-bis(trimethylstannyl)-2,2-bithiophene (0.235 mmol), Pd.sub.2(dba).sub.3 (4.3 mg, 2 mol %), P(o-tol).sub.3 (5.7 mg, 8 mol %), and 10 ml dry toluene solvent were added into a reaction flask. After reaction with agitation at temperature of 110 C. for 24 h, Soxhlet extraction was conducted with chloroform to obtain the product (236 mg, with a yield of 95%). Elemental Anal. Calcd: for (C.sub.70H.sub.104N.sub.2O.sub.2S.sub.2).sub.n: C, 78.52; H, 9.88; N, 2.62. Found: C, 77.78; H, 9.47; N, 2.55.

EXAMPLE 30

[0173] ##STR00074##

[0174] Synthesis of Polymer P3: Under nitrogen protection, M3 (0.229 mmol), 5,5-bis(trimethylstannyl)-2,2-bithiophene (0.229 mmol), Pd.sub.2(dba).sub.3 (4.3 mg, 2 mol %), P(o-tol).sub.3 (5.6 mg, 8 mol %), and 10 ml dry toluene solvent were added into a reaction flask. After reaction with agitation at temperature of 110 C. for 24 h, Soxhlet extraction was conducted with chloroform to obtain the product (238 mg, with a yield of 94%). Elemental Anal. Calcd: for (C.sub.72H.sub.108N.sub.2O.sub.2S.sub.2).sub.n: C, 77.78; H, 9.92; N, 2.55. Found: C, 77.85; H, 9.75; N, 2.48.

EXAMPLE 31

[0175] ##STR00075##

[0176] Synthesis of Polymer P4: Under nitrogen protection, M4 (0.229 mmol), 5,5-bis(trimethylstannyl)-2,2-bithiophene (0.229 mmol), Pd.sub.2(dba).sub.3 (4.2 mg, 2 mol %), P(o-tol).sub.3 (5.6 mg, 8 mol %), and 10 ml dry toluene solvent were added into a reaction flask. After reaction with agitation at temperature of 110 C. for 24 h, Soxhlet extraction was conducted with chloroform to obtain the product (220 mg, with a yield of 87%). Elemental Anal. Calcd. for (C.sub.74H.sub.112N.sub.2O.sub.2S.sub.2).sub.n: C, 78.95; H, 10.03; N, 2.49. Found: C, 78.25; H, 9.91; N, 2.46.

EXAMPLE 32

[0177] The optical physical properties and electrochemical properties of Polymers P2, P3, and P4 were characterized and the data are shown in the following table:

TABLE-US-00001 TABLE 1 The optical physical and electrochemical properties of Polymers P1-P4 Molecular Weight Decomposition M.sub.n Temperature .sub.max sol. .sub.max film E.sub.g.sup.opt E.sub.HOMO E.sub.LUMO E.sub.g.sup.cv E.sub.HOMO PES Polymer (kDa)/PDI ( C.) (nm).sup.a (nm).sup.b (eV).sup.c (eV).sup.d (eV).sup.d (eV).sup.e (eV).sup.f P1 20.4/2.0 390 706, 647 701, 637 1.60 5.70 3.70 2.00 5.54 P2 18.4/2.0 384 711, 647 707, 641 1.60 5.60 3.70 1.90 5.57 P3 39.2/3.2 392 718, 673 719, 653 1.58 5.52 3.74 1.78 5.33 P4 37.3/2.3 374 719, 675 716, 647 1.58 5.50 3.74 1.76 5.26 .sup.aLongest absorption wavelength of the solution (corresponding to 0-0 vibration absorption and 0-1 vibration absorption, respectively), .sup.b longest absorption wavelength of the film (corresponding to 0-0 vibration absorption and 0-1 vibration absorption, respectively); .sup.c band gap in the absorption spectrum; .sup.d electrochemical measurement value; .sup.e electrochemical band gap; .sup.f photoelectron spectrum (PES) measurement value.

[0178] Among them, P1 is a 2-branching polymer (Lei, T.; Cao, Y.; Fan, Y.; Liu, C. J.; Yuan, S. C.; Pei, J. J. Am. Chem. Soc. 2011, 133, 6099), whose structure is as follows:

##STR00076##

[0179] P2P4 are polymers synthesized in the invention. After the introduction of different branching alkyl chains, significant change occurred to the spectra and electrochemistry of P2P4. The absorption spectra apparently shifted to red, the HOMO energy levels apparently increased, and the band gaps apparently reduced. These changes were due to the changes of the mode of stacking between polymers.

EXAMPLE 33

[0180] Device processing and X-ray diffraction characterization of the organic field effect transistor comprising polymers P1-P4:

[0181] Processing of the organic field effect transistor (OTFT) was conducted with the device structure of bottom-gate/top-contact (BG/TC). For the substrate, doped silicon (n.sup.++-Si) was used as a gate electrode, and 300 nm silicon dioxide was used as an insulation layer. The substrate was washed with acetone, a detergent, water and isopropanol successively before dried with nitrogen blow. Then the substrate was cleaned with plasma beam for 15 minutes, and modified with octadecylsilane. Then the dichlorobenzene solution of the polymer was spin coated onto the substrate and annealed at different temperatures. Then at high vacuum, a layer of 30 mm gold electrode was coated by hot vapor deposition with a physical mask as the source electrode and the drain electrode. The measurement of the mobility of the polymer was conducted on a Keithley 4200 semiconductor characterization system.

[0182] The experiments proved that compared to P1, the mobility of P3 had great increase from the initial 0.79 cm.sup.2V.sup.1s.sup.1 (P1) to 3.62 cm.sup.2V.sup.1s.sup.1. The threshold voltage also significantly decreased.

[0183] The X ray diffraction experiment was conducted on Beamline BLI4B1 at Shanghai Synchrotron Radiation Facility with a wavelength of 1.2398 , and the measurement was conducted with an NaI counter. The experiments proved that the type of branching alkyl chains contained in the polymers effectively reduced the - stacking distance between polymers. This result also proved the huge effect of the novel alkyl chain of the disclosure in organic semiconductor devices.

TABLE-US-00002 TABLE 2 Performance of the organic field effect transistors and results of the film glancing X-ray study Annealing Threshold on/off Temperature Mobility Voltage ratio d().sup.b Polymer ( C.) (cm.sup.2V.sup.1s.sup.1).sup.a (V) I.sub.on/I.sub.off L P1 150 0.79 (0.45) 18 >10.sup.6 20.3 3.75 P2 200 0.40 (0.28) 10 >10.sup.5 23.7 3.61 P3 175 3.62 (2.98) 2 >10.sup.6 24.7 3.57 P4 175 1.76 (1.44) 5 >10.sup.6 26.1 3.57 .sup.aThe measurement was conducted in air (RH = 50~60%). Maximal mobility values were shown outside the parentheses, while average values were shown in the parentheses. .sup.bThe layer phase distance (L) and - stacking distance () obtained in the X-ray study.