SUBSTITUTED BENZODITHIOPHENES AND BENZODISELENOPHENES

• US 20090314997A1
• Filed: 06/29/2007
• Published: 12/24/2009
• Est. Priority Date: 07/26/2006
• Status: Abandoned Application

• Current Assignee: Merck Patent Gesellschaft Mit Beschränkter Haftung
• Original Assignee: Merck Patent Gesellschaft Mit Beschränkter Haftung
• Inventors: Heeney, Martin, McCulloch, Iain, Tierney, Steven, Zhang, Weimin
• Application Number:
  US12/374,920
• Publication Number:
  US 20090314997A1
• Time in Patent Office: Days
• US Class Current: 252/500
• CPC Class Codes: C07D 495/04 Ortho-condensed systems
• CPC Class Codes: C07F 7/0812 comprising a heterocyclic ring
• CPC Class Codes: C08G 2261/3243 containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 19/3491 having sulfur as hetero atom
• CPC Class Codes: C09K 19/40 containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
• CPC Class Codes: C09K 2211/1092 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 2211/1096 containing other heteroatoms
• CPC Class Codes: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• CPC Class Codes: H10K 10/464 Lateral top-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 10/466 Lateral bottom-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 85/40 Organosilicon compounds, e.g. TIPS pentacene
• CPC Class Codes: H10K 85/6576 comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
• CPC Class Codes: Y02E 10/549 Organic PV cells

Abstract

The invention relates to novel substituted benzodithiophenes and benzodiselenophenes, their use especially as semiconductors or charge transport materials in optical, electro-optical or electronic devices and to such devices comprising the novel materials.

Claims

1. Compounds of formula I

2. Compounds according to claim 1, characterized in that R′

, R″ and

R′

″

are each independently selected from optionally substituted C_1-10-alkyl and optionally substituted C_6-10-aryl.

3. Compounds according to claim 1, characterized in that Ar¹ and Ar² are independently of each other selected from phenyl in which, in addition, one or more CH groups may be replaced by N, naphthalene, pyridine, naphthalene-2-yl, thiophene-2-yl, thieno[2,3b]thiophene-2-yl, benzo(b)thiophene-2-yl, all of which are optionally mono or polysubstituted with L, wherein L is F, Cl, Br, or an alkyl, alkoxy, alkylcarbonyl, alkylcarbonyloxy or alkoxycarbonyl group with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl.

4. Compounds according to claim 1, characterized in that R¹, R² and R³ are selected from C₁-C₂₀-alkyl that is optionally substituted with one or more fluorine atoms, C₁-C₂₀-alkenyl, C₁-C₂₀-alkynyl, C₁-C₂₀-thioalkyl, C₁-C₂₀-silyl, C₁-C₂₀-ester, C₁-C₂₀-amino, C₁-C₂₀-fluoroalkyl, and optionally substituted aryl or heteroaryl.

5. Compounds according to claim 1, characterized in that Ar¹ and Ar² are substituted by at least one group R³ that denotes P-Sp-.

6. Compounds according to claim 1, characterized in that they are selected from the following subformulae

7. Polymerisable mesogenic or liquid crystalline material comprising one or more compounds according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more further polymerisable compounds.

8. Anisotropic polymer film obtainable by aligning a polymerisable liquid crystalline material according to claim 7 in its liquid crystal phase into macroscopically uniform orientation and polymerising or crosslinking the material to fix the oriented state.

9. Formulation comprising one or more compounds according to claim 1, one or more solvents, and optionally one or more organic binders.

10. Formulation according to claim 9, characterized in that it comprises one or more semiconducting binders.

11. An electronic, optical or electrooptical component or device comprising a compound, material, polymer or formulation according to claim 1.

12. Electronic, optical or electrooptical component or device comprising one or more compounds, materials, polymers or formulations according to claim 1.

13. Device according to claim 12, characterized in that it is an organic field effect transistor (OFET), thin film transistor (TFT), component of integrated circuitry (IC), radio frequency identification (RFID) tag, organic light emitting diode (OLED), electroluminescent display, flat panel display, backlight, photodetector, sensor, logic circuit, memory element, capacitor, photovoltaic (PV) cell, charge injection layer, Schottky diode, planarising layer, antistatic film, conducting substrate or pattern, photoconductor or electrophotographic element.

14. Compound, material or polymer according to claim 1, characterized in that it is oxidatively or reductively doped to form conducting ionic species.

15. Charge injection layer, planarising layer, antistatic film or conducting substrate or pattern for electronic applications or flat panel displays, comprising a compound, material or polymer according to claim 14.

16. Method of preparing a compound according to claim 1, by

a1) subjecting a 4,8-dehydrobenzo[1,2-b:

4,5-b′

]dithiophene-4,8-dione, or 4,8-dehydrobenzo[1,2-b;

4,5-b′

]diselenophene-4,8-dione, to double lithiation with a hindered lithium amide base, followed by reaction with an electrophillic source of bromine, or

a2) synthesizing 2,6-dibromo-4,8-dehydrobenzo[1,2-b;

4,5-b′

]dithiophene-4,8-dione, or 2,6-dibromo-4,8-dehydrobenzo[1,2-b;

4,5-b′

]diselenophene-4,8-dione, by reaction of 2,5-dibromo-3-thiophene carboxylic acid dialkyl amide, or 2,5-dibromo-3-selenophene carboxylic acid dialkyl amide respectively, with an organolithium or organomagnesium reagent and

b) introducing aryl or heteroaryl groups into the 2,6-positions of the product of step a1) or a2) by standard Suzuki, Stille, Negishi or Kumada coupling with an aryl boronic acid or ester, an aryl organotin reagent, an aryl organozinc reagent or an organomagnesium reagent, respectively, in the presence of a suitable palladium or nickel catalyst and

c) introducing an alkynyl group, alkenyl or alkyl group into the 4,8 positions of the product of step b) by reacting it with an excess of the appropriate alkyl, alkenyl or alkynyl organolithium or organomagnesiun reagent followed by reduction of the resulting diol interemediate or

b1) introducing an alkynyl group, alkenyl or alkyl group into the 4,8 positions of the product of step a1) or a2) by reacting it with an excess of the appropriate alkyl, alkenyl organolithium or organomagnesium reagent followed by reduction of the resulting diol interemediate and

c1) introducing aryl or heteroaryl groups into the product of step b1 by standard Suzuki, Still, Negishi or Kumade coupling with an aryl boronic acid or ester, an aryl organotin reagent, an organozinc reagent or an organomagnesium reagent respectively, in the presence of a suitable palladium or nickel catalyst. or

d) introducing alkenyl or alkynyl aryl or heteroaryl groups into the 2,6-positions of the product of step b1) by standard Heck, Sonogashira, or Suzuki coupling with an aryl alkene group, an aryl alkyne group or an aryl alkenyl boronic acid or esters respectively in the presence of a suitable palladium or nickel catalyst.