Reactive mesogenic azulenes

Abstract

The invention relates to new reactive mesogenic azulene derivatives, their use as semiconductors or charge transport materials, in optical, electro-optical or electronic devices like for example liquid crystal displays, optical films, organic field effect transistors (FET or OFET) for thin film transistor liquid crystal displays and integrated circuit devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices, and to a field effect transistor, light emitting device or ID tag comprising the reactive mesogenic azulenes.

1 .- 24 . (canceled)  
     
     
         25 . A reactive liquid crystal mixture comprising: 
 one or more reactive mesogenic azulene compounds of the formula I      P-Sp-T-R 1    I    wherein    P is CH 2 ═CW 1 —COO—,                          CH 2 ═CW 2 —(O) k1 —, CH 3 —CH═CH—O—, HO—CW 2 W 3 —, HS—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 —, Phe-CH═CH—, HOOC—, OCN— and W 4 W 5 W 6 Si—, with W 1  being H, Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W 2  and W 3  being independently of each other H or alkyl with 1 to 5 C-atoms, W 4 , W 5  and W 6  being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene and k 1  and k 2  being independently of each other 0 or 1,    Sp is a single bond or a linear or branched alkylene group having 1 to 20 C atoms, in which one or more non-adjacent CH 2  groups are optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —C(halogen) 2 , —CH(CN)—, —CH═CH— or —C≡C—, or a siloxane group,    R 1  is H, halogen, CN, NO 2 , an aliphatic, alicyclic or aromatic group with up to 40 C atoms that optionally comprises one or more hetero atoms and one or more fused rings, or a group P-Sp-, and    T is a mesogenic group of the formula II      -Z 1 -(A 1 -Z 2 ) m -(T 1 -Z 3 ) n -(A 2 -Z 4 ) 0 -   II    wherein    A 1  and A 2  are independently of each other an aromatic or heteroaromatic group with up to 18 C atoms which is unsubstituted, mono- or polysubstituted with R 1  , and A 1  may also denote T 1 ,    Z 1  to Z 4  are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —CX 1 ═CX 2 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,    X 1  and X 2  are independently of each other H, F, Cl or CN,    T 1  is a group consisting of 1, 2, 3, or 4 azulene groups which are optionally substituted by R 2 ,    R 2  is H, halogen, CN, NO 2 , straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, or denotes an aromatic or heteroaromatic group or a group P-Sp,    R 0  and R 00  are independently of each other H or alkyl with 1 to 12 C-atoms,    m and o are independently of each other 0, 1, 2 or 3, and    n is 1, 2 or 3;    and optionally one or more further reactive compounds, wherein at least one of said azulene compounds and optional further reactive compound has mesogenic or liquid crystalline properties.    
     
     
         26 . An anisotropic polymer film with charge transport properties prepared from a reactive liquid crystal mixture according to  claim 25  that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerized or crosslinked to fix the oriented state.  
     
     
         27 . A side chain liquid crystal polymer obtained by polymerizing one or more azulene compounds according to the following formula I or by grafting one or more azulene compounds according to the following formula I to a polymer backbone in a polymer analoguous reaction, optionally with one or more additional mesogenic or non-mesogenic comonomers:  
         P-Sp-T-R 1    I  
       wherein 
 P is CH 2 ═CW 1 —COO—,  
                     
 CH 2 ═CW 2 —(O) k1 —, CH 3 —CH═CH—O—, HO—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 -, Phe-CH═CH—, HOOC—, OCN— and W 4 W 5 W 6 Si—, with W 1  being H, Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W 2  and W 3  being independently of each other H or alkyl with 1 to 5 C-atoms, W 4 , W 5  and W 6  being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene and k 1  and k 2  being independently of each other 0 or 1,  
 Sp is a single bond or a linear or branched alkylene group having 1 to 20 C atoms, in which one or more non-adjacent CH 2  groups are optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —C(halogen) 2 , —CH(CN)—, —CH═CH— or —C≡C—, or a siloxane group,  
 R 1  is H, halogen, CN, NO 2 , an aliphatic, alicyclic or aromatic group with up to 40 C atoms that optionally comprises one or more hetero atoms and one or more fused rings, or a group P-Sp-, and  
 T is a mesogenic group of the formula II  
   -Z 1 -(A 1 -Z 2 ) m -(T 1 -Z 3 ) n -(A 2 -Z 4 ) 0 -   II  
 wherein  
 A 1  and A 2  are independently of each other an aromatic or heteroaromatic group with up to 18 C atoms which is unsubstituted, mono- or polysubstituted with R 1 , and A 1  may also denote T 1 ,  
 Z 1  to Z 4  are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —CX 1 ═CX 2 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,  
 X 1  and X 2  are independently of each other H, F, Cl or CN,  
 T 1  is a group consisting of 1, 2, 3, or 4 azulene groups which are optionally substituted by R 2 ,  
 R 2  is H, halogen, CN, NO 2 , straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR—, —SiR 0 R 0 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, or denotes an aromatic or heteroaromatic group or a group P-Sp, R 0  and R 00  are independently of each other H or alkyl with 1 to 12 C-atoms,  
 m and o are independently of each other 0, 1, 2 or 3, and  
 n is 1, 2 or 3.  
 
     
     
         28 . A semiconductor or charge transport material, comprising a polymer of  claim 27 .  
     
     
         29 . A field effect transistor, comprising one or more polymers according to  claim 27 .  
     
     
         30 . A security marking or device comprising one or more or polymers according to  claim 27 .  
     
     
         31 . A field effect transistor, comprising one or more polymer films according to  claim 26 .  
     
     
         32 . A security marking or device comprising one or more or polymer films according to  claim 26 .  
     
     
         33 . A polymer film according to  claim 26 , which is oxidatively or reductively doped to form conducting ionic species.  
     
     
         34 . A charge injection layer, planarizing layer, antistatic film or conducting substrate or pattern for electronic applications or flat panel displays, comprising one or more polymer films according to  claim 33 .  
     
     
         35 . A component for integrated circuitry, a thin film transistor, a radio frequency identification tag, an organic light emitting diode, a backlight or light-modulating component for a liquid crystal display, an optical film, an electrode material, a photoconductor or an electrophotographic photovoltaic or sensor device, comprising one or more anisotropic polymer films according to  claim 26 .  
     
     
         36 . A component for integrated circuitry, a radio frequency identification tag, an organic light emitting diode, a backlight or light-modulating component for a liquid crystal display, an optical film, an electrode material, a photoconductor or an electrophotographic photovoltaic or sensor device, comprising one or more polymers according to  claim 27 .  
     
     
         37 . A security marking or device, a radio frequency identification tag, a flat panel display or an integrated circuit comprising a field effect transistor according to  claim 29 .  
     
     
         38 . A security marking or device, a radio frequency identification tag, a flat panel display or an integrated circuit comprising a field effect transistor according to  claim 31 .  
     
     
         39 . The reactive liquid crystal mixture of  claim 25 , wherein the reactive mesogenic azulene compound is of one of the following formulae:  
       
         
           
           
               
               
           
         
       
       wherein 
 P is CH 2 ═CW 1 —COO—,  
                     
 CH 2 ═CW 2 —(O) k1 —, CH 3 —CH═CH—O—, HO—CW 2 W 3 —, HS—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 —, Phe-CH═CH—, HOOC—, OCN— and W 4 W 5 W 6 Si—, with W 1  being H, Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W 2  and W 3  being independently of each other H or alkyl with 1 to 5 C-atoms, W 4 , W 5  and W 6  being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene and k 1  and k 2  being independently of each other 0 or 1,  
 Sp is a linear or branched alkylene group having 1 to 20 C atoms, in which one or more non-adjacent CH 2  groups are optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —C(halogen) 2 , —CH(CN)—, —CH═CH— or —C≡C—, or a siloxane group, provided that the first group adjacent to the azulene ring is —O—, and  
 z are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —CX 1 ═CX 2 —, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH—.  
 
     
     
         40 . The polymer film of  claim 26 , wherein the reactive mesogenic azulene compound is of one of the following formulae:  
       
         
           
           
               
               
           
         
       
       where 
 P is CH 2 ═CW 1 —COO—,  
                     
 CH 2 ═CW 2 —(O) k1 —, CH 3 —CH═CH—O—, HO—CW 2 W 3 —, HS—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 —, Phe-CH═CH—, HOOC—, OCN— and W 4 W 5 W 6 Si—, with W 1  being H, Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W 2  and W 3  being independently of each other H or alkyl with 1 to 5 C-atoms, W 4 , W 5  and W 6  being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene and k 1  and k 2  being independently of each other 0 or 1,  
 Sp is a linear or branched alkylene group having 1 to 20 C atoms, in which one or more non-adjacent CH 2  groups are optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —C(halogen) 2 , —CH(CN)—, —CH═CH— or —C≡C—, or a siloxane group, provided that the first group adjacent to the azulene ring is —O—, and  
 z are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —CX 1 ═CX 2 —, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH—.  
 
     
     
         41 . The polymer of  claim 27 , wherein the reactive mesogenic azulene compound is of one of the following formulae:  
       
         
           
           
               
               
           
         
       
       wherein 
 P is CH 2 ═CW 1 —COO—,  
                     
 CH 2 ═CW 2 —(O) k1 —, CH 3 —CH═CH—O—, HO—CW 2 W 3 —, HS—CW 2 W 3 —, HW 2 N—, HO—CW 2 W 3 —NH—, CH 2 ═CW 1 —CO—NH—, CH 2 ═CH—(COO) k1 -Phe-(O) k2 —, Phe-CH═CH—, HOOC—, OCN— and W 4 W 5 W 6 Si—, with W 1  being H, Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W 2  and W 3  being independently of each other H or alkyl with 1 to 5 C-atoms, W 4 , W 5  and W 6  being independently of each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phe being 1,4-phenylene and k 1  and k 2  being independently of each other 0 or 1,  
 Sp is a linear or branched alkylene group having 1 to 20 C atoms, in which one or more non-adjacent CH 2  groups are optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —C(halogen) 2 , —CH(CN)—, —CH═CH— or —C≡C—, or a siloxane group, provided that the first group adjacent to the azulene ring is —O—, and  
 z are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —CX 1 ═CX 2 —, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH—.  
 
     
     
         42 . A reactive liquid crystal mixture of  claim 25 , wherein, for the reactive mesogenic azulene compound of formula I: 
 T 1  is of one of the following subformulae:                          wherein R 3  to R 8  have independently of each other one of the meanings of R 2  in formula II;    A 1  and A 2  are selected from the group consisting of 1,4-phenylene, 1,4-cyclohexa-1,3-diene, 1,4-cyclohexenylene in which one or more CH groups are optionally replaced by N and one or two non-adjacent CH 2  groups are optionally replaced by O and/or S; thiophene-2,5-diyl, thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl, 1,4-bicyclo-(2,2,2)-octylene, naphthalene-2,6-diyl, furan-2,5-diyl, and indane-2,5-diyl; wherein all of the above are unsubstituted, mono- or polysubstituted by L, with L being halogen, CN, SCN, NO 2 , SF 5  or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 4 C atoms, wherein one or more H atoms are optionally substituted with F or Cl; and    R 1  is H, F, Cl or straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH—or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, or an aromatic or heteroaromatic group.    
     
     
         43 . A polymer film of  claim 26 , wherein, for the reactive mesogenic azulene compound of formula I: 
 T 1  is of one of the following subformulae:                          wherein R 3  to R 8  have independently of each other one of the meanings of R2 in formula II;    A 1  and A 2  are selected from the group consisting of 1,4-phenylene, 1,4-cyclohexa-1,3-diene, 1,4-cyclohexenylene in which one or more CH groups are optionally replaced by N and one or two non-adjacent CH 2  groups are optionally replaced by O and/or S; thiophene-2,5-diyl, thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl, 1,4-bicyclo-(2,2,2)-octylene, naphthalene-2,6-diyl, furan-2,5-diyl, and indane-2,5-diyl; wherein all of the above are unsubstituted, mono- or polysubstituted by L, with L being halogen, CN, SCN, NO 2 , SF 5  or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 4 C atoms, wherein one or more H atoms are optionally substituted with F or Cl; and    R 1  is H, F, Cl or straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, or an aromatic or heteroaromatic group.    
     
     
         44 . A polymer of  claim 27 , wherein, for the reactive mesogenic azulene compound of formula I: 
 T 1  is of one of the following subformulae:                          wherein R 3  to R 8  have independently of each other one of the meanings of R 2  in formula II;    A 1  and A 2  are selected from the group consisting of 1,4-phenylene, 1,4-cyclohexa-1,3-diene, 1,4-cyclohexenylene in which one or more CH groups are optionally replaced by N and one or two non-adjacent CH 2  groups are optionally replaced by O and/or S; thiophene-2,5-diyl, thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl, 1,4-bicyclo-(2,2,2)-octylene, naphthalene-2,6-diyl, furan-2,5-diyl, and indane-2,5-diyl; wherein all of the above are unsubstituted, mono- or polysubstituted by L, with L being halogen, CN, SCN, NO 2 , SF 5  or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 4 C atoms, wherein one or more H atoms are optionally substituted with F or Cl; and    R 1  is H, F, Cl or straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, or an aromatic or heteroaromatic group.