Multifunctional 3,4-alkylenedioxythiophene derivatives and electrically conductive polymers containing them
View Patent ↗Multifunctional 3,4-alkylenedioxythiophene derivatives represented by formula (I) are described, In formula (I), n and m each independently of each other, and independently for each o, are an integer from 1 to 5, and o is 3 or 4. The groups R 1 , R 2 , R 3 and R 4 are independently of each other and independently for each o, selected from, for example, hydrogen, halogen and optionally substituted linear or branched C 1 -C 20 -alkyl. The group R— of formula (I) may be, independently for each o, hydrogen or a thiophene represented by the following formula (II), in which m, n, R 1 , R 2 , R 3 and R 4 are as described in formula (I). The group X— of formula (I) is a polyvalent linking unit (e.g., a triphenylamine radical). Also described are electrically conductive oligomers and polymers comprising the multifunctional 3,4-alkylenedioxythiophene derivatives of the present invention as a repeating or crosslinking unit.
1. A compound represented by the following formula (I),
wherein
n and m each independently of each other, and independently for each o, is an integer from 1 to 5,
o is 3 or 4,
R 1 , R 2 , R 3 and R 4 each independently of each other, and independently for each o, are selected from a member of the group consisting of hydrogen, halogen,
linear or branched C 1 -C 20 -alkyl,
linear or branched substituted C 1 -C 20 -alkyl hydroxyl,
an ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a substituted ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
an ether radical —(CH 2 ) p —O—C q H 2q+1 ,
a substituted ether radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
a substituted radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
an oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a substituted oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a radical containing a mesogenic group,
and R 1 , R 2 , R 3 and R 4 together forming a crown ether structure,
wherein the substituents of the substituted members, from which R 1 , R 2 , R 3 and R 4 , may each be independently selected, are selected independently from the group consisting of hydroxyl, halogen, linear or branched C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl and aryl,
wherein
p in each case represents an integer from 0 to 6,
q in each case represents an integer from 1 to 20,
r represents 0 or 1, and
s represents an integer from 1 to 20, and
R is selected, independently for each o, from the group consisting of hydrogen and a thiophene represented by the following formula (II)
wherein
m, n, are as defined in formula (I),
R 2 , R 3 and R 4 each independently of each other, and independently for each o, are selected from a member of the group consisting of hydrogen, halogen,
linear or branched C 1 -C 20 -alkyl,
linear or branched substituted C 1 -C 20 -alkyl hydroxyl,
an ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a substituted ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
an ether radical —(CH 2 ) p —O—C q H 2q+1 ,
a substituted ether radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
a substituted radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
an oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a substituted oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a radical containing a mesogenic group,
R 1 independently for each o, are selected from a member of the group consisting of halogen,
linear or branched C 1 -C 20 -alkyl,
linear or branched substituted C 1 -C 20 -alkyl hydroxyl,
an ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a substituted ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
an ether radical —(CH 2 ) p —O—C q H 2q+1 ,
a substituted ether radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
a substituted radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
an oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a substituted oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a radical containing a mesogenic group, and
X represents a polyvalent linking unit selected from the group of C 5 -C 14 -aryl, C 12 -C 20 -diaryl, substituted or non-substituted triarylamine and substituted or non-substituted triaryiphosphane.
2. The compound of claim 1 wherein n and m are each 1.
3. The compound of claim 1 wherein R 1 , R 2 , R 3 and R 4 are each hydrogen.
4. The compound of claim 1 wherein R is hydrogen.
5. The compound of claim 1 wherein o represents 3, and the linking unit X is selected from the group consisting of benzene radicals and triphenylamine radicals.
6. The compound of claim 1 wherein o represents 4, and the linking unit X is a biphenyl radical.
7. A compound represented by the following formula (I),
wherein
n and m each independently of each other, and independently for each o, is an integer from 1 to 5,
o is 3,
R 1 , R 2 , R 3 and R 4 each independently of each other, and independently for each o, are selected from a member of the group consisting of hydrogen, halogen,
linear or branched C 1 -C 20 -alkyl,
linear or branched substituted C 1 -C 20 -alkyl hydroxyl,
an ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a substituted ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
an ether radical —(CH 2 ) p —O—C q H 2q+1 ,
a substituted ether radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
a substituted radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
an oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a substituted oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a radical containing a mesogenic group,
and R 1 , R 2 , R 3 and R 4 together forming a crown ether structure,
wherein the substituents of the substituted members, from which R 1 , R 2 , R 3 and R 4 , may each be independently selected, are selected independently from the group consisting of hydroxyl, halogen, liner or branched C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl and aryl,
wherein
p in each case represents an integer from 0 to 6,
q in each case represents an integer from 1 to 20,
r represents 0 or 1, and
s represents an integer from 1 to 20, and
R is selected, independently for each o, from the group consisting of hydrogen and a thiophene represented by the following formula (II),
wherein
m, n, are as defined in formula (I),
R 1 , R 2 , R 3 and R 4 each independently of each other, and independently for each o, are selected from a member of the group consisting of hydrogen, halogen,
linear or branched C 1 -C 20 -alkyl,
linear or branched substituted C 1 -C 20 -alkyl hydroxyl,
an ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a substituted ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
an ether radical —(CH 2 ) p —O—C q H 2q+1 ,
a substituted ether radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
a substituted radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
an oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a substituted oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a radical containing a mesogenic group, and
the linking unit X is a triphenylamine radical, and said compound is represented by the following formula (III),
8. The compound of claim 5 wherein the linking unit X is a benzene radical, and said compound is represented by the following formula (IV),
9. The compound of claim 6 wherein said compound is represented by the following formula (V),
10. A compound represented by the following formula (I),
wherein
n and m each independently of each other, and independently for each o, is an integer from 1 to 5,
o is 3or 4,
R 1 , R 2 , R 3 and R 4 each independently of each other, and independently for each o, are selected from a member of the group consisting of hydrogen, halogen,
linear or branched C 1 -C 20 -alkyl,
linear or branched substituted C 1 -C 20 -alkyl hydroxyl,
an ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a substituted ester radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
an ether radical —(CH 2 ) p —O—C q H 2q+1 ,
a substituted ether radical —(CH 2 ) p —O—CO—C q H 2q+1 ,
a radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
a substituted radical —(CH 2 ) p —O—C q H 2q SO 3 Na,
an oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a substituted oligoethylene glycol radical —(CH 2 ) p —O—(CO) r —(CH 2 CH 2 O) s CH 3 ,
a radical containing a mesogenic group,
and R 1 , R 2 , R 3 and R 4 together forming a crown ether structure,
wherein the substituents of the substituted members, from which R 1 , R 2 , R 3 and R 4 , may each be independently selected, are selected independently from the group consisting of hydroxyl, halogen, liner or branched C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl and aryl,
wherein
p in each case represents an integer from 0 to 6,
q in each case represents an integer from 1 to 20,
r represents 0 or 1, and
s represents an integer from 1 to 20, and
R is selected, independently for each o, from the group consisting of hydrogen and a thiophene represented by the following formula (II),
wherein
m, n, R 1 , R 2 , R 3 and R 4 , are as defined in formula (I), and
X represents a polyvalent linking unit selected from the group of C 5 -C 14 -aryl, C 12 -C 20 -diaryl, substituted triarylamine and substituted or non-substituted triaryiphosphane.