Organic small molecule semiconducting chromophores for use in organic electronic devices
Small organic molecule semi-conducting chromophores containing a pyridalthiadiazole, pyridaloxadiazole, or pyridaltriazole core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.
1. A compound of Formula II:
where X 1 and Y 1 are selected from the group consisting of N and CH, where when X 1 is N, Y 1 is CH, and when X 1 is CH, Y 1 is N; and where, independently of X 1 and Y 1 , X 2 and Y 2 are selected from the group consisting of N and CH, where when X 2 is N, Y 2 is CH, and when X 2 is CH, Y 2 is N;
M is selected from the group consisting of sulfur (S), oxygen (O), and N—R 1 , where R 1 is H, C 1 -C 30 alkyl or C 6 -C 30 aryl;
n is an integer between 0 and 5, inclusive;
A 1 is independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl groups;
each B 1 is independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl groups; and
each B 2 is independently selected from the group consisting of a nonentity, H, F, a C 1 -C 16 alkyl group, and substituted or unsubstituted aryl or heteroaryl groups.
2. A compound according to claim 1 of Formula IIa, Formula IIb, or Formula IIc:
where M is selected from the group consisting of sulfur (S), oxygen (O), and N—R 1 , where R 1 is H, C 1 -C 30 alkyl or C 6 -C 30 aryl;
where A 1 is independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl groups;
B 1 is independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl groups;
each B 2 is independently selected from the group consisting of a nonentity, H, F, a C 1 -C 16 alkyl group, and a substituted or unsubstituted aryl or heteroaryl group; and
n is an integer between 0 and 5 inclusive.
3. The compound of claim 2 , wherein A 1 is independently selected from the group consisting of substituted or unsubstituted thiophene, pyrrole, furan, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, and 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′=C 1 -C 30 alkyl or C 6 -C 30 aryl.
4. The compound of claim 2 , wherein B 1 is independently selected from the group consisting of substituted or unsubstituted thiophene, pyrrole, furan, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
5. A compound of Formula I:
wherein X 1 and Y 1 are selected from the group consisting of N and CH, where when X 1 is N, Y 1 is CH, and when X 1 is CH, Y 1 is N; and
where M is selected from the group consisting of sulfur (S), oxygen (O), and N—R 1 , where R 1 is H, C 1 -C 30 alkyl or C 6 -C 30 aryl;
where, independently of X 1 and Y 1 , X 2 and Y 2 are selected from the group consisting of N and CH, where when X 2 is N, Y 2 is CH, and when X 2 is CH, Y 2 is N;
A 1 is independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl groups;
each B 1 is independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl groups; and
each B 2 is independently selected from the group consisting of a nonentity, H, F, a C 1 -C 16 alkyl group, and a substituted or unsubstituted aryl or heteroaryl group.
6. The compound of claim 5 , wherein A 1 is independently selected from the group consisting of substituted or unsubstituted thiophene, pyrrole, furan, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, and 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene where R and R′=C 1 -C 30 alkyl or C 6 -C 30 aryl.
7. The compound of claim 5 , wherein each B 1 is selected from the group consisting of substituted or unsubstituted thiophene, pyrrole, furan, phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene, terthiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene, cyclopentadithiophene, silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene, naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
8. A compound of claim 5 of the following formulas Ia, Ib, or Ic:
9. A compound selected from Formula 1, Formula 2, Formula 3, Formula 4, or Formula 5:
where:
M is selected from the group consisting of sulfur (S), oxygen (O), and N—R 1 , where R 1 is H, C 1 -C 30 alkyl or C 6 -C 30 aryl;
n is an integer from 0 to 5 inclusive;
m is an integer from 0 to 5 inclusive;
R 2 is selected from the group consisting of H, C 1 -C 16 alkyl, —O—C 1 -C 16 alkyl, C 2 -C 16 alkenyl, and C 2 -C 16 alkynyl;
J is selected from the group consisting of CH and N;
X is S, O, or NH when J is CH; and X is S when J is N;
R 4 is selected from the group consisting of C 6 -C 30 aryl optionally substituted with one or more C 1 -C 16 alkyl groups; R 6 is selected from the group consisting of aryl, perfluoroaryl, and C 6 -C 30 aryl optionally perfluorinated or optionally substituted with one or more C 1 -C 16 alkyl groups; and each DONOR is independently selected from the group consisting of:
where L is C or Si;
A is N or P;
R 11 is selected from C 1 -C 16 alkyl;
R 12 is selected from the group consisting of C 1 -C 16 alkyl, C 6 -C 20 unsubstituted aryl, and C 6 -C 20 aryl substituted with one or more groups selected from the group consisting of —F, C 1 -C 20 alkyl, C 1 -C 20 fluoroalkyl, —O—C 1 -C 20 alkyl, and —C 1 -C 20 fluoroalkyl;
R 13 is selected from the group consisting of C 1 -C 16 alkyl and C 6 -C 20 aryl;
R 14 is selected from the group consisting of C 1 -C 16 alkyl, —O—C 1 -C 16 alkyl, —C(═O)—O—C 1 -C 16 alkyl, and —O—C(═O)—C 1 -C 16 alkyl; and
R 15 is selected from the group consisting of C 1 -C 16 alkyl, C 6 -C 20 unsubstituted aryl, and C 6 -C 20 aryl substituted with one or more groups selected from the group consisting of —F, C 1 -C 20 alkyl, C 1 -C 20 fluoroalkyl, —O—C 1 -C 20 alkyl, or —C 1 -C 20 fluoroalkyl; and
R 16 is selected from the group consisting of C 1 -C 16 alkyl, C 6 -C 20 unsubstituted aryl, and C 6 -C 20 aryl substituted with one or more groups selected from —F, C 1 -C 20 alkyl, C 1 -C 20 fluoroalkyl, —O—C 1 -C 20 alkyl, or —C 1 -C 20 fluoroalkyl.
10. An electronic or optoelectronic device comprising a non-polymeric compound of claim 1 , where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
11. An electronic or optoelectronic device comprising a non-polymeric compound of claim 2 , where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
12. An electronic or optoelectronic device comprising a non-polymeric compound of claim 3 , where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
13. An electronic or optoelectronic device comprising a non-polymeric compound of claim 4 , where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
14. An electronic or optoelectronic device comprising a non-polymeric compound of claim 5 , where said non-polymeric compound is an electron acceptor or is an electron donor in an active layer of the electronic or optoelectronic device.
15. A device comprising:
1) a first hole-collecting electrode optionally coated onto a transparent substrate;
2) an optional layer or layers adjacent to the first electrode selected from an electron-blocking layer, exciton-blocking layer, or hole-transporting layer;
3) a layer comprising a mixture of an electron acceptor material and an organic non-polymeric electron donor, said electron donor comprising a compound of claim 1 ;
4) an optional layer or layers selected from a hole-blocking layer, exciton-blocking layer, or electron-transporting layer; and
5) a second electron-collecting electrode.
16. The device of claim 10 , wherein the non-polymeric compound has a solubility of at least about 5 mg/mL in an organic solvent.
17. The device of claim 16 , wherein the organic solvent is selected from the group consisting of chloroform, toluene, chlorobenzene, methylene dichloride, tetrahydrofuran, and carbon disulfide.
18. The device of claim 10 , wherein the device is prepared by solution processing of the non-polymeric compound.
19. The compound of claim 1 , wherein A 1 is independently selected from the group consisting of C 6 -C 20 substituted or unsubstituted aryl or heteroaryl groups.
20. The compound of claim 1 , wherein A 1 is independently selected from the group consisting of C 6 -C 10 substituted or unsubstituted aryl or heteroaryl groups.
21. The compound of claim 1 , wherein each B 1 is independently selected from the group consisting of C 6 -C 20 substituted or unsubstituted aryl or heteroaryl groups.
22. The compound of claim 1 , wherein each B 1 is independently selected from the group consisting of C 6 -C 10 substituted or unsubstituted aryl or heteroaryl groups.
23. The compound of claim 1 , wherein each B 2 is independently selected from the group consisting of C 6 -C 20 substituted or unsubstituted aryl or heteroaryl groups.
24. The compound of claim 1 , wherein each B 2 is independently selected from the group consisting of C 6 -C 10 substituted or unsubstituted aryl or heteroaryl groups.
25. The compound of claim 1 selected from the group consisting of: