Inert solution-processable molecular chromophores for organic electronic devices

Abstract

Small organic molecule chromophores containing a benzo[c][1,2,5]thiadiazole with an electron-withdrawing substituent W in the 5-position (5BTH), benzo[c][1,2,5]oxadiazole with an electron-withdrawing substituent W in the 5-position (5BO), 2H-benzo[d][1,2,3]triazole (5BTR) with an electron-withdrawing substituent W in the 5-position (5BTR), 5-fluorobenzo[c][1,2,5]thiadiazole (FBTH), 5-fluorobenzo[c][1,2,5]oxadiazole (FBO), or 5-fluoro-2H-benzo[d][1,2,3]triazole (FBTR) core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

1 : An electronic or optoelectronic device comprising a non-polymeric compound, said compound incorporating one or more groups of Formula A: 
       
         
           
           
               
               
           
         
         where said non-polymeric compound is used in an active layer of the electronic or optoelectronic device; 
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where either X 1  is CH and Y 1  is —C(W)—, or X 1  is —C(W)— and Y 1  is CH; and 
         W is selected from F, Cl, Br, I, —CN, —CF 3 , —CHF 2 , or —CH 2 F. 
       
     
     
         2 : The electronic or optoelectronic device according to  claim 1 , wherein the non-polymeric compound is used in an active layer of said device. 
     
     
         3 : The electronic or optoelectronic device according to  claim 1 , wherein said device is a solar cell. 
     
     
         4 : The electronic or optoelectronic device according to  claim 1 , wherein M is sulfur and W is F. 
     
     
         5 : The electronic or optoelectronic device according to  claim 1 , wherein the active layer comprises a compound of Formula II: 
       
         
           
           
               
               
           
         
         where X 1  and Y 1  are selected from —C(W)— and CH, where when X 1  is —C(W)—, Y 1  is CH, and when X 1  is CH, Y 1  is —C(W)—; and where, independently of X 1  and Y 1 , X 2  and Y 2  are selected from —C(W)— and CH, where when X 2  is —C(W)—, Y 2  is CH, and when X 2  is CH, Y 2  is —C(W)—; 
         W is selected from F, Cl, Br, I, —CN, —CF 3 , —CHF 2 , or —CH 2 F; 
         M is selected from sulfur (S), oxygen (O), or 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 C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups, C 6 -C 20  substituted or unsubstituted aryl or heteroaryl groups, and C 6 -C 10  substituted or unsubstituted aryl or heteroaryl groups; 
         each B 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups, C 6 -C 20  substituted or unsubstituted aryl or heteroaryl groups, and C 6 -C 10  substituted or unsubstituted aryl or heteroaryl groups; and 
         each B 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups, C 6 -C 20  substituted or unsubstituted aryl or heteroaryl groups, and C 6 -C 10  substituted or unsubstituted aryl or heteroaryl groups. 
       
     
     
         6 : The electronic or optoelectronic device according to  claim 5 , wherein the active layer comprises a compound of Formula IIa-F, Formula IIb-F, or Formula IIc-F: 
       
         
           
           
               
               
           
         
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where W is selected from F, Cl, Br, I, —CN, —CF 3 , —CHF 2 , or —CH 2 F; 
         where A 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; 
         B 1  is independently selected from a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group; 
         each B 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group; and 
         n is an integer between 0 and 5 inclusive. 
       
     
     
         7 : The electronic or optoelectronic device according to  claim 6 , wherein A 1  is independently selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, 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 and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 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. 
     
     
         8 : The electronic or optoelectronic device according to  claim 6 , wherein B 1  is independently selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, 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. 
     
     
         9 : The electronic or optoelectronic device according to  claim 1 , wherein the active layer comprises a compound of Formula I: 
       
         
           
           
               
               
           
         
         wherein X 1  and Y 1  are selected from —C(W)— and CH, where when X 1  is —C(W)—, Y 1  is CH, and when X 1  is CH, Y 1  is —C(W)—; and 
         where M is selected from sulfur (S), oxygen (O), or 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 —C(W)— and CH, where when X 2  is —C(W)—, Y 2  is CH, and when X 2  is CH, Y 2  is —C(W)—; 
         where W is selected from F, Cl, Br, I, —CN, —CF 3 , —CHF 2 , or —CH 2 F; 
         A 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; 
         each B 1  is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and 
         each B 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         10 : The electronic or optoelectronic device according to  claim 9 , wherein A 1  is independently selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, 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, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 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. 
     
     
         11 : The electronic or optoelectronic device according to  claim 9 , wherein each B 1  is selected from substituted or unsubstituted thiophene, pyrrole, furan, phenyl, 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. 
     
     
         12 : The electronic or optoelectronic device according to  claim 9 , wherein the compound of Formula I is selected from formulas Ia-F, Ib-F, or Ic-F: 
       
         
           
           
               
               
           
         
       
     
     
         13 : The electronic or optoelectronic device according to  claim 1 , wherein the active layer comprises a compound of Formula III-F: 
       
         
           
           
               
               
           
         
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where H 1  is selected from A 1 , -B 1 -B 2 , -A 1 -B 1 -B 2 , or 
       
       
         
           
           
               
               
           
         
         n is an integer between 0 and 5, inclusive; 
         A 1  (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups, C 6 -C 20  substituted or unsubstituted aryl or heteroaryl groups, and C 6 -C 10  substituted or unsubstituted aryl or heteroaryl groups; 
         each B 1  (when present) is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and 
         each B 2  (when present) is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         14 : The electronic or optoelectronic device according to  claim 13 , wherein the compound of Formula III-F is selected from a compound of Formula IIIa-F, Formula IIIb-F, Formula IIIc-F, or Formula IIId-F: 
       
         
           
           
               
               
           
         
       
     
     
         15 : The electronic or optoelectronic device according to  claim 1 , wherein the active layer comprises a compound of Formula IV-V: 
       
         
           
           
               
               
           
         
         where X 1  and Y 1  are selected from —C(W)— and CH, where when X 1  is —C(W)—, Y 1  is CH, and when X 1  is CH, Y 1  is —C(W)—; and where, independently of X 1  and Y 1 , X 2  and Y 2  are selected from —C(W)— and CH, where when X 2  is —C(W)—, Y 2  is CH, and when X 2  is CH, Y 2  is —C(W)—; 
         and where, independently of X 1 , Y 1 , X 2 , and Y 2 , X 3  and Y 3  are selected from —C(W)— and CH, where when X 3  is —C(W)—, Y 3  is CH, and when X 3  is CH, Y 3  is —C(W)—; 
         M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where W is selected from F, Cl, Br, I, —CN, —CF 3 , —CHF 2 , or —CH 2 F; 
         K 1  is independently selected from substituted or unsubstituted aryl or heteroaryl groups, such as C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups, C 6 -C 20  substituted or unsubstituted aryl or heteroaryl groups, and C 6 -C 10  substituted or unsubstituted aryl or heteroaryl groups; 
         each E 1  is independently either absent, or selected from substituted or unsubstituted aryl or heteroaryl groups; 
         each D 1  is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and 
         each D 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         16 : The electronic or optoelectronic device according to  claim 15 , where the compound of Formula IV-V is selected from a compound of Formula IVa-F or Formula IVb-F: 
       
         
           
           
               
               
           
         
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where K 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; 
         each D 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; and 
         each D 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         17 : The electronic or optoelectronic device according to  claim 15 , where the compound of Formula IV-V is selected from a compound of Formula Va-F or Formula Vb-F: 
       
         
           
           
               
               
           
         
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where K 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; 
         each D 1  and E 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; and 
         each D 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         18 : The electronic or optoelectronic device according to  claim 1 , wherein the active layer comprises a compound of Formula VI-VII: 
       
         
           
           
               
               
           
         
         where the moiety 
       
       
         
           
           
               
               
           
         
         is selected from 
       
       
         
           
           
               
               
           
         
         (2,2′,7,7′-yl-9,9′-spirobi[fluorene]), 
       
       
         
           
           
               
               
           
         
         (3,3′,7,7′-yl-5,5′-spirobi[dibenzo[b,d]silole]), 
       
       
         
           
           
               
               
           
         
         (2,2′,6,6′-yl-4,4″-spirobi[cyclopenta[1,2-b:5,4-b′]dithiophene]), or 
       
       
         
           
           
               
               
           
         
         (2,2′,6,6′-yl-4,4′-spirobi[silolo[3,2-b:4,5-b′]dithiophene]); 
         where X 1  and Y 1  are selected from —C(W)— and CH, where when X 1  is —C(W)—, Y 1  is CH, and when X 1  is CH, Y 1  is —C(W)—; and where, independently of X 1  and Y 1 , X 2  and Y 2  are selected from —C(W)— and CH, where when X 2  is —C(W)—, Y 2  is CH, and when X 2  is CH, Y 2  is —C(W)—; 
         and where, independently of X 1 , Y 1 , X 2 , and Y 2 , X 3  and Y 3  are selected from —C(W)— and CH, where when X 3  is —C(W)—, Y 3  is CH, and when X 3  is CH, Y 3  is —C(W)—; and where, independently of X 1 , Y 1 , X 2 , Y 2 , X 3 , and Y 3 , X 4  and Y 4  are selected from —C(W)— and CH, where when X 4  is —C(W)—, Y 4  is CH, and when X 4  is CH, Y 4  is —C(W)—; 
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where W is selected from F, Cl, Br, I, —CN, —CF 3 , —CHF 2 , or —CH 2 F; 
         each F 1  is independently selected from substituted or unsubstituted aryl or heteroaryl groups; 
         each G 1  is independently selected from substituted or unsubstituted aryl or heteroaryl groups; and 
         each G 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         19 : The electronic or optoelectronic device according to  claim 18 , wherein the compound of Formula VI-VII is selected from a compound of Formula VIa-F or Formula VIb-F: 
       
         
           
           
               
               
           
         
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where each F 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; 
         each G 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; and 
         each G 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         20 : The electronic or optoelectronic device according to  claim 18 , wherein the compound of Formula VI-VII is selected from a compound of Formula VIIa-F or Formula VIIb-F: 
       
         
           
           
               
               
           
         
         where M is selected from sulfur (S), oxygen (O), or N—R 1 , where R 1  is H, C 1 -C 30  alkyl or C 6 -C 30  aryl; 
         where each F 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; 
         each G 1  is independently selected from C 6 -C 30  substituted or unsubstituted aryl or heteroaryl groups; and 
         each G 2  is independently selected from a nonentity, H, F, a C 1 -C 16  alkyl group, or a C 6 -C 30  substituted or unsubstituted aryl or heteroaryl group. 
       
     
     
         21 - 41 . (canceled)