Conjugated monomers and polymers and preparation and use thereof

Abstract

Disclosed are new conjugated compounds (e.g., monomers and polymers) that include ladder-type moieties which can be used for preparing semiconducting materials. Such conjugated compounds can exhibit high n-type carrier mobility and/or good current modulation characteristics. Compounds of the present teachings also can exhibit ambipolar semiconducting activity. In addition, the compounds of the present teachings can possess certain processing advantages such as solution-processability and/or good stability in ambient conditions.

What is claimed is: 
     
       1. A compound of formula I: 
       
         
           
           
               
               
           
         
         wherein: 
         R a  and R a′  independently are a) H, b) a C 1-30  alkyl group, c) a C 2-30  alkenyl group, d) a C 2-30  alkynyl group, e) a C 1-30  haloalkyl group, f) a —Y—C 3-14  cycloalkyl group, g) a —Y—C 6-14  aryl group, h) a —Y-3-14 membered cycloheteroalkyl group, or i) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, the C 1-30  haloalkyl group, the C 3-14  cycloalkyl group, the C 6-14  aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 R i  groups; 
         R b , R b′ , R c , and R c′  independently are a) H, b) halogen, c) —CN, d) —NO 2 , e) —OS(O) 2 R e , f) —Sn(R e ) 3 , g) —B(OR e ) 2 , h) —Y—R f , i) a C 1-30  alkyl group, j) a C 2-30  alkenyl group, k) a C 2-30  alkynyl group, or l) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R i  groups, or alternatively, 
         each of R b  and R c , and R b′  and R c′ , together with each pair of carbon atoms to which each group is attached, independently forms a C 6-14  aryl group optionally substituted with 1-5 R d  groups; 
         W, at each occurrence, independently is O, S, NR e , or C(CN) 2 ; 
         R d , at each occurrence, independently is a) halogen, b) —CN, c) —NO 2 , d) —OS(O) 2 R e , e) —Sn(R e ) 3 , f) —B(OR e ) 2 , g) —Y—R f , h) ═W, i) a C 1-30  alkyl group, j) a C 2-30  alkenyl group, k) a C 2-30  alkynyl group, or l) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R i  groups; 
         R e , at each occurrence, independently is H or a C 1-30  alkyl group optionally substituted with 1-5 R i  groups; 
         R f , at each occurrence, independently is -(L) r -R g ; 
         L, at each occurrence, independently is a) a divalent C 3-14  cycloalkyl group, b) a divalent C 6-14  aryl group, c) a divalent 3-14 cycloheteroalkyl group, or d) a divalent 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R i  groups; 
         R g , at each occurrence, independently is a) a C 3-14  cycloalkyl group, b) a C 6-14  aryl group, c) a 3-14 cycloheteroalkyl group, or d) a 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R h  groups; 
         R h , at each occurrence, independently is a) halogen, b) —CN, c) —NO 2 , d) —OS(O) 2 R e , e) —Sn(R e ) 3 , f) —B(OR e ) 2 , g) a C 1-30  alkyl group, h) a C 2-30  alkenyl group, i) a C 2-30  alkynyl group, or j) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R i  groups; 
         R i , at each occurrence, independently is a) halogen, b) —CN, e) —NO 2 , f) —OH, g) —NH 2 , h) —OC 1-10  alkyl, i) —NH(C 1-10  alkyl), j) —N(C 1-10  alkyl) 2 , k) CHO, l) —C(O)OH, m) —C(O)(C 1-10  alkyl), n) —C(O)O(C 1-10  alkyl), o) —C(O)NH 2 , p) —C(O)NH(C 1-10  alkyl), q) —C(O)N(C 1-10  alkyl) 2 , r) a C 1-30  alkyl group, s) a C 2-30  alkenyl group, t) a C 2-30  alkynyl group, u) a C 1-30  haloalkyl group, v) a C 3-14  cycloalkyl group, w) a C 6-14  aryl group, x) a 3-14 membered cycloheteroalkyl group, or y) a 5-14 membered heteroaryl group; 
         Y, at each occurrence, independently is a) a divalent C 1-10  alkyl group, b) a divalent C 2-10  alkenyl group, c) a divalent C 2-10  alkynyl group, d) a divalent C 1-10  haloalkyl group, or e) a covalent bond; and 
         r, at each occurrence, independently is 0, 1, 2, 3, 4, 5, or 6; 
         provided that when W is O and each of R b  and R c , and R b′  and R c′ , together with each pair of carbon atoms to which each group is attached, forms a phenyl group, each of R a  and R a′  is not H or an unsubstituted phenyl group. 
       
     
     
       2. The compound of  claim 1 , wherein W is C(CN) 2 . 
     
     
       3. The compound of  claim 1 , wherein the compound has formula I′ or formula I″: 
       
         
           
           
               
               
           
         
         wherein R b , R b′ , R c , and R c′  independently are a) H, b) halogen, c) —CN, d) —NO 2 , e) —OS(O) 2 R e , f) —Sn (R e ) 3 , g) —B(OR e ) 2 , h) —Y—R f , i) a C 1-30  alkyl group, j) a C 2-30  alkenyl group, k) a C 2-30  alkynyl group, or l) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R i  groups; and 
         R a , R a′ , R d , R e , R f , R i , and Y are as defined in  claim 1 . 
       
     
     
       4. The compound of  claim 1 , wherein R a  and R a′  independently are H, a C 1-30  alkyl group, or a C 1-30  haloalkyl group. 
     
     
       5. The compound of  claim 1 , wherein R b , R b′ , R c , and R c′  independently are H, halogen, —CN, —NO 2 , —OS(O) 2 R e , —Sn(R e ) 3 , —B(OR e ) 2 , or —Y—R f , and R e , R f , and Y are as defined in  claim 1 . 
     
     
       6. The compound of  claim 5 , wherein R b , R b′ , R c , and R c′  independently are H or halogen. 
     
     
       7. The compound of  claim 1 , wherein R b , R b′ , R c , and R c′  independently are H or -(L) r -R g , wherein -(L) r -R g , at each occurrence, independently is selected from: 
       
         
           
           
               
               
           
         
         r is 0, 1, or 2; R j , at each occurrence, independently is H or R i ; R k , at each occurrence, independently is H or R h ; and R h  and R i  are as defined in  claim 1 . 
       
     
     
       8. The compound of  claim 1 , wherein R d , at each occurrence, independently is selected from halogen, —CN, —NO 2 , —OS(O) 2 R e , —Sn(R e ) 3 , —B(OR e ) 2 , and —Y—R f , and R e , R f , and Y are as defined in  claim 1 . 
     
     
       9. The compound of  claim 1 , wherein R d , at each occurrence, independently is selected from halogen and -(L) r -R g , wherein -(L) r -R 9 , at each occurrence, independently is selected from: 
       
         
           
           
               
               
           
         
         r is 0, 1, or 2; R j , at each occurrence, independently is H or R i ; R k , at each occurrence, independently is H or R h ; and R h  and R i  are as defined in  claim 1 . 
       
     
     
       10. The compound of  claim 1  selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       
        
       
     
     
       11. A compound of formula III, formula IV, or formula V: 
       
         
           
           
               
               
           
         
         wherein: 
         a, d, e, f, g, j, k and l independently are CR 1 , N, or P; 
         b, c, h and i independently are CR 2 , N, or P; 
         p is CR 3 ; 
         q is CR 4 ; 
         W, at each occurrence, independently is O, S, NR 1 , or C(CN) 2 ; 
         Y, at each occurrence, independently is a) a divalent C 1-10  alkyl group, b) a divalent C 2-10  alkenyl group, c) a divalent C 2-10  alkynyl group, d) a divalent C 1-10  haloalkyl group, or e) a covalent bond; 
         Z is CR 3 R 4  or SiR 3 R 4 ; 
         R 1 , at each occurrence, independently is a) H, b) halogen, c) —CN, d) —NO 2 , e) a C 1-30  alkyl group, f) a C 2-30  alkenyl group, g) a C 2-30  alkynyl group, h) a C 1-30  haloalkyl group, i) a —Y—C 3-14  cycloalkyl group, j) a —Y—C 6-14  aryl group, k) a —Y-3-14 membered cycloheteroalkyl group, or l) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, the C 1-30  haloalkyl group, the C 3-14  cycloalkyl group, the C 6-14  aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 R 9  groups; 
         R 2 , at each occurrence, independently is a) H, b) halogen, c) —CN, d) —NO 2 , e) —OS(O) 2 R 5 , f) —Sn(R 5 ) 3 , g) —B(OR 5 ) 2 , h) —Y—R 6 , i) a C 1-30  alkyl group, j) a C 2-30  alkenyl group, k) a C 2-30  alkynyl group, or l) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R 9  groups; 
         R 3  and R 4  independently are a) a C 1-30  alkyl group, b) a C 2-30  alkenyl group, c) a C 2-30  alkynyl group, d) a C 1-30  haloalkyl group, e) a —Y—C 3-14  cycloalkyl group, f) a —Y—C 6-14  aryl group, g) a —Y-3-14 membered cycloheteroalkyl group, or h) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, the C 1-30  haloalkyl group, the C 3-14  cycloalkyl group, the C 6-14  aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 R 9  groups; 
         R 5 , at each occurrence, independently is H or a C 1-30  alkyl group; 
         R 6 , at each occurrence, independently is -(L) r -R 7 ; 
         L, at each occurrence, independently is a) a divalent C 3-14  cycloalkyl group, b) a divalent C 6-14  aryl group, c) a divalent 3-14 cycloheteroalkyl group, or d) a divalent 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R 9  groups; 
         R 7 , at each occurrence, is a) a C 3-14  cycloalkyl group, b) a C 6-14  aryl group, c) a 3-14 cycloheteroalkyl group, or d) a 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R 8  groups; 
         R 8 , at each occurrence, independently is a) halogen, b) —CN, c) —NO 2 , d) —OS(O) 2 R 5 , e) —Sn(R 5 ) 3 , f) —B(OR 5 ) 2 , g) a C 1-30  alkyl group, h) a C 2-30  alkenyl group, i) a C 2-30  alkynyl group, or j) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R 9  groups; 
         R 9 , at each occurrence, independently is a) halogen, b) —CN, e) —NO 2 , f) —OH, g) —NH 2 , h) —OC 1-10  alkyl, i) —NH(C 1-10  alkyl), j) —N(C 1-10  alkyl) 2 , k) —CHO, l) —C(O)OH, m) —C(O)(C 1-10  alkyl), n) —C(O)O(C 1-10  alkyl), o) —C(O)NH 2 , p) —C(O)NH(C 1-10  alkyl), q) —C(O)N(C 1-10  alkyl) 2 , r) a C 1-30  alkyl group, s) a C 2-30  alkenyl group, t) a C 2-30  alkynyl group, u) a C 1-30  haloalkyl group, v) a C 3-14  cycloalkyl group, w) a C 6-14  aryl group, x) a 3-14 membered cycloheteroalkyl group, or y) a 5-14 membered heteroaryl group; and 
         r, at each occurrence, independently is 0, 1, 2, 3, 4, 5, or 6. 
       
     
     
       12. The compound of  claim 11 , wherein b, c, h, and i independently are CR 2 , and R 2 , at each occurrence, independently is selected from H, halogen, —OS(O) 2 R 5 , —SN(R 5 ) 3 , —B(OR 5 ) 2 , and a —Y—R 6  group. 
     
     
       13. The compound of  claim 11 , wherein each of c and h is CH; each of b and i is C(Br) CR 2 , and R 2  is Br or a -(L) r -R 7  group and each of c and h is CH, wherein r is 0, 1, or 2; L, at each occurrence, is a divalent 5-membered heteroaryl group optionally substituted with 1-5 R 9  groups; and R 7  is a 5-membered heteroaryl group optionally substituted with 1-5 R 8  groups. 
     
     
       14. The compound of  claim 11 , wherein a, d, e, f, g, j, k, and l independently are CR 1 . 
     
     
       15. The compound of claim  14  13 according to formula III, wherein each of a, d, e, f, g, j, k, and l is CH; Z is CR 3 R 4 , wherein each of R 3  and R 4  independently is a C 6-20  alkyl group; and W is O or C(CN) 2 . 
     
     
       16. The compound of claim  11  13 according to formula V, wherein each of p and q independently is a C(C 6-20  alkyl) group or a C(C 6-20  haloalkyl) group; and W is O or C(CN) 2 . 
     
     
       17. The compound of  claim 11 , wherein W is O or C(CN) 2 . 
     
     
       18. The compound of  claim 11 , wherein Z is CR 3 R 4 , and each of R 3  and R 4  independently is a C 6-20  alkyl group or a C 6-20  haloalkyl group. 
     
     
       19. The compound of  claim 11  selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       20. A compound of formula VII, formula VIII, or formula IX: 
       
         
           
           
               
               
           
         
         wherein: 
         p is CR 3′ ; 
         q is CR 4′ ; 
         W, at each occurrence, independently is O, S, NR 1 , or C(CN) 2 ; 
         Y, at each occurrence, independently is a) a divalent C 1-10  alkyl group, b) a divalent C 2-10  alkenyl group, c) a divalent C 2-10  alkynyl group, d) a divalent C 1-10  haloalkyl group, or e) a covalent bond; 
         Z is a) CR 3′ R 4′ , b) or SiR 3′ R 4′ , c) C(O), d) C(S), e) C(NR 5 ), or f) C(CR 1 R 1 ); 
         R 1 , at each occurrence, independently is a) H, b) halogen, c) —CN, d) —NO 2 , e) a C 1-30  alkyl group, f) a C 2-30  alkenyl group, g) a C 2-30  alkynyl group, h) a C 1-30  haloalkyl group, i) a —Y—C 3-14  cycloalkyl group, j) a —Y—C 6-14  aryl group, k) a —Y-3-14 membered cycloheteroalkyl group, or l) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, the C 1-30  haloalkyl group, the C 3-14  cycloalkyl group, the C 6-14  aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 R 9  groups; 
         R 3′  and R 4′  independently are a) H, b) a C 1-30  alkenyl group, c) a C 2-30  alkenyl group, d) a C 2-30  alkynyl group, e) a C 1-30  haloalkyl group, f) a —Y—C 3-14  cycloalkyl group, g) a —Y—C 6-14  aryl group, h) a —Y-3-14 membered cycloheteroaryl group, or i) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, the C 1-30  haloalkyl group, the C 3-14  cycloalkyl group, the C 6-14  aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 R 9  groups; 
         R 5 , at each occurrence, independently is H or a C 1-30  alkyl group; 
         L, at each occurrence, independently is a) a divalent C 3-14  cycloalkyl group, b) a divalent C 6-14  aryl group, c) a divalent 3-14 cycloheteroalkyl group, or d) a divalent 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R 9  groups; 
         R 7 , at each occurrence, is a) a C 3-14  cycloalkyl group, b) a C 6-14  aryl group, c) a 3-14 cycloheteroalkyl group, or d) a 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R 8  groups; 
         R 8 , at each occurrence, independently is a) halogen, b) —CN, c) —NO 2 , d) —OS(O) 2 R 5 , e) —Sn(R 5 ) 3 , f) —B(OR 5 ) 2 , g) a C 1-30  alkyl group, h) a C 2-30  alkenyl group, i) a C 2-30  alkynyl group, or j) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R 9  groups; 
         R 9 , at each occurrence, independently is a) halogen, b) —CN, e) —NO 2 , f) —OH, g) —NH 2 , h) —OC 1-10  alkyl, i) —NH(C 1-10  alkyl), j) —N(C 1-10  alkyl) 2 , k) —CHO, l) —C(O)OH, m) —C(O)(C 1-10  alkyl), n) —C(O)O(C 1-10  alkyl), o) —C(O)NH 2 , p) —C(O)NH(C 1-10  alkyl), q) —C(O)N(C 1-10  alkyl) 2 , r) a C 1-30  alkyl group, s) a C 2-30  alkenyl group, t) a C 2-30  alkynyl group, u) a C 1-30  haloalkyl group, v) a C 3-14  cycloalkyl group, w) a C 6-14  aryl group, x) a 3-14 membered cycloheteroalkyl group, or y) a 5-14 membered heteroaryl group; and 
         r, at each occurrence, independently is 0, 1, 2, 3, 4, 5, or 6. 
       
     
     
       21. The compound of  claim 20 , wherein W, at each occurrence, independently is C(CN) 2 . 
     
     
       22. The compound of  claim 20  selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       23. An article of manufacture comprising one or more compounds of claim  1  11. 
     
     
       24. The article of manufacture of  claim 23 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       25. A thin film semiconductor comprising one or more compounds of  claim 1 . 
     
     
       26. A composite comprising a substrate and the thin film semiconductor of  claim 25  deposited on the substrate. 
     
     
       27. A field effect transistor device comprising the thin film semiconductor of  claim 25 . 
     
     
       28. A field effect transistor device comprising the composite of  claim 26 . 
     
     
       29. The field effect transistor device of  claim 27  comprising a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material. 
     
     
       30. A photovoltaic device comprising the thin film semiconductor of  claim 25 . 
     
     
       31. A photovoltaic device comprising the composite of  claim 26 . 
     
     
       32. The photovoltaic device of  claim 30  comprising a p-type semiconducting material adjacent to the one or more compounds of formula I. 
     
     
       33. An organic light emitting diode device comprising the thin film semiconductor of  claim 25 . 
     
     
       34. An organic light emitting diode device comprising the composite of  claim 26 . 
     
     
       35. A method of making an article of manufacture, the method comprising depositing a composition comprising one or more compounds of  claim 1  dissolved in a liquid medium onto a substrate. 
     
     
       36. The method of  claim 35 , wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying. 
     
     
       37. The compound of  claim 1 , wherein each of R b  and R c , and R b′  and R C′ , together with each pair of carbon atoms to which each group is attached, independently forms a C 6-14  aryl group substituted with 1-5 R d  groups, wherein R d , at each occurrence, independently is selected from halogen and 
       
         
           
           
               
               
           
         
         wherein r is 0, 1, or 2; R j , at each occurrence, independently is H or R i ; R k , at each occurrence, independently is H or R h ; and R h  and R i  are as defined in  claim 1 . 
       
     
     
       38. The field effect transistor device of  claim 28  comprising a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material. 
     
     
       39. The photovoltaic device of  claim 31  comprising a p-type semiconducting material adjacent to the one or more compounds of formula I. 
     
     
       40. An article of manufacture comprising one or more compounds of  claim 10 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       41. A thin film semiconductor comprising one or more compounds of  claim 10 . 
     
     
       42. A field effect transistor device comprising the thin film semiconductor of  claim 41 . 
     
     
       43. A thin film semiconductor comprising one or more compounds of  claim 11 . 
     
     
       44. A composite comprising a substrate and the thin film semiconductor of  claim 43  deposited on the substrate. 
     
     
       45. An article of manufacture comprising the composite of  claim 44 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       46. An electronic, optical, or optoelectronic device comprising the thin film semiconductor of  claim 43 , wherein the device is a field effect transistor, a photovoltaic device, or an organic light emitting diode device. 
     
     
       47. An electronic, optical, or optoelectronic device comprising the composite of  claim 44 , wherein the device is a field effect transistor, a photovoltaic device, or an organic light emitting diode device. 
     
     
       48. A method of making an article of manufacture, the method comprising depositing a composition comprising one or more compounds of  claim 11  dissolved in a liquid medium onto a substrate. 
     
     
       49. The method of  claim 48 , wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying. 
     
     
       50. An article of manufacture comprising one or more compounds of  claim 19 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       51. A thin film semiconductor comprising one or more compounds of  claim 19 . 
     
     
       52. A field effect transistor device comprising the thin film semiconductor of  claim 51 . 
     
     
       53. A thin film semiconductor comprising one or more compounds of  claim 20 . 
     
     
       54. A composite comprising a substrate and the thin film semiconductor of  claim 53  deposited on the substrate. 
     
     
       55. An article of manufacture comprising one or more compounds of  claim 20 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       56. An electronic, optical, or optoelectronic device comprising the thin film semiconductor of  claim 53 , wherein the device is a field effect transistor, a photovoltaic device, or an organic light emitting diode device. 
     
     
       57. An electronic, optical, or optoelectronic device comprising the composite of  claim 54 , wherein the device is a field effect transistor, a photovoltaic device, or an organic light emitting diode device. 
     
     
       58. A method of making an article of manufacture, the method comprising depositing a composition comprising one or more compounds of  claim 20  dissolved in a liquid medium onto a substrate. 
     
     
       59. The method of  claim 58 , wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying. 
     
     
       60. A thin film semiconductor comprising one or more compounds of  claim 22 . 
     
     
       61. A composite comprising a substrate and the thin film semiconductor of  claim 60  deposited on the substrate. 
     
     
       62. An article of manufacture comprising the thin film semiconductor of  claim 60 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       63. An article of manufacture comprising the composite of  claim 61 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device. 
     
     
       64. A field effect transistor device comprising the thin film semiconductor of  claim 60 . 
     
     
       65. A field effect transistor device comprising the composite of  claim 61 . 
     
     
       66. A photovoltaic device comprising the thin film semiconductor of  claim 60 . 
     
     
       67. A photovoltaic device comprising the composite of  claim 61 . 
     
     
       68. An organic light emitting diode device comprising the thin film semiconductor of  claim 60 . 
     
     
       69. An organic light emitting diode device comprising the composite of  claim 61 . 
     
     
       70. A method of making an article of manufacture, the method comprising depositing a composition comprising one or more compounds of  claim 22  dissolved in a liquid medium onto a substrate. 
     
     
       71. The method of  claim 70 , wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying. 
     
     
       72. A compound of formula IV: 
       
         
           
           
               
               
           
         
         wherein: 
         a, d, g and j are CH; 
         b and i are CR 2 ; 
         c and h are CH; 
         p is CR 3 ; 
         q is CR 4 ; 
         W, at each occurrence, independently is O, S, or C(CN) 2 ; 
         Y, at each occurrence, independently is a) a divalent C 1-10  alkyl group, b) a divalent C 2-10  alkenyl group, c) a divalent C 2-10  alkynyl group, d) a divalent C 1-10  haloalkyl group, or e) a covalent bond; 
         R 2 , at each occurrence, independently is a) H, b) halogen, c) —CN, d) —NO 2 , e) —OS(O) 2 R 5 , f) —Sn(R 5 ) 3 , g) —B(OR 5 ) 2 , h) —Y—R 6 , i) a C 1-30  alkyl group, j) a C 2-30  alkenyl group, k) a C 2-30  alkynyl group, or l) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R 9  groups; 
         each of R 3  and R 4  independently is a C 6-20  alkyl group; 
         R 5 , at each occurrence, independently is H or a C 1-30  alkyl group; 
         R 6 , at each occurrence, independently is —(L) r -R 7 ; 
         L, at each occurrence, independently is a) a divalent C 3-14  cycloalkyl group, b) a divalent C 6-14  aryl group, c) a divalent 3-14 cycloheteroalkyl group, or d) a divalent 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R 9  groups; 
         R 7 , at each occurrence, is a) a C 3-14  cycloalkyl group, b) a C 6-14  aryl group, c) a 3-14 cycloheteroalkyl group, or d) a 5-14 membered heteroaryl group, wherein each of a)-d) optionally is substituted with 1-5 R 8  groups; 
         R 8 , at each occurrence, independently is a) halogen, b) —CN, c) —NO 2 , d) —OS(O) 2 R 5 , e) —Sn(R 5 ) 3 , f) —B(OR 5 ) 2 , g) a C 1-30  alkyl group, h) a C 2-30  alkenyl group, i) a C 2-30  alkynyl group, or j) a C 1-30  haloalkyl group, wherein each of the C 1-30  alkyl group, the C 2-30  alkenyl group, the C 2-30  alkynyl group, and the C 1-30  haloalkyl group optionally is substituted with 1-5 R 9  groups; 
         R 9 , at each occurrence, independently is a) halogen, b) —CN, e) —NO 2 , f) —OH, g) —NH 2 , h) —OC 1-10  alkyl, i) —NH(C 1-10  alkyl), j) —N(C 1-10  alkyl) 2 , k) —CHO, l) —C(O)OH, m) —C(O)(C 1-10  alkyl), n) —C(O)O(C 1-10  alkyl), o) —C(O)NH 2 , p) —C(O)NH(C 1-10  alkyl), q) —C(O)N(C 1-10  alkyl) 2 , r) a C 1-30  alkyl group, s) a C 2-30  alkenyl group, t) a C 2-30  alkynyl group, u) a C 1-30  haloalkyl group, v) a C 3-14  cycloalkyl group, w) a C 6-14  aryl group, x) a 3-14 membered cycloheteroalkyl group, or y) a 5-14 membered heteroaryl group; and 
         r, at each occurrence, independently is 0, 1, 2, 3, 4, 5, or 6.  
       
     
     
       73. The compound of claim 72, wherein R 2 , at each occurrence, independently is selected from a halogen, —OS(O) 2 R 5 , —Sn(R 5 ) 3 , —B(OR 5 ) 2 , and a —Y—R 6  group.  
     
     
       74. The compound of claim 72, wherein each R 2  is a —(L) r -R 7  group, wherein r is 0, 1, or 2; L, at each occurrence, is a divalent 5-membered heteroaryl group optionally substituted with 1-5 R 9  groups; and R 7  is a 5-membered heteroaryl group optionally substituted with 1-5 R 8  groups.  
     
     
       75. The compound of claim 74, wherein W is O.  
     
     
       76. The compound of claim 72 selected from: 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       77. An article of manufacture comprising one or more compounds of claim 20.  
     
     
       78. The article of manufacture of claim 77, wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device.  
     
     
       79. An article of manufacture comprising one or more compounds of claim 72.  
     
     
       80. The article of manufacture of claim 79, wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device.