Synthesis of aza-acenes as novel n-type materials for organic electronics

Abstract

Acenes, such as aza-acenes are attractive materials for organic semiconductors, specifically for n-type materials. There are disclosed new derivatives of acenes that are fabricated using novel synthesis. For example, the disclosed fabrication strategies have allowed for the first time new aza-tetracene and aza-pentacene derivatives. The HOMO and LUMO energy levels of these materials are tunable through appropriate substitution and as predicted, deepened. There are also disclosed organic photosensitive devices comprising at least one aza-acene such as aza-tetracene and aza-pentacene.

What is claimed is: 
     
         1 . A method of synthesizing an aza-tetracene or an aza-pentacene, comprising aromatizing a compound having a general formula selected from 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein Y n  are independently selected from C and N, R n  are independently selected from saturated carbocyclic, saturated heterocyclic, unsaturated carbocyclic, and unsaturated heterocyclic rings with adjacent R n , a H, an aryl, a halide, a pseudohalide, an alkyl, and an electron acceptor with the proviso that any of R n  is H when the Y to which it is bonded is N, and Z is selected from CH and CH 2 . 
     
     
         2 . The method of  claim 1 , wherein the compound is aromatized using an oxyphilic reagent. 
     
     
         3 . The method of  claim 2 , wherein the oxyphilic reagent is POCL 3 . 
     
     
         4 . The method of  claim 1 , wherein the compound is aromatized by bonding a protective group to the quinolone nitrogens of the compound and treating the compound with a reagent selected from alkyl or aryl organolithium reagents and alkyl or aryl Grignard reagents. 
     
     
         5 . The method of  claim 4 , wherein the protective group is MEM. 
     
     
         6 . The method of  claim 1 , wherein the aza-tetracene is selected from diaza-tetracenes, triaza-tetracenes, and tetraaza-tetracenes and the aza-pentacene is selected from diaza-pentacenes, triaaza-pentacenes, tetraaza-pentacenes, and pentaaza-pentacenes. 
     
     
         7 . The method of  claim 1 , wherein Y n  are C, and wherein the method further comprises synthesizing the compound selected from I through XIX using an aniline or a derivative thereof having a general formula 
       
         
           
           
               
               
           
         
       
       wherein R 1-4  are independently selected from saturated carbocyclic, saturated heterocyclic, unsaturated carbocyclic, and unsaturated heterocyclic rings with adjacent R n , a H, an aryl, a halide, a pseudohalide, an alkyl, and an electron acceptor, and W is selected from H, —CO 2 H, —CO 2 R, —COSR, and —CONR 2 . 
     
     
         8 . The method of  claim 1 , wherein the compound selected from I through XIX has at least 3 nitrogens in its core, and wherein the method further comprises synthesizing the compound selected from I through XIX using an aminopyridine or a derivative thereof having a general formula selected from 
       
         
           
           
               
               
           
         
       
       wherein X 1-3  are independently selected from N and C, R 1-3  are independently selected from saturated carbocyclic, saturated heterocyclic, unsaturated carbocyclic, and unsaturated heterocyclic rings with adjacent R n , a H, an aryl, a halide, a pseudohalide, an alkyl, and an electron acceptor, with the proviso that any of R 1-3  is H when the X to which it is bonded is N, and W is selected from H, —CO 2 H, —CO 2 R, —COSR, and —CONR 2 . 
     
     
         9 . An organic photosensitive optoelectronic device comprising at least one heterojunction at the interface of at least one donor material and at least one acceptor material, wherein the acceptor material comprises at least one aza-acene. 
     
     
         10 . The device of  claim 9 , wherein the aza-acene is selected from aza-tetracenes and aza-pentacenes. 
     
     
         11 . The device of  claim 10 , wherein the aza-acene is aza-tetracene selected from diaza-tetracenes, triaza-tetracenes, and tetraaza-tetracenes. 
     
     
         12 . The device of  claim 10 , wherein the aza-acene is aza-pentacene selected from diaza-pentacene, triaza-pentacene, tetraaza-pentacene, and pentaaza-pentacene. 
     
     
         13 . The device of  claim 11 , wherein the aza-tetracene is diaza-tetracene selected from 4,10-diphenyl-3,9-diaza-tetracene (DPDAT), 4,8,10,14-tetraphenyl-3,9-diaza-tetracene (TPDAT), 4,10-dichloro-3,9-diaza-tetracene (DCDAT), 8,14-diphenyl-4,10-dichloro-3,9-diaza-tetracene (DPDCDAT), 8,14-diphenyl-4,10-dicyano-3,9-diaza-tetracene (DPDCNDAT), and 4,10-dicyano-3,9-diaza-tetracene (DCNDAT). 
     
     
         14 . The device of  claim 13 , wherein the diaza-tetracene is DPDCNDAT and the at least one donor material is SubPc. 
     
     
         15 . The device of  claim 14  having a structure ITO/SubPc/DPDCNDAT/BCP/Al.