Dibenzosilol Polymers, Their Preparation and Uses

Abstract

A polymer containing an optionally substituted repeat unit of formula (I) wherein each R is the same or different and represents H or an electron withdrawing group, and each R 1 is the same or different and represents a substituent.

1 . A polymer comprising an optionally substituted repeat unit of formula (I):  
     
       
         
         
             
             
         
       
       wherein each R is the same or different and represents H or an electron withdrawing group; and each R 1  is the same or different and represents a substituent.  
     
   
   
       2 . A polymer according to  claim 1  wherein at least one R is a solubilizing group.  
   
   
       3 . A polymer according to  claim 1  wherein each R 1  is the same or different and is independently selected from the group consisting of optionally substituted C 1-20  alkyl, C 1-20  alkoxy, aryl and heteroaryl groups.  
   
   
       4 . A polymer according to  claim 1  comprising an optionally substituted aryl or heteroaryl second repeat unit.  
   
   
       5 . A monomer comprising a repeat unit of formula (II):  
     
       
         
         
             
             
         
       
       wherein each R is the same or different and represents H or an electron withdrawing group, and each R 1  is the same or different and represents a substituent and each X independently represents a polymerizable group.  
     
   
   
       6 . A monomer according to  claim 5  wherein each X is the same or different and is selected from the group consisting of boronic acid groups, boronic ester groups, borane groups, and halide functional groups.  
   
   
       7 . A method of forming a polymer comprising the step of polymerizing a monomer according to  claim 5 .  
   
   
       8 . A method according to  claim 7  wherein each X is the same or different and is a halide functional group, and comprising performing the polymerization in the presence of a nickel complex catalyst.  
   
   
       9 . A method according to  claim 7  comprising the step of polymerizing: 
 (a) a monomer of formula (II) wherein each X is a boron the same or different and is a boron derivative functional group selected from the group consisting of boronic acid, boronic esters, and boranes, and an aromatic monomer having at least two reactive halide functional groups; or    (b) a monomer of formula (II) wherein each X is the same or different and is a reactive halide functional group, and an aromatic monomer having at least two boron derivative functional group selected from the group consisting of boronic acid, boronic esters, and boranes; or    (c) a monomer of formula (II) wherein one X is a reactive halide functional group and the other X is a boron derivative functional group selected from the group consisting of boronic acid, boronic esters, and boranes,    wherein the reaction mixture comprises a catalytic amount of a palladium catalyst suitable for catalyzing the polymerization of the aromatic monomers, and a base in an amount sufficient to convert the boron derivative functional groups into boronate anionic groups.    
   
   
       10 . An optical device comprising a polymer according to  claim 1 .  
   
   
       11 . An optical device according to  claim 10  comprising an anode, a cathode and a layer of the polymer disposed between the anode and the cathode.  
   
   
       12 . An optical device according to  claim 11  comprising an electroluminescent device.  
   
   
       13 . A switching device comprising a polymer according to  claim 1 .  
   
   
       14 . A switching device according to  claim 13  comprising a thin film transistor.  
   
   
       15 . An optionally substituted compound of formula (IV):  
     
       
         
         
             
             
         
       
       wherein R is the same or different and represents H or an electron withdrawing group; each X 1  and each X 2  are the same or different and represent a leaving group capable of participating in a transmetallation reaction and X 2  has an electronegativity less than that of X 1 .  
     
   
   
       16 . The compound of  claim 15 , wherein each X 1  and X 2  is independently a halogen.  
   
   
       17 . A method of forming a monomer of formula (VI) from a compound of formula (V) according to the following scheme::  
     
       
         
         
             
             
         
       
       wherein the method comprises reacting the compound of formula (V) with a transmetallating agent followed by reaction with a compound of formula LG-Y-LG, wherein X 1  is a leaving group capable of participating in a transmetallation reaction and R is H or an electron withdrawing group; each X 3  is the same or different and represents a leaving group capable of participating in a transmetallation having an electronegativity less than or the same as that of X 1 ; Y represents a divalent residue comprising a backbone of 1-3 atoms; and each LG is the same or different and represents a leaving group.  
     
   
   
       18 . A method according to  claim 17  wherein Y comprises a single atom in its backbone selected from the group consisting of —CR 3   2 —, —SiR 3   2 —, —NR 3 —, —PR 3 —, —GeR 3   2 —, —SnR 3   2 —, O, and S, wherein R 3  is selected from the group consisting of optionally substituted alkyl, alkoxy, aryl, and heteroaryl.  
   
   
       19 . A method according to  claim 17  wherein each X 3  is the same or different and has an electronegativity less than that of X 1 .  
   
   
       20 . A method according to  claim 17  wherein each LG is the same or different and is a halogen.  
   
   
       21 . A method according to  claim 17  wherein the transmetallating agent is a compound of formula R 4 -M wherein R 4  is alkyl or aryl and M is a metal.  
   
   
       22 . A polymer comprising an optionally substituted first repeat unit of formula (VII):  
     
       
         
         
             
             
         
       
       wherein each R 2  is the same or different and represents a substituent; the R 2  groups may be linked to form a ring; and bond (a) is not linked to the 2-position of the repeat unit of formula (VII).  
     
   
   
       23 . A polymer according to  claim 22  wherein bond (b) is not bound to the 7-position of the repeat unit of formula (VII).  
   
   
       24 . A polymer according to  claim 22  wherein bond (a) is bound to the 3-position of the repeat unit of formula (VII).  
   
   
       25 . A polymer according to  claim 22  wherein bond (b) is bound to the 6-position of the repeat unit of formula (VII).  
   
   
       26 . A polymer according to  claim 22  wherein at least one R 2  is a solubilising group.  
   
   
       27 . A polymer according to  claim 22  wherein each R 2  is the same or different and is selected from the group consisting of optionally substituted C 1-20  alkyl, C 1-20  alkoxy, aryl and heteroaryl.  
   
   
       28 . A polymer according to  claim 22  wherein the polymer comprises an optionally substituted aryl or heteroaryl second repeat unit.  
   
   
       29 . An optionally substituted monomer of formula (VIII):  
     
       
         
         
             
             
         
       
       wherein each R 2  is the same or different and represents a substituent; each X independently represents a polymerizable group and at least one X is not linked to the 2-position of the repeat unit of formula (VIII).  
     
   
   
       30 . An electroluminescent device comprising an anode, a cathode and an electroluminescent layer located between the anode and cathode wherein the electroluminescent layer comprises a polymeric host material comprising an optionally substituted first repeat unit of formula (IX) and a luminescent dopant  
     
       
         
         
             
             
         
       
       wherein R 1  is the same or different and represents a substituent.  
     
   
   
       31 . An electroluminescent device according to  claim 30  wherein the repeat unit of formula (IX) is linked through its 3- and 6-positions.  
   
   
       32 . An electroluminescent device according to  claim 30  wherein the polymeric host material comprises a second repeat unit  
   
   
       33 . An electroluminescent device according to  claim 30  wherein the second repeat unit comprises a hole transporting material.  
   
   
       34 . An electroluminescent device according to  claim 30  wherein the luminescent dopant is phosphorescent.  
   
   
       35 . A method of forming an optionally substituted compound of formula (X) according to the following process:  
     
       
         
         
             
             
         
       
       wherein each R 8  is independently selected from the group consisting of C 1-20  alkyl and aryl; each R 9  is different from R 8  and is independently selected from the group consisting of C 1-20  alkyl, aryl and heteroaryl; M 1  is a metal; and Z is a reactive group capable of undergoing reaction with M 1 -R 9 .  
     
   
   
       36 . A method according to  claim 35  wherein M 1  is lithium.  
   
   
       37 . A method according to  claim 35  wherein R 8  is methyl.  
   
   
       38 . A method according to  claim 35  wherein Z is trialkylsilyl.  
   
   
       39 . A method according to  claim 35  wherein, in the case of reaction with M 1 -R 9 , the two groups R 10  are not linked to form a ring.  
   
   
       40 . A polymer according to  claim 22 , wherein R 2  is a C 4-10  alkyl group.  
   
   
       41 . A polymer according to  claim 40 , wherein R 2  is a m-hexyl group or an n-octyl group.  
   
   
       42 . As method according to  claim 35 , wherein Z is trimethylsilyl.