Metal complexes, methods, and uses thereof

Abstract

Metal complexes that exhibit multiple radiative decay mechanisms, together with methods for the preparation and use thereof.

1 . A metal-assisted delayed fluorescent emitter represented by one or more of formulas 
       
         
           
           
               
               
           
         
         wherein A is an accepting group comprising one or more of the following structures, which can optionally be substituted 
       
       
         
           
           
               
               
           
         
         wherein D is a donor group comprising one or more of the following structures, 
         which can optionally be substituted, 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein C in structure (a) or (b) comprises one or more of the following structures, which can optionally be substituted 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein N in structure (a) or (b) comprises one or more of the following structures, which can optionally be substituted 
       
       
         
           
           
               
               
           
         
         wherein each of a 0 , a 1 , and a 2  in dependently is present or absent, and if present, comprises 
       
       
         
           
           
               
               
           
         
         a direct bond and/or linking group comprising one or more of the following, 
         wherein b 1  and b 2  independently is present or absent, and if present, comprises a linking group comprising one or more of the following 
       
       
         
           
           
               
               
           
         
         wherein X is B, C, N, O, Si, P, S, Ge, As, Se, Sn, Sb, or Te, 
         wherein Y is O, S, S═O, SO 2 , Se, N, NR 3 , PR 3 , RP═O, CR 1 R 2 , C═O, SiR 1 R 2 , GeR 1 R 2 , BH, P(O)H, PH, NH, CR 1 H, CH 2 , SiH 2 , SiHR 1 , BH, or BR 3 , 
         wherein each of R, R 1 , R 2 , and R 3  independently is hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, deuterium, halogen, hydroxyl, thiol, nitro, cyano, amino, a mono- or di-alkylamino, a mono- or diaryl amino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, nitrile, isonitrile, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureidc, phosphoramide, amercapto, sulfo, carboxyl, hydrzino, substituted silyl, or polymerizable, or any conjugate or combination thereof, 
         wherein n is a number that satisfies the valency of Y, 
         wherein M is platinum (II), palladium (II), nickel (I), manganese (II), zinc (II), gold (III), silver (III), copper (III), iridium (I), rhodium (I), and/or cobalt (I). 
       
     
     
         2 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein a 2  is absent in structure A. 
     
     
         3 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein a 2  and b 2  are absent. 
     
     
         4 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein X is N. 
     
     
         5 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein A is 
       
         
           
           
               
               
           
         
       
       wherein a 2  is absent, wherein b 2  are absent, wherein D is 
       
         
           
           
               
               
           
         
       
     
     
         6 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein C in structure (a) or (b) is 
       
         
           
           
               
               
           
         
       
     
     
         7 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein N in structure (a) or (b) is 
       
         
           
           
               
               
           
         
       
       or R substituted 
       
         
           
           
               
               
           
         
       
     
     
         8 . The metal-assisted delayed fluorescent emitter of  claim 1 , wherein M is Palladium (II). 
     
     
         9 . The metal-assisted delayed fluorescent emitter of  claim 1 , represented by any one of 
       
         
           
           
               
               
           
         
       
     
     
         10 . A metal-assisted delayed fluorescent emitter having the structure 
       
         
           
           
               
               
           
         
         wherein M comprises Ir, Rh, Mn, Ni, Cu, or Ag;
 wherein each of R 1  and R 2  independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein each of Y 1a  and Y 1b  independently is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
 wherein each of Y 2a , Y 2b , Y 2c , and Y 2d  independently is N, NR 6a , or CR 6b , wherein each of R 6a  and R 6b  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 each of Y 3a , Y 3b , Y 3c , Y 3d , Y 4a , Y 4b , Y 4c , and Y 4d  independently is N, O, S, NR 6a , CR 6b , wherein each of R 6a  and R 6b  independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; or Z(R 6c ) 2 , wherein Z is C or Si, and wherein each R 6c  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein each of m and n independently are an integer 1 or 2; 
 wherein each of   independently is partial or full unsaturation of the ring with which it is associated. 
 
       
     
     
         11 . The metal-assisted delayed fluorescent emitter of  claim 10 , wherein Y 2b  is CH, wherein Y 2c , Y 3b  and Y 4b  is N, wherein M is Ir or Rh. 
     
     
         12 . A metal-assisted delayed fluorescent emitter having the structure 
       
         
           
           
               
               
           
         
         wherein M comprises Pt, Pd and Au; 
         wherein each of R 1  and R 2  independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
         wherein each of Y 1a  and Y 1b  independently is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
         wherein each of Y 2a , Y 2b , Y 2c , and Y 2d  independently is N, NR 6a , or CR 6b , wherein each of R 6a  and R 6b  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
         each of Y 3a , Y 3b , Y 3c , Y 3d , Y 3e , Y 3f , Y 4a , Y 4b , Y 4c , and Y 4d  independently is N, O, S, NR 6a , CR 6b , wherein each of R 6a  and R 6b  independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; or Z(R 6c ) 2 , wherein Z is C or Si, and wherein each R 6c  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
         wherein each of m is an integer 1 or 2; 
         wherein each of   independently is partial or full unsaturation of the ring with which it is associated. 
       
     
     
         13 . The metal-assisted delayed fluorescent emitter of  claim 12 , wherein Y 2b  and Y 2c  is C, wherein Y 3b  and Y 4b  is N, wherein each of Y 1a  and Y 1b  independently is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
 wherein M is Pt or Pd. 
 
     
     
         14 . The metal-assisted delayed fluorescent emitter of  claim 12 , wherein Y 2b , Y 2c  and Y 4b  is CH, wherein Y 3b  is N, wherein each of Y 1a  and Y 1b  independently is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; wherein M is Au. 
     
     
         15 . A metal-assisted delayed fluorescent emitter having the structure 
       
         
           
           
               
               
           
         
         wherein M comprises Pt, Pd, Au, Ag;
 wherein each of R 1  and R 2  independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein one of Y 1a  and Y 1b  is B(R 2 ) 2  and the other of Y 1a  and Y 1b  is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
 wherein each of Y 2a , Y 2b , Y 2c , and Y 2d  independently is N, NR 6a , or CR 6b , wherein each of R 6a  and R 6b  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 each of Y 3a , Y 3b , Y 3c , Y 3d , Y 4a , Y 4b , Y 4c , and Y 4d  independently is N, O, S, NR 6a , CR 6b , wherein each of R 6a  and R 6b  independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; or Z(R 6c ) 2 , wherein Z is C or Si, and wherein each R 6c  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein each of in and n independently are an integer 1 or 2; 
 
         wherein each of   independently is partial or full unsaturation of the ring with which it is associated. 
       
     
     
         16 . A metal-assisted delayed fluorescent emitter having the structure: 
       
         
           
           
               
               
           
         
         wherein M comprises Ir, Rh, Pt, Os, Zr, Co, or Ru; 
         wherein each of R 1  and R 2  independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
         wherein each of Y 1a , Y 1b , Y 1c  and Y 1d  independently is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
       
       wherein Y 1e  is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, or nothing, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloakane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
 wherein each of Y 2a , Y 2b , Y 2c , and Y 2d  independently is N, NR 6a , or CR 6b , wherein each of R 6a  and R 6b  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein each of Y 3a , Y 3b , Y 3c , Y 3d , Y 3e , Y 4a , Y 4b , Y 4c , and Y 4d  independently is N, O, S, NR 6a , CR 6b , wherein each of R 6a  and R 6b  independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; or Z(R 6c ) 2 , wherein Z is C or Si, and wherein each R 6c  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein in each of each of Y 5a , Y 5b , Y 5c , Y 5d , Y 6a , Y 6b , Y 6c , and Y 6d  independently is N, O, S, NR 6a , or CR 6b ; 
 wherein each of m, n, l and p independently are an integer 1 or 2; 
 
       wherein each of   independently is partial or full unsaturation of the ring with which it is associated. 
     
     
         17 . A metal-assisted delayed fluorescent emitter having the structure 
       
         
           
           
               
               
           
         
         wherein M comprises Pd, Ir, Rh, Au, Co, Mn, Ni, Ag, or Cu;
 wherein each of Y 1a  and Y 1b  independently is O, NR 2 , CR 2 R 3 , S, AsR 2 , BR 2 , B(R 2 ) 2 ,PR 2 , P(O)R 2 , or SiR 2 R 3 , or a combination thereof, wherein each of R 2  and R 3  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R 2  and R 3  together form C═O, wherein each of R 2  and R 3  independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; 
 wherein each of Y 2a , Y 2b , Y 2c , Y 2d , Y 2e , Y 2f , Y 2g , and Y 2h  independently is N, NR 6a , or CR 6b , wherein each of R 6a  and R 6b  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 each of Y 3a , Y 3b , Y 3c , Y 3d , Y 3e Y 4a , Y 4b , Y 4c , Y 4d  and Y 4e  independently is N, O, S, NR 6a , CR 6b , wherein each of R 6a  and R 6b  independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocycyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; or Z(R 6c ) 2 , wherein Z is C or Si, and wherein each R 6c  independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; 
 wherein each of m is the integer 1 or 2; 
 wherein each of n is the integer 1 or 2; 
 wherein each of   independently is partial or full unsaturation of the ring with which it is associated. 
 
       
       wherein each of Fl 1 , Fl 2 , Fl 3  and Fl 4  independently are fluorescent emitters with tunable singlet excited state energies which are covenantly bonded to selected atoms among Y 2a , Y 2d , Y 2e , Y 2f , Y 2g , Y 2h , Y 3c , Y 3d , Y 3e Y 4c , Y 4d  and Y 4e . 
     
     
         18 . A metal-assisted delayed fluorescent emitter, having a singlet excited state/states energy from 0 to 0.2 eV higher than a lowest triplet state energy, and being capable of emitting simultaneously from the lowest triplet state and the singlet excited state/states at room temperature or elevated temperature and harvesting both electrogenerated singlet and triplet excitons. 
     
     
         19 . A device comprising the metal-assisted delayed fluorescent emitter of  claim 1 . 
     
     
         20 . The device of  claim 19 , wherein the metal-assisted delayed fluorescent emitter is selected to have 100% internal quantum efficiency in the device settings. 
     
     
         21 . The device of  claim 19 , wherein the device is an organic light emitting diode. 
     
     
         22 . The device of  claim 19 , wherein the device is a fall color display.