METAL COMPLEXES, METHODS, AND USES THEREOF
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.