Luminescent and dispersible hybrid materials combining ionic and coordinate bonds in molecular crystals
View Patent ↗Inorganic-organic hybrid structures having both ionic and coordinate bonds in a molecular cluster possessing the features of structural diversity, high luminescence and stability, and excellent dispersibility, suitable for use as lighting phosphors.
1. A phosphor compound of Cu m X m+n (L) n wherein:
X is a halide,
L is a cationic organic ligand, wherein at least two atoms of the ligand are heteroatoms independently selected from the group consisting of N, O and S, one of the at least two atoms is positively charged N and the other of the at least two atoms is coordinated to Cu,
m is an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, and
n is an integer selected from the group consisting of 1, 2, 3, 4, and 5,
wherein the positively charged N is sp3 hybridized, and
wherein the other of the at least two atoms is sp 2 hybridized N.
2. A method of emitting a visible light comprising
(a) placing a chip coated with a phosphor compound of claim 1 in conductive contact between an anode and a cathode within a reflective cavity; and
(b) passing a current from the anode to the cathode.
3. The method of claim 2 , wherein the phosphor compound emits red, green, yellow, orange, pink, or blue light wavelengths.
4. The method of claim 2 , wherein the phosphor compound displays intense luminescence with internal quantum yields (IQYs) greater than 60%.
5. A method of preparing the phosphor compound of claim 1 , comprising the steps of
(a) providing a compound of CuX, wherein X is a halogen,
(b) mixing said CuX with the ligand L in a solution; and
(c) isolating said phosphor compound.
6. The method of claim 5 , further comprising introducing triphenylphosphine in step (b).
7. The phosphor compound of claim 1 , wherein X is I.
8. The phosphor compound of claim 1 , wherein m is selected from the group consisting of 2, 3, 4, 5, 6, 7, and 8, and n is 2.
9. The phosphor compound of claim 1 , wherein the positively charged N is bonded to at least three groups independently selected from C1-C10 alkyls, said alkyls optionally substituted with one or more groups selected from halogen, —OR 1 , —SR 1 , —C 1 -C 4 SR 1 , —NO 2 , —CN and —NR a R b , wherein R 1 at each occurrence is independently hydrogen (H) or C 1 -C 4 alkyl, and R a and R b are independently hydrogen or C 1 -C 4 alkyl.
10. The phosphor compound of claim 1 , wherein the positively charged N is bonded to three alkyl groups independently selected from methyl, ethyl, isopropyl, butyl, said alkyls optionally substituted with one or more chlorine or bromine.
11. The phosphor compound of claim 1 , wherein the other of the at least two atoms is a ring atom of benzotriazole, said benzotriazole optionally substituted with one or more substituents selected from the group consisting of C1-C10 alkyl, halogen, —OR 1 , —SR 1 , —C 1 -C 4 SR 1 , —NO 2 , —CN and —NR a R b , wherein R 1 at each occurrence is independently hydrogen (H) or C 1 -C 4 alkyl, and R a and R b are independently hydrogen or C 1 -C 4 alkyl.
12. The phosphor compound of claim 1 , wherein the copper is coordinated to no more than 3 iodides.
13. The phosphor compound of claim 1 , wherein the copper is coordinated to three iodides.
14. The phosphor compound of claim 1 , wherein the ligand is selected from the group consisting of 1-(1H-benzo[d] [1,2,3]triazol-1-yl)-N,N,N-tri-methylmethanaminium (bttmm), N-((1H-benzo[d] [1,2,3]triazol-1-yl)methyl)-N,N-di-methyl ethanaminium (btmdme), N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-di-butylbutan-1-aminium (btmdb), 3-(1H-benzo[d] [1,2,3]triazol-1-yl)-N,N,N-trimethyl-propan-1-aminium (bttmp), 5-(1H-benzo[d] [1,2,3]triazol-1-yl)-N,N,N-trimethyl-pentan-1-aminium (bttmpe), 2-(1H-benzo[d] [1,2,3]triazol-1-yl)-N,N,N-triethylethan-1-aminium (btte), 2-(1H-benzo[d] [1,2,3]triazol-1-yl)-N,N,N-trimethylethan-1-aminium (bttme), 2-(1H-benzo[d] [1,2,3]triazol-1-yl)-N-ethyl-N,N-dimethylethan-1-aminium (btedm), N-((1H-benzo[d] [1,2,3]triazol-1-yl)methyl)-N,N-dimethylpropan-2-aminium (btmdp), 4-(1H-benzo[d] [1,2,3]triazol-1-yl)-N,N,N-trimethylbutan-1-aminium (bttmbu), and 6-(2H-benzo[d] [1,2,3]triazol-2-yl)-N,N,N-trimethylhexan-1-aminium (bttmhe).
15. The phosphor compound of claim 1 , which is selected from the group consisting of Cu 4 I 6 (tpp) 2 (bttmm) 2 , Cu 4 I 6 (tpp)2(btmdme)2, Cu 6 I 8 (btmdb)2, 1D-Cu 2 Br 3 (bttmp), 1D-Cu 2 I 3 (bttmpe), 1D-Cu 2 I 3 (btte), 1D-Cu 4 I 6 (bttme) 2 , 1D-Cu 4 I 6 (btedm) 2 , 1D-Cu 6 I 8 (btmdp) 2 , 1D-Cu 6 I 8 (bambu) 2 , and 1D-Cu 6 I 8 (bttmhe) 2 .
16. A light-emitting diode characterized by a die in conductive contact with an anode and a cathode, said die comprising the phosphor compound according to claim 1 .
17. A phosphor compound of Cu m X m+n (L) n wherein:
X is a halide,
L is a cationic organic ligand, wherein at least two atoms of the ligand are heteroatoms independently selected from the group consisting of N, O and S, one of the at least two atoms is positively charged N and the other of the at least two atoms is coordinated to Cu,
m is an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, and
n is an integer selected from the group consisting of 1, 2, 3, 4, and 5,
wherein the positively charged N is sp3 hybridized, and
wherein the compound is in a 1D, 2D or 3D crystalline lattice structure.
18. The phosphor compound of claim 17 , wherein the other of the at least two atoms is sp 3 hybridized N.
19. The phosphor compound of claim 17 , wherein the positively charged N is bonded to at least three groups independently selected from C1-C10 alkyls, said alkyls optionally substituted with one or more groups selected from halogen, —OR 1 , —C 1 -C 4 SR 1 , —NO 2 , —CN and —NR a R b , wherein R 1 at each occurrence is independently hydrogen (H) or C 1 -C 4 alkyl, and R a and R b are independently hydrogen or C 1 -C 4 alkyl.
20. The phosphor compound of claim 17 , wherein the ligand is selected from the group consisting of 1-benzyl-1,4-diazabicyclo[2.2.2]octan-1-ium ((bz-ted), 1-(3-chloro-propyl)-1,4-diazabicyclo[2.2.2]octan-1-ium ((3-Cl-pr-ted), 1-propyl-1,4-diazabi-cyclo[2.2.2]octan-1-ium (pr-ted), 1-(2-bromoethyl)-1,4-diazabi-cyclo [2.2.2]octan-1-ium (2-Br-et-ted), 1-isopropyl-1,4-diazabicyclo[2.2.2] octan-1-ium (i-pr-ted), and 1-butyl-1,4-di-azabicyclo[2.2.2]octan-1-ium (bu-ted).
21. The phosphor compound of claim 17 , which the compound is selected from the group consisting of Cu 3 I 5 (bz-ted) 2 , Cu 4 I 6 (3-Cl-pr-ted) 2 , Cu 4 I 6 (pr-ted) 2 , Cu 4 I 6 (2-Br-et-ted) 2 , Cu 4 I 6 (i-pr-ted) 2 , and Cu 6 I 8 (bu-ted) 2 .