Method of making axially fluorinated-phthalocyanines with an aprotic fluoride compound
Disclosed is a method of making axially fluorinated metal phthalocyanines and their use in photovoltaic applications.
1. A method of making an axially fluorinated metal phthalocyanine, the method comprising:
(a) obtaining a composition comprising an aprotic fluoride compound, a solvent, and a compound having the following structure:
X m Y n -MPc; and
(b) heating the composition for a sufficient period of time to produce an axially fluorinated metal phthalocyanine having the following structure:
F m Y n -MPc,
where
X and Y are each individually Cl, Br, I, or —OH,
m is 1 or 2,
n is 0 or 1,
M is a trivalent or tetravalent metal, and
Pc is a phthalocyanine,
wherein the aprotic fluoride compound has the following structure:
Z(F) o ,
wherein Z is a group I or II metal, a tetra alkylated ammonium ion, or a tetra alkylated phosphonium ion, and o is 1 or 2.
2. The method of claim 1 , wherein Z is a group I metal selected from Cs, Rb, K, Na, or Li, or more preferably Cs, Rb, or K.
3. The method of claim 1 , wherein Z is a group II metal selected from Ba, Sr, Ca, Mg, or Be, or more preferably Ba, Sr, or Ca.
4. The method of claim 1 , wherein X is Cl, m is 1 or 2, and n is 0.
5. The method of claim 1 , wherein m is 1 and n is 1.
6. The method of claim 1 , wherein M is a Group III metal selected from the group consisting of Al, Ga, or In.
7. The method of claim 1 , wherein M is a Group IV metal selected from the group consisting of Si, Ge, or Sn.
8. The method of claim 1 , wherein the produced axially fluorinated metal phthalocyanine has the following structure:
where
R 1 , R 2 , R 3 , and R 4 are each individually a hydrogen, a hydrocarbon, or a halogen, and
p is an integer from 0 and 4.
9. The method of claim 8 , wherein R 1 to R 4 are each individually a substituted or un-substituted hydrocarbon.
10. The method of claim 9 , wherein the hydrocarbon is a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl group.
11. The method of claim 8 , wherein R 1 to R 4 are each individually a halogen selected from F, Cl, Br, or I.
12. The method of claim 1 , wherein the composition further comprises a chelating agent.
13. The method of claim 12 , wherein the chelating agent is a glycol, glycol mono ether, glycol bis ether, polyethylene glycol, polyethylene glycol mono ether, polyethylene glycol bis ether or a crown ether.
14. The method of claim 13 , wherein the crown ether is 18-crown-6 or dicyclohexyl-18-crown-6, dibenzo-18-crown-6, 15-crown-5, 12-crown-4, benzo-15-crown-5, benzo-18-crown-6, 4-aminobenzo-18-crown-6, 4 ′-nitrobenzo-15-crown-5 or the like.
15. The method of claim 1 , wherein the aprotic fluoride compound and the compound having the structure X m Y n -MPc are each partially or fully solubilized in the composition.
16. The method of claim 15 , wherein the chelating agent is partially or fully solubilized in the composition.
17. The method of claim 1 , wherein the solvent is an aprotic solvent.
18. The method of any one of claim 1 , wherein the composition is heated to a temperature of 30 to 250° C. for 1 to 600 minutes.
19. The method of claim 1 , wherein the composition in step (a) comprises 0.5 to 45% wt. of aprotic fluoride compound, and 0.1 to 50% wt. of the compound having the structure X m Y n -MPc.
20. The method of claim 1 , further comprising purifying or isolating the produced compound.
21. The method of claim 1 , wherein the composition in step (a) does not include a protic compound or does not include a protic fluoride compound or does not include an acid.
22. The method of claim 21 , wherein the protic fluoride compound is hydrogen fluoride.
23. The method of claim 1 , wherein the method does not produce hydrogen fluoride or hydrofluoric acid as a by-product or produces only trace amounts of said hydrogen fluoride or hydrochloric acid.
24. A process for making a photoactive layer on a substrate, wherein the photoactive layer comprises an axially fluorinated metal phthalocyanine, the process comprising depositing the axially fluorinated metal phthalocyanine on at least a portion of a surface of the substrate, wherein the axially fluorinated metal phthalocvanine is obtained by:
(a) obtaining a composition comprising an aprotic fluoride compound, a solvent, and a compound having the following structure:
X m Y n -MPc; and
(b) heating the composition for a sufficient period of time to produce an axially fluorinated metal phthalocyanine having the following structure:
F m Y n -MPc,
where
X and Y are each individually Cl, Br, I, or —OH,
m is 1 or 2,
n is 0 or 1,
M is a trivalent or tetravalent metal, and
Pc is a phthalocyanine,
wherein the aprotic fluoride compound has the following structure:
Z(F) o,
wherein Z is a group I or II metal, a tetra alkylated ammonium ion, or a tetra alkylated phosphonium ion, and o is 1 or 2.
25. A composition comprising:
(a) an aprotic fluoride compound, wherein the aprotic fluoride compound has the following structure:
Z(F) o ,
wherein Z is a group I or II metal, a tetra alkylated ammonium ion, or a tetra alkylated phosphonium ion, and o is 1 or 2;
(b) a solvent; and
(c) a compound having the following structure:
X m Y n -MPc; and
where
X and Y are each individually Cl, Br, I, or —OH,
m is 1 or 2,
n is 0 or 1,
M is a trivalent or tetravalent metal, and
Pc is a phthalocyanine.