Porphyrin compositions
View Patent ↗Novel metal porphyrin compositions useful as organic phosphors are provided. The novel compositions are prepared from commercially available porphyrin-containing starting materials. In one instance a novel palladium-containing porphyrin composition having a number average molecular weight of greater than 12,000 grams per mole was prepared from 5,10,15,20-tetrakis(3′,5′-di(hydroxy)phenyl)-21H-23H-porphyrin by reaction first with palladium(II) acetylacetonate, followed by reaction with 2-bromo-2-methylpropionyl bromide, and subsequent group transfer reaction of the alpha-bromo ester groups with 9,9-dioctyl-2-vinylfluorene in the presence of CuBr as a radical initiator. The product polymer exhibited a number average molecular weight of 12,884 grams per mole, a weight average molecular weight of 14,338 grams per mole, and a robust red phosphorescent emission. Porphyrin containing copoylmers comprising structural units derived from 9,9-dioctyl-2-vinylfluorene and 9-anthracenylmethyl methacrylate were prepared in a similar fashion.
1. A composition comprising heterocyclic structure I
wherein M is a divalent, trivalent or tetravalent metal ion; “a” is 0, 1, 2, or a non-zero fraction having a value between 0 and 1; Y is independently at each occurrence a charge balancing counterion; R 1 and R 2 are independently at each occurrence a hydrogen, a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, a C 2 -C 20 aromatic radical, or R 1 and R 2 may together form a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical; R 3 is independently at each occurrence an organic radical having structure II
wherein Ar 1 is a C 2 -C 50 aromatic radical; L 1 is a C 1 -C 2 -aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; F is independently at each occurrence a structural unit derived from an olefin monomer of formula III,
R 4 and R 5 are independently hydrogen, C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; L 2 is a bond, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 6 is hydrogen, halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
“n” is independently at each occurrence an integer from 1 to 200;
Q is independently at each occurrence a hydrogen, a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and
“m” is independently at each occurrence an integer from 1 to 10.
2. The composition according to claim 1 , wherein “a” is 0, and M is selected from the group consisting of Pd 2+ and Pt 2+ .
3. The composition according to claim 1 , wherein “a” is 0, and M is Pt 2+ .
4. The composition according to claim 1 , wherein “a” is 0, and M is Pd 2+ .
5. The composition according to claim 1 , wherein “a” is 0; M is selected from the group consisting of Pd 2+ and Pt 2+ ; R 1 and R 2 are H; Ar 1 is an aromatic radical of formula XII;
L 1 is a divalent aliphatic radical having structure XIII;
F is a moiety having structure XIV
wherein R 4 and R 5 are independently at each occurrence hydrogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical, and R 6 is independently at each occurrence a hydrogen, a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
“n” is independently at each occurrence an integer from 2 to 10;
Q is Br; and
“m” is 1 or 2.
6. The composition according to claim 1 , wherein “a” is 0; M is selected from the group consisting of Pd 2+ and Pt 2+ ; R 1 and R 2 are H; Ar 1 is an aromatic radical selected from the group consisting of divalent aromatic radicals XI and XII;
L 1 is a divalent aliphatic radical having structure XIII;
F is a moiety having structure XV
wherein R 4 is independently at each occurrence hydrogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; L 2 is a bond, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 6 is independently at each occurrence a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
“b” is independently at each occurrence 0, 1, or 2;
“c” is a number from 0 to 10;
“n” is independently at each occurrence an integer from 2 to 10;
Q is Br; and
“m” is 1 or 2.
7. The composition according to claim 1 , said composition having a number average molecular weight in a range from 1000 grams per mole to 500,000 grams per mole.
8. The composition according to claim 1 , said composition having a number average molecular weight in a range from 1000 grams per mole to 25,000 grams per mole.
9. The composition according to claim 1 , said composition having a number average molecular weight in a range from 2000 grams per mole to 10,000 grams per mole.
10. The composition according to claim 1 , wherein the group Q is a C 9 cycloaliphatic radical having structure XVI
11. An organic phosphor comprising heterocyclic structure I
wherein M is a divalent, trivalent or tetravalent metal ion; “a” is 0, 1, 2, or a non-zero fraction having a value between 0 and 1; Y is independently at each occurrence a charge balancing counterion; R1 and R2 are independently at each occurrence a hydrogen, a halogen, a C1-C20 aliphatic radical, a C3-C20 cycloaliphatic radical, a C2-C20 aromatic radical, or R1 and R2 may together form a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical; R3 is independently at each occurrence an organic radical having structure II
wherein Ar1 is a C2-C50 aromatic radical; L1is a C1-C20 aliphatic radical, a C3-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; F is independently at each occurrence a structural unit derived from an olefin monomer of formula III,
R 4 and R 5 are independently hydrogen, C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; L 2 is a bond, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 6 is hydrogen, halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
“n” is independently at each occurrence an integer from 1 to 200;
Q is independently at each occurrence a hydrogen, a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and
“m” is independently at each occurrence an integer from 1 to 10.
12. The organic phosphor according to claim 11 , wherein “a” is 0, and M is selected from the group consisting of Pd 2+ and Pt 2+ .
13. The organic phosphor according to claim 11 , wherein “a” is 0, and M is Pt 2+ .
14. The organic phosphor according to claim 11 , wherein “a” is 0, and M is Pd 2+ .
15. The organic phosphor according to claim 11 , wherein “a” is 0; M is selected from the group consisting of Pd 2+ and Pt 2+ ; R 1 and R 2 are H; Ar 1 is an aromatic radical of formula XII;
L 1 is a divalent aliphatic radical having structure XIII;
F is a moiety having structure XIV
wherein R 4 and R 5 are independently at each occurrence hydrogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical, and R 6 is independently at each occurrence a hydrogen, a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
“n” is independently at each occurrence an integer from 2 to 10;
Q is Br; and
“m” is 1 or 2.
16. The organic phosphor according to claim 11 , wherein “a” is 0; M is selected from the group consisting of Pd 2+ and Pt 2+ ; R 1 and R 2 are H; Ar 1 is an aromatic radical selected from the group consisting of divalent aromatic radicals XI and XII;
L 1 is a divalent aliphatic radical having structure XIII;
F is a moiety having structure XV
wherein R 4 is independently at each occurrence hydrogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical, and R 6 is independently at each occurrence a halogen, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; L 2 is a bond, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
“b” is independently at each occurrence 0, 1, or 2;
“c” is a number from 0 to 10;
“n” is independently at each occurrence an integer from 2 to 10;
Q is Br; and
“m” is 1 or 2.
17. The organic phosphor according to claim 11 , said composition having a number average molecular weight in a range from 1000 grams per mole to 500,000 grams per mole.
18. The organic phosphor according to claim 11 , said composition having a number average molecular weight in a range from 2000 grams per mole to 10,000 grams per mole.
19. The organic phosphor according to claim 11 , wherein the group Q is a C 9 cycloaliphatic radical having structure XVI
20. The organic phosphor according to claim 11 , wherein the phosphor is characterized by a red phosphorescence.