Compositions and methods of promoting organic photocatalysis
The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization.
1. A compound, or a salt or solvate thereof, selected from the group consisting of:
wherein:
each occurrence of R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O)2(phenyl),
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R,
wherein:
if the compound is
then
each occurrence of R is independently selected from the group consisting of C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, substituted phenyl, —O(C 2 -C 6 alkyl), —NO 2 , —C(═O)OH, —C(═O)O(C 2 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
if the compound is
then
each occurrence of R is independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 2 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
if the compound is
then
each occurrence of R 1 is independently selected from the group consisting of 1-naphthyl and 2-naphthyl, each of which is independently substituted with at least one R.
2. The compound of claim 1 , wherein R 1 is 1-naphthyl or R 1 is phenyl substituted by at least one substituent selected from the group consisting of CF 3 and C(═O)OH.
3. The compound of claim 2 , wherein the compound is selected from the group consisting of:
4. The compound of claim 1 , having the structure of
wherein
R 1 is independently selected from the group consisting of 1-naphthyl and 2-naphthyl, each of which is independently substituted with at least one R; and
R 2 and R 3 are independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R.
5. The compound of claim 1 , wherein if the compound is
wherein R 2 and R 3 are independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R,
then R 1 is 1-naphthyl.
6. The compound of claim 5 , having the structure:
7. The compound of claim 1 , wherein the compound has the structure:
wherein
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R; and
each occurrence of R is independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 2 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl).
8. The compound of claim 7 , wherein the compound is
9. A compound, or a salt or solvate thereof, having a structure selected from the group consisting of:
wherein:
each occurrence of R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl),
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R.
10. The compound of claim 9 , having the structure
wherein
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R.
11. The compound of claim 9 , having the structure of:
wherein R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R.
12. A compound, or a salt or solvate thereof, having a structure selected from the group consisting of:
wherein R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl).