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EP-4735461-A2 - ALKYLATED BODIPY COMPOUND AND METHODS OF USING THE ALKYLATED BODIPY COMPOUND

EP4735461A2EP 4735461 A2EP4735461 A2EP 4735461A2EP-4735461-A2

Abstract

A compound having a structure according to Formula (I) or Formula (II) is disclosed, wherein R 1 , R 2 , R 3 , R 4 , Ar, X 1 , X 2 , and Z are defined herein. The compound can be particularly useful as a Type I photoinitiator. Curable compositions and methods of using the compounds are also described.

Inventors

  • PAGE, ZACHARIAH A.
  • CHUNG, Kun-You

Assignees

  • Board of Regents, The University of Texas System

Dates

Publication Date
20260506
Application Date
20240610

Claims (20)

  1. 1. A compound having a structure according to Formula (I) or Formula (II) wherein in the foregoing Formulas, X 1 is B or Ga; X 2 is independently at each occurrence hydrogen, Cl, Br, or I; Z is carbon or nitrogen; R 1 is independently at each occurrence a substituted or unsubstituted Ci-6 alkyl group, optionally substituted with one or more in-chain or pendent sulfur atoms, optionally wherein each occurrence of R 1 can combine to form a cycloalkyl group; R 2 is a substituted or unsubstituted Ci-6 alkyl group or a substituted or unsubstituted C6-20 aryl group; R 3 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-20 aryl group; R 4 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-20 aryl group; and Ar is a substituted or unsubstituted fused aryl group optionally substituted with one or more in-chain or pendent heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur; provided that when each occurrence of X 2 is I, each occurrence of R 1 is methyl, and each occurrence of R 3 and R 4 is methyl, R 2 is not a -CH2OH group, a -CH2OCH2PI1 group, or a group having the structure when each occurrence of X 2 is hydrogen, each occurrence of R 1 is methyl, and each occurrence of R 3 and R 4 is methyl, R 2 is not a -CFFBr group, a -CH2CI group, a phenyl group, a p-tolyl group, a -CH2OCH2PI1 group, or a group having the structure when each occurrence of X 2 is hydrogen, each occurrence of R 1 is methyl, and each occurrence of R 3 and R 4 is hydrogen, R 2 is not a phenyl group or a 2,4,6-trimethyl phenyl group.
  2. 2. The compound of claim 1, wherein X 1 is B.
  3. 3. The compound of claim 1, wherein Z is carbon.
  4. 4. The compound of claim 1, having a structure according to Formula (I), wherein each occurrence of X 2 is Br, Cl, or hydrogen, preferably Br or hydrogen, more preferably Br.
  5. 5. The compound of claim 1, wherein each occurrence of R 1 is a substituted or unsubstituted C1-6 alkyl group.
  6. 6. The compound of claim 1, wherein at least one occurrence of R 1 is a substituted or unsubstituted C1-6 alkyl group substituted with one or more in-chain or pendent sulfur atoms, preferably wherein each occurrence of R 1 is a C1-6 alkyl thioether group.
  7. 7. The compound of claim 1, wherein R 2 is a substituted or unsubstituted C1-6 alkyl group, preferably a halogenated C1-6 alkyl group or a hydroxyl-substituted C1-6 alkyl group.
  8. 8. The compound of claim 1, having a structure according to Formula (I), wherein each occurrence of R 3 and R 4 is an unsubstituted C1-6 alkyl group, preferably a methyl group.
  9. 9. The compound of claim 1, having a structure according to Formula (II), wherein Ar is a substituted or unsubstituted fused aryl group substituted with one or more in-chain heteroatoms selected from the group consisting of oxygen and sulfur.
  10. 10. The compound of claim 1, wherein X 1 is Ga.
  11. 11. The compound of claim 10, having a structure according to Formula (II), wherein R 1 , R 2 , R 3 , and R 4 are substituted or unsubstituted C1-6 alkyl groups, and each occurrence of X 2 is Br.
  12. 12. The compound of claim 1, wherein the compound is:
  13. 13. The compound of claim 1, wherein the compound is:
  14. 14. The compound of claim 1, having the structure according to Formula (I), wherein X 1 is B; X 2 is independently at each occurrence hydrogen or Br; Z is carbon; R 1 is independently at each occurrence a substituted or unsubstituted Ci-6 alkyl group, optionally substituted with one or more in-chain or pendent sulfur atoms, optionally wherein each occurrence of R 1 can combine to form a cycloalkyl group; R 2 is a substituted or unsubstituted Ci-6 alkyl group or a substituted or unsubstituted C6-12 aryl group; R 3 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-12 aryl group; R 4 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-12 aryl group.
  15. 15. A curable composition comprising: a photoinitiator comprising the compound of claim 1 ; an ethylenically unsaturated compound; and optionally a crosslinker.
  16. 16. A cured composition derived from the curable composition of claim 15.
  17. 17. A process for converting a reactant to a reaction product, the method comprising exposing a reaction mixture to light having a wavelength of 400 to 1000 nm, preferably 450 to 750 nm to provide the reaction product, wherein the reaction mixture comprises: the reactant; and a photoinitiator comprising the compound of claim 1.
  18. 18. A process for photopolymerization, the process comprising: exposing a reaction mixture to light having a wavelength of 400 to 1000 nm, preferably 450 to 750 nm to provide a polymer comprising repeating units derived from an ethylenically unsaturated compound, wherein the reaction mixture comprises: the ethylenically unsaturated compound; and a photoinitiator comprising the compound of claim 1.
  19. 19. The process of claim 18, wherein the photoinitiator comprises a compound having the structure:
  20. 20. The process of claims 18, wherein the reaction mixture further comprises a crosslinker.

Description

ALKYLATED BODIPY COMPOUND AND METHODS OF USING THE ALKYLATED BODIPY COMPOUND CROSS REFERENCE TO RELATED APPLICATION This application claims priority to U.S. Provisional Patent Application No. 63/523,426, filed on June 27, 2023, the contents of which is hereby incorporated by reference in its entirety. FEDERAL RESEARCH STATEMENT This invention was made with government support under Grant no. CHE2107877 awarded by the National Science Foundation. The government has certain rights in the invention. BACKGROUND [0001 ] Visible light has emerged as a promising stimulus to drive polymerizations for a variety of applications, particularly in the biomedical and advanced manufacturing (e.g., 3D printing) arenas. This arises in part from the spatiotemporal control, high penetration depth, low energy, and discrete absorption it offers to enable benign and wavelength-selective fabrication of multifunctional soft materials. A major hurdle limiting the implementation of visible light driven polymerizations is its low efficiency relative to ultraviolet-light driven processes, arising from a difference in mechanism to generate initiating species for polymerization, such as radicals, which has been predominantly restricted to bimolecular processes for long wavelength light (>500 nm) (i.e., Type II, photoredox), and unimolecular processes for short wavelength light (<500 nm) (i.e., Type I, photolysis). In turn, the requirement for cocatalysts such as tertiary amines, iodonium salts, and/or borate salts in Type II processes are intrinsically diffusion limited, slowing overall photocuring rates, increasing complexity and cost, and potentially decreasing biocompatibility of the concomitant resin formulations. Therefore, long wavelength (>500 nm) Type I photoinitiators offer a compelling alternative yet remain elusive. [0002] It would therefore be advantageous to provide long wavelength (e.g., >500 nanometers (nm)) Type I photoinitiators. Such photoinitiators would be particularly useful for visible light driven polymerizations. SUMMARY [0003] An aspect of the present disclosure is a compound having a structure according to Formula (I) or Formula (II) wherein in the foregoing Formulas, X1 is B or Ga; X2 is independently at each occurrence hydrogen, Cl, Br, or I; Z is carbon or nitrogen; R1 is independently at each occurrence a substituted or unsubstituted C1-6 alkyl group, optionally substituted with one or more in-chain or pendent sulfur atoms, optionally wherein each occurrence of R1 can combine to form a cycloalkyl group; R2 is a substituted or unsubstituted C1-6 alkyl group or a substituted or unsubstituted C6-20 aryl group; R3 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-20 aryl group; R4 is independently at each occurrence hydrogen, a substituted or unsubstituted Ci-6 alkyl group, or a substituted or unsubstituted C6-20 aryl group; and Ar is a substituted or unsubstituted fused aryl group optionally substituted with one or more in-chain or pendent heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur; provided that when each occurrence of X2 is I, each occurrence of R1 is methyl, and each occurrence of R3 and R4 is methyl, R2 is not a -CH2OH group, a -CH2OCH2PI1 group, or a group having the structure when each occurrence of X2 is hydrogen, each occurrence of R1 is methyl, and each occurrence of R3 and R4 is methyl, R2 is not a -C FBr group, a -CH2CI group, a phenyl group, a p-tolyl *— Q group, a -CH2OCH2PI1 group, or a group having the structure ; and when each occurrence of X2 is hydrogen, each occurrence of R1 is methyl, and each occurrence of R3 and R4is hydrogen, R2 is not a phenyl group or a 2,4,6-trimethyl phenyl group. [0004] Another aspect is a curable composition comprising: a photoinitiator comprising a compound having a structure according to Formula (I) or Formula (II) wherein in the foregoing Formulas, X1 is B or Ga; X2 is independently at each occurrence hydrogen, Cl, Br, or I; Z is carbon or nitrogen; R1 is independently at each occurrence a substituted or unsubstituted C1-6 alkyl group optionally substituted with one or more in-chain or pendent heteroatoms selected from the group consisting of oxygen and sulfur, optionally wherein each occurrence of R1 can combine to form a cycloalkyl group; R2 is a substituted or unsubstituted C1-6 alkyl group or a substituted or unsubstituted C6-20 aryl group; R3 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-20 aryl group; R4 is independently at each occurrence hydrogen, a substituted or unsubstituted C1-6 alkyl group, or a substituted or unsubstituted C6-20 aryl group; and Ar is a substituted or unsubstituted fused aryl group optionally substituted with one or more in-chain or pendent heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur