Photo-oxidants for energy conversion and catalysts and systems and methods of using same

Patent metadata

Field	Value
Publication number	US-11117911-B2
Application number	US-201816000554-A
Country	US
Kind code	B2
Filing date	Jun 5, 2018
Priority date	Jun 5, 2017
Publication date	Sep 14, 2021
Grant date	Sep 14, 2021

Abstract

High-potential photo-oxidants are provided with a supermolecule structure at least including a conjugated macrocycle linked to a metal complex. The conjugated macrocycle is electron-accepting relative to hydrogen or bears electron withdrawing substituents such as fluoroalkyl, fluoroaryl, fluoro, halo, cyano, or nitro. The metal complex is also electron-accepting relative to hydrogen or bears electron withdrawing substituents such as fluoroalkyl, fluoroaryl, fluoro, halo, cyano, or nitro. The linker can be thynyl, vinyl, thiophenyl, diethynylaryl, divinylaryl, diethynyl(unsaturated heterocycloalkenyl), divinyl(unsaturated heterocycloalkenyl), diethynyl(unsaturated heterocycloalkynyl), or divynyl(unsaturated heterocycloalkynyl). A specific implementation is an ethyne-bridged eDef-Rutpy-(porphinato)Zn(II) (eDef-RuPZn) supermolecule.

First claim

What is claimed is:

1. A compound of a formula comprising:
A - L - B
wherein:
A is a conjugated macrocycle bearing electron withdrawing substituents or is electron-accepting relative to hydrogen;
B is a metal complex bearing electron withdrawing substituents or is electron-accepting relative to hydrogen; and
L is ethynyl, vinyl, thiophenyl, diethynylaryl, divinylaryl, diethynyl(unsaturated heterocycloalkenyl), divinyl(unsaturated heterocycloalkenyl), diethynyl(unsaturated heterocycloalkynyl), or divynyl(unsaturated heterocycloalkynyl).

2. The compound of claim 1 , wherein the macrocycle of the conjugated macrocycle is porphyrin, porphycene, rubyrin, rosarin, hexaphyrin, sapphyrin, chlorophyl, chlorin, phthalocyanine, porphyrazine, bacteriochlorophyl, pheophytin, or texaphyrin.

3. The compound of claim 1 , wherein the conjugated macrocycle is a porphyrin complexed to metal atom M 1 .

4. The compound of claim 3 , wherein M 1 is Zn, Mg, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Cd, Ge, Sn, Hf, Ta, W, Re, Os, Ir, Pt, Au, or Pb.

5. The compound of claim 1 , wherein A is a conjugated macrocycle bearing an electron withdrawing substituent of perfluoroalkyl or perfluoroaryl.

6. The compound of claim 1 , wherein the metal complex is a (polypyridyl)metal species.

7. The compound of claim 6 , wherein a polypyridyl ligand of the (polypyridyl)metal species is terpyridyl or bipyridyl.

8. The compound of claim 1 , wherein the metal complex is a (poly-heterocyclic)metal species.

9. The compound of claim 1 wherein the metal complex is neutral.

10. The compound of claim 1 , wherein the metal complex is charged.

11. The compound of claim 1 , wherein the metal complex comprises a transition metal.

12. The compound of claim 1 , wherein the metal complex comprises a Group 8 transition metal.

13. The compound of claim 1 , wherein the metal complex comprises Fe, Ru, Os, Re, Ir, Rh, or Pt.

14. The compound of claim 1 , wherein L is ethynyl.

15. The compound of claim 1 , wherein the formula is
A - L - B.

16. The compound of claim 1 , wherein the formula is
A - L - B - L - A.

17. The compound of claim 1 , wherein the formula is
B - L - A - L - B.

18. The compound of claim 1 , wherein A is eDef-Rutpy-(porphinato)Zn(II), B is eDef-RuPZn, and L is ethyne.

19. A compound of a formula comprising:
A - L - B
wherein:
A is a conjugated macrocycle bearing electron withdrawing substituents or is electron-accepting relative to hydrogen;
B is a metal complex bearing electron withdrawing substituents or is electron-accepting relative to hydrogen; and
L is ethynyl, diethynylaryl, diethynyl(unsaturated heterocycloalkenyl), or diethynyl(unsaturated heterocycloalkynyl).

20. A compound of a formula comprising:
A - L - B
wherein:
A is a conjugated macrocycle bearing an electron withdrawing substituent selected from the group consisting of fluoroaryl, fluoroalkyl, fluoro, halo, cyano, and nitro;
B is a metal complex bearing an electron withdrawing substituent selected from the group consisting of fluoroaryl, fluoroalkyl, fluoro, halo, cyano, and nitro; and
L is ethynyl, vinyl, thiophenyl, diethynylaryl, divinylaryl, diethynyl(unsaturated heterocycloalkenyl), divinyl(unsaturated heterocycloalkenyl), diethynyl(unsaturated heterocycloalkynyl), or divynyl(unsaturated heterocycloalkynyl).

Assignees

• Univ Duke

Inventors

• Therien Michael
• Jiang Ting
• Polizzi Nicholas
• Rawson Jeffrey

Classifications

• B01J31/1815 Primary

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title

• B01J2540/225

  comprising perfluoroalkyl groups or moieties · CPC title

• B01J2531/0216

  Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp · CPC title

• B01J2531/0244

  Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds · CPC title

• B01J2531/025

  Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles · CPC title