Half-phthalocyanine-like chelates and synthesis thereof

Patent metadata

Field	Value
Publication number	US-9273078-B2
Application number	US-201414561955-A
Country	US
Kind code	B2
Filing date	Dec 5, 2014
Priority date	Dec 5, 2013
Publication date	Mar 1, 2016
Grant date	Mar 1, 2016

Abstract

Half-phthalocyanine-like chelates, such as bis(iminoisoindolinyl)azomethene (BIAM), bis(oxoisoindolinyl) azomethene (BOAM), are provided, as well as chelates based thereon. Methods for synthesizing and synthetically modifying the novel chelate compounds are also provided. The half-phthalocyanine-like chelates have useful properties, particularly with regard to UV-visible absorption and emission as well as electron or energy transfer.

First claim

What is claimed is:

1. A compound represented by the structure:

where M is selected from the group consisting of boron, gallium, phosphorus, rhenium, ruthenium, cobalt, and chromium, where each L is independently selected from ligands that form a coordination complex with M, where n is an integer from 0 to 4, X 1 and X 2 are independently selected from the group consisting of oxygen, sulfur, NR a , and C(R b ) 2 , wherein R a and each R b are independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups, and where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently selected from the group consisting of C 1 -C 30 alkyl, C 1 -C 30 alkenyl, C 1 -C 30 alkenyl, C 1 -C 30 aryl, C 1 -C 30 alkoxy, C 1 -C 30 phenoxy, C 1 -C 30 thioalkyl, C 1 -C 30 thioaryl, C 1 -C 30 C(O)OR 11 , N(R 12 )(R 13 ), C(O)N(R 11 )(R 12 ), F, Cl, Br, NO 2 , CN, acyl, carboxylate, and hydroxyl moieties, and where R 11 , R 12 and R 13 are independently selected from the group consisting of hydrogen, C 1 -C 30 alkyl, and C 1 -C 30 aryl moieties, or where two or more R groups, R 1 -R 8 , may together be a cyclic or heterocyclic moiety.

2. The compound of claim 1 , wherein each L is independently selected from pyridine, N-methyl imidazole, and phenyl groups.

3. The compound of claim 1 , wherein the compound is a bis(iminoisoindolinyl)azomethene complex with rhenium or boron.

4. The compound of claim 1 , wherein the compound is a bis(oxoisoindolyl)azomethene complex with rhenium or boron.

5. A chromophoric chelate comprising a compound that is composed of two isoindoline moieties coordinated through the isoindolinyl nitrogen to a central atom, a bridging nitrogen atom that is covalently bonded to a carbon atom that is alpha to the isoindolinyl nitrogen in the 5-member ring of each isoindoline moiety, and a substituent that is doubly bonded to one or both of the alternate alpha carbons.

6. The compound of claim 5 , wherein the central atom is an element that is capable of templating the formation of a chelate.

7. The compound of claim 6 , wherein the substituent is selected from the group consisting of oxygen, sulfur, NR a and CR b , where R a and each R b are independently selected from hydrogen, an alkyl group, and an aryl group.

8. The compound of claim 5 , wherein the chelate further comprises ligands that are coordinated to the central atom and prevent the formation of a macrocycle.

9. A method for preparing a compound of claim 1 , the method comprising the step of reacting ingredients including a metal-based or main group-based Lewis acid and an isoindoline having at least one imino group in an alpha position, in the presence of a Bronsted-Lowry base, and optionally in the presence of a solvent.

10. The method of claim 9 , wherein the ingredients further include a second isoindoline having at least one imino group in an alpha position.

11. The method of claim 9 , wherein the ingredients further include a coordinating ligand compound.

12. The method of claim 9 , wherein the step of reacting occurs in the substantial absence of water.

13. The method of claim 9 , wherein the step of reacting occurs in the presence of water.

14. The compound of claim 1 , wherein M is rhenium or boron, each L is independently selected from pyridine groups, phenyl groups, and N-methyl imidazole groups, n is 1, X 1 and X 2 are each independently either oxygen or an imine group, and each R 1 -R 8 is independently selected from the group consisting of hydrogen, alkyl groups, and cyano groups.

15. The compound of claim 1 , wherein the compound is bis(iminoisoindolinyl)azomethene, bis(oxoisoindolinyl)azomethene, or a chelate thereof.

16. The method of claim 9 , wherein the method may be represented by Scheme 2A or 2B below:

where each S is a labile group.

17. The method of claim 9 , wherein the Lewis acid is selected from the group consisting of boron trifluoride, phenyl boronic acid, and pentacarbonylchlororhemium, triphenylboron.

18. The method of claim 17 , wherein the isoindoline is a substituted or unsubstituted 1,3-diiminoisoindoline.

Assignees

• Ziegler Christopher J
• Crandall Laura
• Herrick Richard S
• Univ Akron

Inventors

• Ziegler Christopher J
• Crandall Laura
• Herrick Richard S

Classifications

• C07F15/06

  Cobalt compounds · CPC title

• C07F13/00 Primary

  Compounds containing elements of Groups 7 or 17 of the Periodic Table · CPC title

• C07F5/02

  Boron compounds · CPC title

• C07F9/6521

  Six-membered rings · CPC title

• C07F9/65211

  Chemistry & Metallurgy · mapped topic