# US 9,040,689 B2 · Compounds useful as ligands and particularly as organic chromophores for complexing lanthanides and applications thereof

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- Number: US 9,040,689 B2
- Document ID: US9040689B2
- Status: Granted
- Kind: B2
- Application number: 12/733,675
- Filed: 2008-09-17
- Published: 2011-05-12
- Granted: 2015-05-26
- Earliest claimed: 2007-09-17
- Assignees: Commissariat a l'Energie Atomique
- Applicants: Marion Giraud; Renaud Demadrille; Marinella Mazzanti; Eugen Sorin Andreiadis
- Inventors: Marion Giraud; Renaud Demadrille; Marinella Mazzanti; Eugen Sorin Andreiadis
- Web page: https://patentgrep.com/patent/US9040689B2

## CPC

- H10K 85/351: {Metal complexes comprising lanthanides or actinides, e.g. comprising europium}
- C07D 401/04: directly linked by a ring-member-to-ring-member bond
- C07D 401/14: containing three or more hetero rings
- C07D 409/14: containing three or more hetero rings
- C07F 7/0814: {said ring is substituted at a C ring atom by Si}
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 2101/10: Triplet emission
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The invention relates to the use of compounds comprising at least one 2-(1H-tetrazol-5-yl)pyridine unit, of formula (I) below: as ligands for lanthanides and, more especially, as organic chromophores for complexing these elements. It also relates to lanthanide complexes using these compounds as complexing organic chromophores, and to new compounds containing one or more 2-(1H-tetrazol-5-yl)pyridine units, which are useful as ligands for lanthanides and, in particular, as organic chromophores for complexing these elements. Applications: photonics and optoelectronics, especially for forming light-emitting devices such as electroluminescent diodes; biology, as for example for the preparation of luminescent probes.

## Claims

### Claim 1

A process for complexing a lanthanide with an organic chromophore, comprising putting the lanthanide in contact with the organic chromophore to form a complex, the organic chromophore being a compound of formula (II):
wherein:
either a group of formula:
wherein:
R1 is (a) a hydrogen atom; (b) a halogen atom; (c) a 5-membered aromatic ring or a 6-membered aromatic ring, the ring comprising one or more heteroatoms or one or more non-cyclic substituents; (d) a sequence of at least two 5-membered aromatic rings or a sequence of at least two 6-membered aromatic rings, the rings being bonded to one another by a covalent bond and at least one of the rings optionally comprising one or more heteroatoms or one or more non-cyclic substituents; or (e) a linear or branched C1 to C12 hydrocarbon group optionally comprising one or more heteroatoms; and
R2 is (a) a carboxylic acid group; (b) a 5-membered aromatic ring or a 6-membered aromatic ring, the ring optionally comprising one or more heteroatoms or one or more non-cyclic cyclic substituents; or (c) a 2-(1H-tetrazol-5-yl)pyridine unit;
or Y is (a) a non-aromatic ring optionally comprising one or more heteroatoms or one or more substituents; or (b) a group —(CH2)p—Z where p is an integer from 1 to 6 and Z is a non-aromatic ring, optionally comprising one or more heteroatoms or one or more substituents;
whereby the lanthanide is complexed with the organic chromophore.

### Claim 2 (depends on 1)

The process of claim 1, wherein Y is a group of formula —(CH2)p—Z where p is 1 or 2 and Z is a 5-membered to 9-membered non-aromatic ring.

### Claim 3 (depends on 2)

The process of claim 2, wherein Z is a 9-membered non-aromatic ring comprising 2 to 5 heteroatoms.

### Claim 4 (depends on 3)

The process of claim 3, wherein Z is a triazacyclononane ring or a tetraazacyclononane ring.

### Claim 5 (depends on 1)

The process of claim 1, wherein the compound comprises one of formulae (II-a) to (II-j):

### Claim 6 (depends on 1)

The process of claim 1, wherein the lanthanide is europium, terbium or neodymium.

### Claim 7

A complex, comprising at least one compound of formula (II):
wherein:
n is an integer from 1 to 5; and
either Y is a group of formula:
wherein
R1 is (a) a hydrogen atom; (b) a halogen atom; (c) a 5-membered aromatic ring or a 6-membered aromatic ring, the ring comprising one or more heteroatoms or one or more non-cyclic substituents; (d) a sequence of at least two 5-membered aromatic rings or a sequence of at least two 6-membered aromatic rings, the rings being bonded to one another by a covalent bond and at least one of the rings optionally comprising one or more heteroatoms or one or more non-cyclic substituents; or (e) a linear or branched C1 to C12 hydrocarbon group optionally comprising one or more heteroatoms; and
R2 is (a) a carboxylic acid group; (b) a 5-membered aromatic ring or a 6-membered aromatic ring, the ring optionally comprising one or more heteroatoms or one or more non-cyclic cyclic substituents; or (c) a 2-(1H-tetrazol-5-yl)pyridine unit;
or Y is (a) a non-aromatic ring optionally comprising one or more heteroatoms or one or more substituents or (b) a group —(CH2)p—Z where p is an integer from 1 to 6 and Z is a non-aromatic ring, optionally comprising one or more heteroatoms or one or more substituents;
and a lanthanide complexed with the compound.

### Claim 8 (depends on 7)

The complex of claim 7, wherein Y is —(CH2)p—Z where p is 1 or 2 and Z is a 5-membered to 9-membered non-aromatic ring.

### Claim 9 (depends on 8)

The complex of claim 8, wherein Z is a 9-membered non-aromatic ring comprising 2 to 5 hetero-atoms.

### Claim 10 (depends on 9)

The complex of claim 9, wherein Z is a triazacyclononane ring or a tetraazacyclononane ring.

### Claim 11 (depends on 7)

The complex of claim 7, wherein the compound comprises one of formulae (II-a) to (II-j):

### Claim 12 (depends on 7)

The complex of claim 7, wherein the lanthanide is selected from europium, terbium and neodymium.