High molecular extinction coefficient metal dyes

Patent metadata

Field	Value
Publication number	US-9716240-B2
Application number	US-73594209-A
Country	US
Kind code	B2
Filing date	Feb 27, 2009
Priority date	Feb 27, 2008
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

The present invention relates to novel compounds that are useful as ligands in organometallic dyes. More particularly, the invention relates to dyes comprising the compounds, said dyes being sensitizing dyes useful in solar cell technology. According to an embodiment, the present invention discloses new ruthenium dyes and their application in dye-sensitized solar cells (DSC). The referred ruthenium dyes with new structural features can be easily synthesized, show more than 85% light-to-electricity conversion efficiency and a higher than 9% cell efficiency.

First claim

The invention claimed is:

1. A dye of formula (35):
ML 1 L 2 (L 3 ) 2   (35)

wherein:
M is a metal atom selected from Ru, Os, Ir, Re, Rh, and Fe;

L 1 is a ligand selected from the compounds of formula (1):

wherein
R 1 is selected from the group consisting of the moieties of formulae (4)-(25) to (28)-(33):

wherein n is ≧1;
wherein A of a moiety according to any one of formulae (4)-(6), (12), (14), (15), (18) and (23)-(25) is selected from O atom or S atom, each said A in a same moiety being selected from the same atom; and
wherein, in moiety according to any one of formulae (7)-(11), (13), (16), (17) and (19)-(22), A is selected from O atom and B is selected from S atom; or
wherein, in moiety according to any one of formulae (7)-(11), (13), (16), (17) and (19)-(22), A is selected from S atom and B is selected from O atom;

wherein, in moiety (28), X is selected from any one of C, Si, Ge, Sn or Pb;
wherein substituents R 2 represent, independently, hydrogen, halogen, hydroxyl, sulfhydryl, nitryl, cyanate, isocyanate, amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl, wherein said alkyl, alkenyl, alkynyl may be linear, branched or cyclic, and wherein said amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl may be further substituted, and
wherein one or more carbon atom in said alkyl, alkenyl, alkynyl, and aryl may be replaced by any heteroatom and/or group selected from the group of —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, SO 2 —, —S(O) 2 O—, —N═, —P═, —NR′—, —PR′—, —P(O)(OR′)—, —P(O)(OR′)O—, —P(O)(NR′R′)—, —P(O)(NR′R′)O—, P(O)(NR′R′)NR′—, —S(O)NR′—, and —S(O) 2 NR′, with R′ being H, a C1-C6 alkyl, optionally partially or totally perfluorinated, and/or a phenyl or a monocyclic aromatic heterocycle, optionally partially or totally perfluorinated;

wherein Ar is a substituted or unsubstituted ar-diyl devoid of any heteroatom;
wherein R 3 to R 24 represent, independently, hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, aralkyl, alkylthio, alkyl halide or halogen; and
wherein carbon atoms at positions 3, 3′, 5, 5′ and 6, 6′ of the 2,2′-bipyridine structure of formula (1) may be further substituted;
L 2 is an anchoring ligand;
L 3 is a spectator ligand.

2. The dye according to claim 1 , wherein said spectator ligand L 3 may be selected, independently, from the group consisting of H 2 O, —Cl, —Br, —I, —CN, —NCO, —NCS and —NCSe.

3. The dye according to claim 1 , wherein the anchoring ligand L 2 is a bi-pyridine compound of formula (36):

wherein R 30 and R 31 are independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aryl, said alkyl, alkenyl and/or aryl being substituted or unsubstituted, and from anchoring groups —COOH, —PO 3 H 2 , —PO 4 H 2 , —SO 3 H 2 , SO 4 H 2 , —CONHOH − , acetylacetonate, deprotonated forms of the aforementioned and chelating anchoring groups with Π-conducting character; with the proviso that at least one of the substituents R 30 and R 31 comprises an anchoring group.

4. The dye according to claim 1 , wherein L 2 is bi-pyridine ligand of formula (37)

wherein A 1 and A 2 are optional and, if present, are independently selected from the group consisting of an aromatic mono- and bicyclic ring system optionally comprising one or more heteroatoms, and R 32 and R 33 are independently selected from H and from the anchoring groups —COOH, —PO 3 H 2 , —PO 4 H 2 , —SO 3 H 2 , SO 4 H 2 , —CONHOH, acetylacetonate, deprotonated forms of the aforementioned and chelating anchoring groups with Π-conducting character selected from an oxyme, dioxyme, hydroxyquinoline, salicylate and α-keto-enolate group, provided that at least one of R 32 and R 33 is an anchoring group.

5. The dye according to claim 1 , which is compound (41) below:

6. The dye according to claim 1 , wherein L 1 is selected from the group consisting of a compound according to any one of formula (II), (III), (IV) and (VI) below:

wherein substituents R 2 represent, independently, hydrogen, halogen, hydroxyl, sulfhydryl, nitryl, cyanate, isocyanate, amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl, wherein said alkyl, alkenyl, alkynyl may be linear, branched or cyclic, and wherein said amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl may be further substituted, and
wherein one or more carbon atom in said alkyl, alkenyl, alkynyl, and aryl may be replaced by any heteroatom and/or group selected from the group of —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, SO 2 —, —S(O) 2 O—, —N═, —P═, —NR′—, —PR′—, —P(O)(OR′)—, —P(O)(OR′)O—, —P(O)(NR′R′)—, —P(O)(NR′R′)O—, P(O)(NR′R′)NR′—, —S(O)NR′—, and —S(O) 2 NR′, with R′ being H, a C1-C6 alkyl, optionally partially or totally perfluorinated, and/or a phenyl or a monocyclic aromatic heterocycle, optionally partially or totally perfluorinated.

7. The dye according to claim 1 , wherein the anchoring ligand L 2 is a bi-pyridine compound of formula (36):

wherein R 30 and R 31 are independently selected from the group consisting of H, alkyl, alkenyl, alkynyl and aryl, said alkyl, alkenyl and/or aryl being substituted or unsubstituted, and from anchoring groups —COOH, —PO 3 H 2 , —PO 4 H 2 , —SO 3 H 2 , SO 4 H 2 , —CONHOH − , acetylacetonate, deprotonated forms of the aforementioned and chelating anchoring groups with Π-conducting character; with the proviso that at least one of the substituents R 30 and R 31 comprises an anchoring group; and
wherein said spectator ligand L 3 may be independently selected from the group consisting of H 2 O, —Cl, —Br, —I, —CN, —NCO, —NCS and —NCSe.

Assignees

• Gao Feifei
• Wang Yuan
• Zhang Jing
• Wang Peng
• Zakeeruddin Shaik Mohammad
• Graetzel Michael
• Ecole Polytechnique Fed De Lausanne (Epfl)

Inventors

• Gao Feifei
• Wang Yuan
• Zhang Jing
• Wang Peng
• Zakeeruddin Shaik Mohammad
• Graetzel Michael

Classifications

• H01L51/0086 Primary

  Electricity · mapped topic

• C07F15/0053 Primary

  without a metal-carbon linkage · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• C09B57/10 Primary

  Metal complexes of organic compounds not being dyes in uncomplexed form · CPC title

• H01G9/2013

  the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide · CPC title