Azaallyl-containing moieties as chelate for metals

1. A compound of formula II

wherein

A is optionally substituted phenyl or optionally substituted pyridinyl;

D is optionally substituted phenyl or optionally substituted pyridinyl;

is a delocalized bond;

R 1 and R 2 are each independently selected from hydrogen, halogen, an optionally substituted (C 1 -C 20 ) hydrocarbon, —C(═O)—R 10 , —C(═O)NR 10 R 11 , —C(═O)OR 10 , —C(═S)NR 10 R 11 , —C(═S)—R 10 and —C(═S)OR 10 ; or

R 1 and R 2 , together with the carbons to which they are attached, may be an optionally substituted non-aromatic ring;

R 10 and R 11 are each selected independently from hydrogen, an optionally substituted (C 1 -C 20 ) hydrocarbon and a polar, neutral moeity;

represents a coordinate covalent bond to a metal; and

M is a metal that forms additional bonds to A and D;

with the proviso that, when two azaallyl moieties are present, A and D are both unsubstituted pyridinyl, and R 1 and R 2 are both hydrogen, the metal cannot be zinc, iron, cobalt, or nickel.

2. A compound of formula IIa according to claim 1 wherein M has one additional substituent bond:

3. A compound according to claim 2 wherein the additional substituent bonded to M is selected from NR 20 R 21 and OR 22 ;

R 20 and R 21 are each selected independently in each occurrence from Si[(C 1 -C 6 )alkyl] 3 and (C 1 -C 20 ) hydrocarbon; and

R 22 is (C 1 -C 20 ) hydrocarbon.

4. A compound according to claim 1 wherein M has three additional substituent bonds as in formula III:

5. A compound according to claim 4 of formula IIIa or IIIb:

wherein

R 1′ and R 2′ are each independently in each occurrence selected from hydrogen, halogen, an optionally substituted (C 1 -C 20 ) hydrocarbon, —C(═O)—R 10 , —C(═O)NR 10 R 11 , —C(═O)OR 10 ,—C(═S)NR 10 R 11 , —C(═S)—R 10 and —C(═S)OR 10 ; or

R 1′ and R 2′ , together with the carbons to which they are attached, may be an optionally substituted non-aromatic ring;

R 1a and R 2a are each independently selected from hydrogen and (C 1 -C 6 )alkyl;

A′ is an optionally substituted phenyl or optionally substituted pyridinyl; and

D′ is an optionally substituted phenyl or optionallt substituted pyridinyl.

6. A compound according to claim 1 wherein said metal is chosen from lithium, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, molybdenum, ruthenium, rhodium and iridium.

7. A compound according to claim 1 wherein A and D are each optionally substituted with one or more substituents selected from hydrogen, (C 1 -C 6 )alkyl, halogen, alkoxy, nitro, nitroso, haloalkyl, haloalkoxy, oxaalkyl, acyl and cyano.

8. A compound according to claim 1 wherein R 1 and R 2 are each selected independently from hydrogen, (C 1 -C 6 )alkyl, fluoro(C 1 -C 6 )alkyl, —C(═O)—R 10 and —C(═O)NR 10 R 11 .

9. A compound according to claim 8 wherein R 2 is selected from hydrogen and (C 1 -C 6 )alkyl and, when R 1 is —C(═O)—R 10 or C(═O)NR 10 R 11 , R 10 is selected from hydrogen and (C 1 -C 6 )alkyl, and R 11 is (C 1 -C 20 ) hydrocarbon optionally substituted with fluorine.

10. A compound according to claim 1 wherein A and D are each optionally substituted with one or more substituents selected from hydrogen, (C 1 -C 6 )alkyl, halogen, alkoxy, nitro, nitroso, haloalkyl, haloalkoxy, oxaalkyl, acyl and cyano.

11. A compound according to claim 5 wherein

M is chosen from lithium, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, molybdenum, ruthenium, rhodium and iridium;

A, D, A′ and D′ are each independently selected from optionally substituted phenyl or optionally substituted pyridinyl; each optionally substituted with one or more substituents selected from hydrogen, (C 1 -C 6 )alkyl, halogen, alkoxy, nitro, nitroso, haloalkyl, haloalkoxy, oxaalkyl, acyl and cyano;

R 1 and R 2 are each independently selected from hydrogen, (C 1 -C 6 )alkyl, —C(═O)—R 10 and —C(═O)NR 10 R 11 ; and

R 1a and R 2a are each independently selected from hydrogen and (C 1 -C 6 )alkyl.

12. A compound according to claim 11 wherein

A, D, A′ and D′ are each independently chosen from optionally substituted phenyl and optionally substituted pyridinyl;

R 1 is —C(═O)NR 10 R 11 ;

R 2 is hydrogen or (C 1 -C 6 )alkyl;

R 10 is selected from H and (C 1 -C 6 )alkyl; and

R 11 is (C 1 -C 20 ) hydrocarbon optionally substituted with fluorine.

13. A photovoltaic cell comprising a compound of formula II:

wherein

A is optionally substituted phenyl or optionally substituted pyridinyl;

D is optionally substituted phenyl or optioally substituted pyridinyl;

is a delocalized bond;

R 1 and R 2 are each independently selected from hydrogen, halogen, an optionally substituted (C 1 -C 20 ) hydrocarbon, —C(═O)—R 10 , —C(═O)NR 10 R 11 , —C(═O)OR 10 , —C(═S)NR 10 R 11 ,—C(═S)—R 10 and —C(═S)OR 10 ; or

R 1 and R 2 , together with the carbons to which they are attached, may be an optionally substituted non-aromatic ring;

R 10 and R 11 are each selected independently from hydrogen, an optionally substituted (C 1 -C 20 ) hydrocarbon and a polar, neutral moeity;

M is a metal that forms additional bonds to A and D; and

represents a coordinate covalent bond to a metal.

14. An organic light emitting diode comprising a compound of formula II:

wherein

A is optionally substituted phenyl or optionally substituted pyridinyl;

D is optionally substituted phenyl or optionally substituted pyridinyl;

is a delocalized bond;

R 1 and R 2 are each independently selected from hydrogen, halogen, an optionally substituted (C 1-C 20) hydrocarbon, —C(═O)—R 10 , —C(═O)NR 10 R 11 ,—C(═O)OR 10 , —C(═S)NR 10 R 11 ,—C(═S)—R 10 and —C(═S)OR 10 ; or

R 1 and R 2 , together with the carbons to which they are attached, may be an optionally substituted non-aromatic ring;

R 10 and R 11 are each selected independently from hydrogen, an optionally substituted (C 1 -C 20 ) hydrocarbon, and a polar, neutral moiety;

M is a metal that forms additional bonds to A and D; and

represents a coordinate covalent bond to a metal.

15. A compound according to claim 6 of formula

wherein M is selected from lithium, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, molybdenum, ruthenium, rhodium and iridium.

16. A compound according to claim 15 of formula

17. A compound according to claim 2 of formula

18. A compound according to claim 1 selected from:

(smif) 2 V,

(smif) 2 Cr,

(smif) 2 Mn,

(smif) 2 Mg,

(smif)CrN(SiMe 3 ) 2 ,

(smif)FeN(SiMe 3 ) 2 ,

(smif)FeOCHPh 2 ,

(smif)(dpma)Fe,

Li(smif),

Na(smif),

Na t BuNCOsmif,

( t BuNCOsmif) 2 Fe,

(2,6- i PrPhNCOsmif) 2 Fe,

(smif)(dpma)Ti,

(smif) 2 Ti,

(κ-N am ,N py 2 -2,3,5,6-tetrakis(pyridin-2-yl)piperazin-1-yl)(smif)Ti,

Lithium[(k-C,N am ,N im ,N py 3 -1,2-bis(pyridin-2-yl)-2-(pyridin-2-ylmethyleneamino)ethyl)(pyridin-2-ylmethideyl)amido)Ti(smif)],

(smif) 2 Ru,

((κ-N am ,N im ,N py -1,2-bis(pyridine-2-yl)-2-(pyridine-2-methyleneamino)ethyl)(pyridine-2-ylmethyl)amido)Mo(smif),

19. A crystalline compound of formula II:

wherein

A is optionally substituted pyridinyl or optionally substituted phenyl;

D is optionally substituted pyridinyl or optionally substituted phenyl;

is delocalized bond;

R 1 and R 2 are each independently selected from hydrogen, halogen, an optionally substituted (C 1 -C 20 ) hydrocarbon, —C(═O)—R 10 , —C(═O)NR 10 R 11 ,—C(═O)OR 10 , —C(═S)NR 10 R 11 ,—C(═S)—R 10 and —C(═S)OR 10 ; or

R 1 and R 2 , together with the carbons to which they are attached, may be an optionally substituted non-aromatic ring;

R 10 and R 11 are each selected independently from hydrogen, an optionally substituted (C 1 -C 20 ) hydrocarbon, and a polar, neutral moiety;

M is a metal that forms additional bonds to A and D; and

represents a coordinate covalent bond to a metal.

20. The crystalline compound according to claim 19 selected from:

(smif) 2 V,

(smif) 2 Cr,

(smif) 2 Mn,

(smif) 2 Fe,

(smif) 2 Co,

(smif) 2 Ni,

(smif) 2 Mg,

(smif)CrN(SiMe 3 ) 2 ,

(smif)FeN(SiMe 3 ) 2 ,

(smif)FeOCHPh 2 ,

(smif)(dpma)Fe,

Li(smif),

Na(smif),

Na t BuNCOsmif,

( t BuNCOsmif) 2 Fe,

(2,6- i PrPhNCOsmif) 2 Fe,

(smif)(dpma)Ti,

(smif) 2 Ti,

(κ-N am ,N py 2 -2,3,5,6-tetrakis(pyridin-2-yl)piperazin-1-yl)(smif)Ti,

Lithium[(k-C,N am ,N im ,N py 3 -1,2-bis(pyridin-2-yl)-2-(pyridin-2-ylmethyleneamino)ethyl)(pyridin-2-ylmethideyl)amido)Ti(smif)],

(smif) 2 Ru,

((κ-N am ,N im ,N py -1,2-bis(pyridine-2-yl)-2-(pyridine-2-methyleneamino)ethyl)(pyridine-2-ylmethyl)amido)Mo(smif),

21. A compound according to claim 1 , wherein A is optionally substituted pyridinyl and D is optionally substituted pyridinyl.

22. A compound according to claim 1 , wherein A is optionally substituted phenyl and D is optionally substituted phenyl.