Phenyl xanthene dyes

• US 20040242902A1
• Filed: 05/04/2004
• Published: 12/02/2004
• Est. Priority Date: 05/09/2003
• Status: Active Grant

• Current Assignee: Applied Biosystems LLC (Thermo Fisher Scientific Incorporated)
• Original Assignee: Applied Biosystems LLC (Thermo Fisher Scientific Incorporated)
• Inventors: Menchen, Steven M., Benson, Scott C., Zou, Ruiming, Lam, Joe Y.L.
• Granted Patent: US 7,491,830 B2
• Time in Patent Office: Days
• US Class Current: 549/225
• CPC Class Codes: C07D 311/82 Xanthenes
• CPC Class Codes: C07D 491/14 Ortho-condensed systems
• CPC Class Codes: C09B 11/06 Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
• CPC Class Codes: C09B 11/12 without any OH group bound to an aryl nucleus
• CPC Class Codes: C09B 11/22 containing OH groups bound to an aryl nucleus and their ethers and esters
• CPC Class Codes: C09B 11/24 Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
• CPC Class Codes: C09B 11/26 Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic phthaleins C09B11/24
• CPC Class Codes: C09B 13/00 Oxyketone dyes
• CPC Class Codes: C09B 57/00 Other synthetic dyes of known constitution
• CPC Class Codes: C09B 62/0025 Specific dyes not provided for in groups C09B62/004 - C09B62/018

Abstract

Fluorescent phenyl xanthene dyes are described that comprise any fluorescein, rhodamine or rhodol comprising a particular C9 phenyl ring. One or both of the ortho groups on the lower C9 phenyl ring is ortho substituted with a group selected from alkyl, heteroalkyl, alkoxy, halo, haloalkyl, amino, mercapto, alkylthio, cyano, isocyano, cyanato, mercaptocyanato, nitroso, nitro, azido, sulfeno, sulfinyl, and sulfino. In one embodiment, halo and/or hydroxy groups are used. Optimal dyes contain a lower C9 phenyl ring in which both ortho groups are the same and the lower ring exhibits some form a symmetry relative to an imaginary axis running from the phenyl rings point of attachment to the remainder of the xanthene dye through a point para to the point of attachment. The phenyl xanthene dyes may be activated. Furthermore, the phenyl xanthene dyes may be conjugated to one or more substances including other dyes. The phenyl xanthene dyes are useful for a number of purposes, including labels for use in automated DNA sequencing as well the formation of fluorescent “bar codes” for polymeric particles used in the multiplexed analysis of analytes.

Claims

1. A fluorescent phenyl xanthene dye comprising a fluorescein, rhodol or rhodamine that comprises a C9 phenyl ring comprising the following structure:

3. The phenyl xanthene dye of claim 1 wherein at least one of R¹¹ and R¹⁵ is selected from an alkoxy, a halo, a haloalkyl and/or a nitrile.

4. The phenyl xanthene dye of claim 1 wherein R¹¹ and R¹⁵ are selected, independently, from alkoxy, halo and/or haloalkyl groups.

5. The phenyl xanthene dye of claim 1 wherein the phenyl ring is only substituted with hydrogen, alkoxy, halo and haloalkyl groups.

6. The phenyl xanthene dye of claim 1 wherein R¹¹ and R¹⁵ are identical.

7. The phenyl xanthene dye of claim 1 wherein the phenyl ring is symmetrical relative to an imaginary axis running from the phenyl ring'"'"'s point of attachment through a point para to attachment.

8. The phenyl xanthene dye of claim 1 wherein R¹¹ and R¹⁵ are identical and R¹², R¹³, and R¹⁴ are, identically, selected from hydrogen or a substituent that is different from R¹¹ and R¹⁵.

9. The phenyl xanthene dye of claim 1 wherein R¹¹, R¹³ and R¹⁵ are identical first substituents and R¹² and R¹⁴ are, identically, selected from hydrogen or a substituent different from R¹¹, R¹³ and R¹⁵.

10. The phenyl xanthene dye of claim 1 wherein R¹¹, R¹², R¹⁴ and R¹⁵ are and R¹³ is selected from hydrogen or a substituent different from R¹¹, R¹², R¹⁴ and R¹⁵.

11. The phenyl xanthene dye of claim 1 wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical.

12. The phenyl xanthene dye of claim 1 wherein said dye is a fluorescein.

13. The phenyl xanthene dye of claim 1 wherein said dye is a rhodol.

14. The phenyl xanthene dye of claim 1 wherein said dye is a rhodamine.

15. The phenyl xanthene dye of claim 1 wherein the dye is lipid soluble due to the presence of one or more lipophilic groups.

16. The phenyl xanthene dye of claim 15 wherein the lipophilic groups are selected from (C4-C20) alkyls, (C5-C40) aryls, and/or (C6-C40) arylalkyls.

17. The phenyl xanthene dye of claim 15 wherein said dye is a rhodamine and at least one of the exocyclic amine and the exocyclic imminium nitrogens are substituted with one or more lipophilic groups.

18. The phenyl xanthene dye of claim 15 wherein said dye is a rhodol and the exocyclic amine nitrogen is substituted with one or more lipophilic groups.

19. The phenyl xanthene dye of claim 1 wherein said dye contains one or more linkers that contain a linking group capable of forming a covalent or non-covalent linkage to a second substance.

20. The phenyl xanthene dye of claim 19 wherein said second substance is selected from a biomolecule, a glass substrate, a metal substrate, and a polymer substrate.

21. The phenyl xanthene dye of claim 19 wherein said second substance is another dye and the phenyl xanthene dye is part of an energy transfer network.

22. The phenyl xanthene dye of claim 1 wherein said dye is linked to at least one second substance.

23. The phenyl xanthene dye of claim 22 wherein said second substance is selected from a biomolecule, a glass substrate, a metal substrate, and a polymer substrate.

24. The phenyl xanthene dye of claim 22 wherein said second substance is another dye and the phenyl xanthene dye is part of an energy transfer network.

25. A lipid soluble fluorescent phenyl xanthene dye comprising a fluorescein, rhodol or rhodamine that comprises a C9 phenyl ring comprising the following structure:

26. The lipid soluble phenyl xanthene dye of claim 25 where R¹¹ and R¹⁵ are selected from alkyl, heteroalkyl, alkoxy, halo, haloalkyl, amino, alkylthio, cyano, isocyano, cyanato, mercaptocyanato, nitro, and sulfinyl.

27. The lipid soluble phenyl xanthene dye of claim 25 wherein R¹², R¹³, and R¹⁴ are, independently, selected from hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, halo, haloalkyl, amino, alkylthio, cyano, isocyano, cyanato, mercaptocyanato, nitro, sulfinyl, sulfonyl, sulfonamide, carboxyl, and carboxyamide.

28. The lipid soluble phenyl xanthene dye of claim 25 wherein at least one of R¹¹ and R¹⁵ is selected from an alkoxy, halo, haloalkyl and nitrile.

29. The lipid soluble phenyl xanthene dye of claim 25 wherein both of R¹¹ and R¹⁵ are selected, independently, from alkoxy, halo and haloalkyl groups.

30. The lipid soluble phenyl xanthene dye of claim 25 wherein the phenyl ring is only substituted with hydrogen, alkoxy, halo, haloalkyl and halo groups.

31. The lipid soluble phenyl xanthene dye of claim 25 wherein R¹¹ and R¹⁵ are identical.

32. The lipid soluble phenyl xanthene dye of claim 25 wherein the phenyl ring is symmetrical relative to an imaginary axis running from the phenyl ring'"'"'s point of attachment through a point para to the attachment.

33. The lipid soluble phenyl xanthene dye of claim 25 wherein R¹¹ and R¹⁵ are identical and R¹², R¹³, and R¹⁴ are, identically, selected from hydrogen and a substituent that is different from R¹¹ and R¹⁵.

34. The lipid soluble phenyl xanthene dye of claim 25 wherein R¹¹, R¹³ and R¹⁵ are identical and R¹² and R¹⁴ are, identically, selected from hydrogen and a substituent that is different from R¹¹, R¹³ and R¹⁵.

35. The lipid soluble phenyl xanthene dye of claim 25 wherein R¹¹ , R¹², R¹⁴ and R¹⁵ are identical and R¹³ is selected from hydrogen or a substituent different from R¹¹, R¹², R¹⁴ and R¹⁵.

36. The lipid soluble phenyl xanthene dye of claim 25 wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical.

37. The lipid soluble phenyl xanthene dye of claim 25 wherein said dye is a fluorescein.

38. The lipid soluble phenyl xanthene dye of claim 25 wherein said dye is a rhodol.

39. The lipid soluble phenyl xanthene dye of claim 25 wherein said dye is a rhodamine.

40. The lipid soluble phenyl xanthene dye of claim 25 wherein the lipophilic groups are selected from (C4-C20) alkyls, (C5-C40) aryls, and/or (C6-C40) arylalkyls.

41. The lipid soluble phenyl xanthene dye of claim 40 wherein said dye is a rhodamine in which one or both of the exocyclic amine and the exocyclic imminium nitrogens are substituted with one or two lipophilic groups.

42. The lipid soluble phenyl xanthene dye of claim 40 wherein said dye is a rhodol in which the exocyclic amine nitrogen is substituted with one or two lipophilic groups.

43. The lipid soluble phenyl xanthene dye of claim 40 wherein said dye contains one or more linkers that contain a linking group capable of forming a covalent or a non-covalent linkage to a second substance.

44. The lipid soluble phenyl xanthene dye of claim 43 wherein said second substance is selected from a biomolecule, a glass substrate, a metal substrate and a polymer substrate.

45. The lipid soluble phenyl xanthene dye of claim 43 wherein said second substance is another dye and the phenyl xanthene dye is part of an energy transfer network.

46. The lipid soluble phenyl xanthene dye of claim 25 wherein said dye is linked to at least one second substance.

47. The lipid soluble phenyl xanthene dye of claim 46 wherein said second substance is selected from a biomolecule, a glass substrate, a metal substrate, and a polymer substrate.

2. The phenyl xanthene dye of claim 1 wherein R¹², R¹³, and R¹⁴ are independently selected from hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, halo, haloalkyl, amino, alkylthio, cyano, isocyano, cyanato, mercaptocyanato, nitro, sulfinyl, sulfonyl, sulfonamide, carboxyl, and carboxyamide.

48. The lipid soluble phenyl xanthene dye of claim 46 wherein said second substance is another dye and the phenyl xanthene dye is part of an energy transfer network.

49. The phenyl xanthene dye of claim 47 wherein the dye comprises core structure (II) and, additionally, the substituents therein are defined as follows:

R¹ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R¹ may be taken together with R² form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R² is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R² may be taken together with R¹ or R^2′

to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^2′

is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^2′

may be taken together with R² to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when A is —

NR^3′

R^3″

, R^2′

may be taken together with R^3′

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^3′

, when present, is selected from hydrogen, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^3′

may be taken together with R^2′

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^3″

, when present, is selected from (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^3″

may be taken together with R⁴ to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁴ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when A is —

N R^3′

R^3″

, R⁴ may be taken together with R^3″

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R⁴ may be taken together with R^4′

to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^4′

is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^4′

may be taken together with R⁴ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups,

R⁵ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b group or, alternatively, when B is —

NR^6′

R<sup>6″

+</sup>, R⁵ may be taken together with R^6″

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^6″

, when present, is selected from (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups or, alternatively R^6″

may be taken together with R⁵ to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^6′

, when present, is selected from hydrogen, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^6′

may be taken together with R⁷ to form a 5- or 6-membered ring optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁷ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or R^b groups, or, alternatively, R⁷ may be taken together with R⁸ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when B is —

NR^6′

R<sup>6″

+</sup>, R⁷ may be taken together with R^6′

to form a 5- or 6-membered ring optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁸ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R⁸ together with R⁷ may form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R¹¹ and R¹⁵ are each, independently of one another, selected from halo, (C1-C20) alkyl, haloalkyl, —

OR^y, —

SR^y, —

SOR^y, —

SO₂R^y, and nitrile;

R¹², R¹³ and R¹⁴ are each, independently of one another, selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^x is selected from —

NR^cR^c, —

OR^d, —

SR^d, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂,—

N₃, —

S(O)R^d, —

S(O)₂R^d, —

S(O)₂OR^d, —

S(O)NR^cR^c, —

S(O)₂NR^cR^c, —

OS(O)R^d, —

OS(O)₂R^d, —

OS(O)₂OR^d, —

OS(O)₂NR^cR^c, —

C(O)R^d, —

C(O)OR^d, —

C(O)NR^cR^c, —

C(NH)NR^cR^c, —

OC(O)R^d, —

OC(O)OR^d, —

OC(O)NR^cR^c and —

OC(NH)NR^cR^c;

R^y is selected from (C1-C20) alkyls or heteroalkyls optionally substituted with lipophilic substituents, (C5-C20) aryls or heteroaryls optionally substituted with lipophilic substituents and (C2-C26) arylalkyl or heteroarylalkyls optionally substituted with lipophilic substituents;

R^a is selected from hydrogen, (C1-C8) alkyl or heteroalkyl, (C5-C20) aryl or heteroaryl and (C6-C28) arylalkyl or heteroarylalkyl;

R^b is selected from —

NR^cR^c, ═

O, —

OR^d, ═

S, —

SR^d, ═

NR^d, ═

NOR^d, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, ═

N₂, —

N₃, —

S(O)R^d, —

S(O)₂R^d, —

S(O)₂OR^d, —

S(O)NR^cR^c, —

S(O)₂NR^cR^c, —

OS(O)R^d, —

OS(O)₂R^d, —

OS(O)₂OR^d, —

OS(O)₂NR^cR^c, —

C(O)R^d, —

C(O)OR^d, —

C(O)NR^cR^c, —

C(NH)NR^cR^c, —

OC(O)R^d, —

OC(O)OR^d, —

OC(O)NR^cR^c and —

OC(NH)NR^cR^c;

each R^c is independently hydrogen or R^d, or, alternatively, each R^c is taken together with the nitrogen atom to which it is bonded to form a 5 to 8-membered saturated or unsaturated ring which may optionally include one or more of the same or different additional heteroatoms and which may optionally be substituted with one or more of the same or different R^a or R^d groups;

each R^d is independently R^a or R^a substituted with one or more of the same or different R^a or R^e groups; and

each R^e is selected from —

NR^aR^a, ═

O, —

OR^a, ═

S, —

SR^a, ═

NR^a, ═

NOR^a, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, ═

N₂, —

N₃, —

S(O)R^a, —

S(O)₂R^a, —

S(O)₂OR^a, —

S(O)NR^aR^a, —

S(O)₂NR^aR^a, —

OS(O)R^a, —

OS(O)₂R^a, —

OS(O)₂OR^a, —

OS(O)₂NR^aR^a, —

C(O)R^a, C(O)OR^a, C(O)NR^aR^a, —

C(NH)NR^aR^a, —

OC(O)R^a, —

OC(O)OR^a, —

OC(O)NR^aR^a and —

OC(NH)NR^aR^a, or, alternatively, one or more of R², R^2′

, R^3′

, R^3″

, R⁴, R⁵ , R^6′

, R^6″

, R⁷, R¹², R¹³ and R¹⁴ are each, independently of one another, selected from the group consisting of —

S-LG and —

S¹-LK-S²—

CS, wherein

each S, which may be the same or different, is a direct bond or linker,

each LG, which may be the same or different, is a linking group;

each S¹ and S², independently, is a direct bond or linker,

each LK is a linkage formed from a reacted linking group, and

each CS, which may be the same or different is a conjugated substance.

50. The phenyl xanthene dye of claim 47 wherein the dye comprises core structure (III) and, additionally, the substituents therein are defined as follows:

R¹ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^b or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R¹ may be taken together with R² form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R² is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R² may be taken together with R¹ or R^2′

to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^2′

is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^2′

may be taken together with R² to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when A is —

NR^3′

R^3″

, R^2′

may be taken together with R^3′

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^3′

, when present, is selected from hydrogen, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^3′

may be taken together with R^2′

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^3″

, when present, is selected from (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^3″

may be taken together with R⁴ to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁴ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when A is —

NR^3′

R^3″

, R⁴ may be taken together with R^3″

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R⁴ may be taken together with R^4′

to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^4′

is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^4′

may be taken together with R⁴ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups,

R^5′

is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b group or, alternatively R⁵ may be taken together with R⁵ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁵ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b group or, alternatively, when B is —

NR^3′

R<sup>3″

+</sup>, R⁵ may be taken together with R^6″

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R⁵ may be taken together with R^5′

to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^6″

, when present, is selected from (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups or, alternatively R^6″

may be taken together with R⁵ to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^6′

, when present, is selected from hydrogen, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^6′

may be taken together with R^7′

to form a 5- or 6-membered ring optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^7′

is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or R^b groups, or, alternatively, when B is —

NR^3′

R<sup>3″

+</sup>, R^7′

may be taken together with R^6′

to form a 5- or 6-membered ring optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^7′

may be taken together with R⁷ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups; and

R⁷ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or R^b groups, or, alternatively, R⁷ may be taken together with R^7′

or R⁸ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups.

R⁸ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R⁸ together with R⁷ may form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R¹¹ and R¹⁵ are each, independently of one another, selected from halo, (C1-C20) alkyl, haloalkyl, —

OR^y, —

SR^y, —

SOR^y, —

SO₂R^y, and nitrile;

R¹², R¹³ and R¹⁴ are each, independently of one another, selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^x is selected from —

NR^cR^c, —

OR^d, —

SR^d, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, —

N₃, —

S(O)R^d, —

S(O)₂R^d, —

S(O)₂OR^d, —

S(O)NR^cR^c, —

S(O)₂NR^cR^c, —

OS(O)R^d, —

OS(O)₂R^d, —

OS(O)₂OR^d, —

OS(O)₂NR^cR^c, —

C(O)R^d, —

C(O)OR^d, —

C(O)NR^cR^c, —

C(NH)NR^cR^c, —

OC(O)R^d, —

OC(O)OR^d, —

OC(O)NR^cR^c and —

OC(NH)NR^cR^c;

R^y is selected from (C1-C20) alkyls or heteroalkyls optionally substituted with lipophilic substituents, (C5-C20) aryls or heteroaryls optionally substituted with lipophilic substituents and (C2-C26) arylalkyl or heteroarylalkyls optionally substituted with lipophilic substituents;

R^a is selected from hydrogen, (C1-C8) alkyl or heteroalkyl, (C5-C20) aryl or heteroaryl and (C6-C28) arylalkyl or heteroarylalkyl;

R^b is selected from —

NR^cR^c, ═

O, —

OR^d, ═

S, —

SR^d, ═

NR^d, ═

NOR^d, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, ═

N₂, —

N₃, —

S(O)R^d, —

S(O)₂R^d, —

S(O)₂OR^d, —

S(O)NR^cR^c, —

S(O)₂NR^cR^c, —

OS(O)R^d, —

OS(O)₂R^d, —

OS(O)₂OR^d, —

OS(O)₂NR^cR^c, —

C(O)R^d, —

C(O)OR^d, —

C(O)NR^cR^c, —

C(NH)NR^cR^c, —

OC(O)R^d, —

OC(O)OR^d, —

OC(O)NR^cR^c and —

OC(NH)NR^cR^c;

each R^c is independently hydrogen or R^d, or, alternatively, each R^c is taken together with the nitrogen atom to which it is bonded to form a 5 to 8-membered saturated or unsaturated ring which may optionally include one or more of the same or different additional heteroatoms and which may optionally be substituted with one or more of the same or different R^a or R^d groups;

each R^d is independently R^a or R^a substituted with one or more of the same or different R^a or R^e groups; and

each R^e is selected from —

NR^aR^a, ═

O, —

OR^a, ═

S, —

SR^a, ═

NR^a, ═

NOR^a, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, ═

N₂, —

N₃, —

S(O)R^a, —

S(O)₂R^a, —

S(O)₂OR^a, —

S(O)NR^aR^a, —

S(O)₂NR^aR^a, —

OS(O)R^a, —

OS(O)₂R^a, —

OS(O)₂OR^a, —

OS(O)₂NR^aR^a, —

C(O)R^a, —

C(O)OR^a, —

C(O)NR^aR^a, —

C(NH)NR^aR^a, —

OC(O)R^a, OC(O)OR^a, —

OC(O)NR^aR^a and —

OC(NH)NR^aR^a,

or, alternatively, one or more of R², R^2′

, R^3′

, R^3″

, R⁴, R^4′

, R⁵, R^5′

, R^6′

, R^6″

, R⁷, R^7′

, R¹², R¹³ and R¹⁴ are each, independently of one another, selected from the group consisting of—

S-LG and —

S¹-LK-S²—

CS, wherein

each S, which may be the same or different, is a direct bond or linker;

each LG, which may be the same or different, is a linking group;

each S¹ and S², independently, is a direct bond or linker;

each LK is a linkage formed from a reacted linking group, and each CS, which may be the same or different is a conjugated substance.

51. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein at least one of R¹¹ and R¹⁵ is selected from an alkoxy, halo, haloalkyl and nitrile.

52. The phenyl xanthene dye of any of claims 48, 49 and 50 wherein both of R¹¹ and R¹⁵ are selected, independently, from an alkoxy, halo and haloalkyl groups.

53. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein the R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are, independently, selected from hydrogen, alkoxy, halo and haloalkyl groups.

54. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein R¹¹ and R¹⁵ are identical.

55. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein R¹¹ and R¹⁵ are identical and R¹², R¹³, and R¹⁴ are, identically, selected from hydrogen or a substituent different than R¹¹and R¹⁵.

56. The phenyl xanthene dye of claim any one of claims 48, 49 and 50 wherein R¹¹, R¹³ and R¹⁵ are identical and R¹² and R¹⁴ are, identically, selected from hydrogen or a substituent different from R¹¹, R¹³ and R¹⁵.

57. The phenyl xanthene dye of claim any one of claims 48, 49 and 50 wherein R¹¹, R¹², R¹⁴ and R¹⁵ are and R¹³ is hydrogen or a substituent different from R¹¹, R¹², R¹⁴ and R¹⁵.

58. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are identical.

59. The phenyl xanthene dye of any one of claims 48, 49, and 50 wherein A is a hydroxyl and B is an oxo.

60. The phenyl xanthene dye of any one of claims 48, 49, and 50 wherein A is an amine and B is an oxo.

61. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein A is an amine and B is an imminium.

62. The phenyl xanthene dye of any one of claims 48, 49, and 50, wherein the dye is lipid soluble due to the presence of one or more lipophilic groups.

63. The phenyl xanthene dye of any one of claim 62 wherein the lipophilic groups are selected from (C4-C20) alkyls, (C5-C40) aryls, (C6-C40) arylalkyls.

64. The phenyl xanthene dye of any of claims 62 wherein said dye is a lipid soluble rhodamine in at least one of the exocyclic amine and the exocyclic imminium nitrogens are substituted with one or more lipophilic groups.

65. The phenyl xanthene dye of any one of claims 62 wherein said dye is a lipid soluble rhodol in which the exocyclic amine nitrogen is substituted with one or more lipophilic groups.

66. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein one of R², R^2′

, R⁴, R^4′

, R^5′

, R⁵, R^7′

, R⁷, R¹², R¹³, and R¹⁴ is selected from —

S-LG and —

S¹-LK-S²—

SC.

67. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein one of R², R^2′

, R⁴, R^4′

R^5′

, R⁵, R^7′

, R⁷, R¹², R¹³, and R¹⁴is —

S-LG.

68. The phenyl xanthene dye of claim 67 wherein —

S is a direct bond.

69. The phenyl xanthene dye of claim 67 in wherein —

S is a spacing moiety.

70. The phenyl xanthene of claim 69 wherein S is a spacing moiety selected from substituted and unsubstituted alkyldiyls, heteroalkyldiyls, aryldiyl and heteroaryldiyls.

71. The phenyl xanthene dye of claim 67 wherein -LG is an electrophilic group selected from activated esters, acrylamides, acyl azides, acyl halides, acyl nitriles, aldehydes, ketones, alkyl halides, alkyl sulfonates, anhydrides, aryl halides, aziridines, boronates, carboxylic acids, carbodiimides, diazoalkenes, epoxides, haloacetamides, halotriazines, imido esters, isocyanates, isothiocyanates, maleimides, phosphoramidites, silyl halides, sulfonate esters, and sulfonyl halides.

72. The phenyl xanthene dye of claim 67 wherein -LG is a nucleophilic group selected from amines, anilines, alcohols, phenols, thiols, hydrazines, and hydroxylamines.

73. The phenyl xanthene dye of any one of claims 48, 49 and 50 wherein one of R², R^2′

, R⁴, R^4′

, R^5′

, R⁵, R^7′

, R⁷, R¹², R¹³, and R¹⁴ is —

S¹-LK-S²—

CS.

74. The phenyl xanthene dye of claim 73 wherein S¹ and S² are, independently, spacing moieties selected from substituted and unsubstituted alkyldiyls, heteroalkyldiyls, aryldiyl and heteroaryldiyls.

75. The phenyl xanthene dye of claim 73 wherein —

CS is a polymer, glass or metal substrate.

77. The phenyl xanthene dye of claim 73 wherein —

CS is a biomolecule.

78. The phenyl xanthene dye of claim 77 wherein the biological molecule is selected from peptides, polypeptides, proteins, enzymes, receptors, antibodies, hormones, polysaccharides, carbohydrates, oligonucleotides, polynucleotides and nucleic acids.

79. The phenyl xanthene dye of claim 73, wherein —

CS is an amino acid or a nucleoside.

80. The phenyl xanthene dye of claim 73 in which —

CS is a second dye.

81. The phenyl xanthene dye of claim 80 in which the second dye is an energy transfer donor or an energy transfer acceptor.

82. The phenyl xanthene dye of claim 80 in which the second dye is selected from phenyl xanthene dyes, cyanine dyes, phthalocyanine dyes, squaraine dyes, acridine dyes, alizarene dyes, azo dyes, anthraquinine dyes, bodipy dyes, coumarin dyes, lanthanide complexes, oxazine dyes, phenazathionium dyes, phenazoxonium dyes, porphyorin dyes, pyrene dyes, pyrilium dyes, perylene dyes, phenoxazine dyes, and phenezine dyes.

83. The phenyl xanthene dye of claim 80 in which the second dye is a phenyl xanthene dye.

84. The phenyl xanthene dye of claim 80 in which the second dye is a phenyl xanthene that comprises one of core structures (I), (II) and (III).

47-1. A fluorescent phenyl xanthene dye comprising one of the following core structures:

48-2. The phenyl xanthene dye of claim 47 wherein the dye comprises core structure (I) and the substituents therein are further defined as follows:

R¹ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R¹ may be taken together with R² form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R² is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R² may be taken together with R¹, to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when A is —

NR^3′

R^3″

, R² may be taken together with R^3′

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^3′

, when present, is selected from hydrogen, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^3′

may be taken together with R² to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^3″

, when present, is selected from (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^3″

may be taken together with R⁴ to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁴ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when B is —

NR^3′

R^3″

, R⁴ may be taken together with R^3″

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁵ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b group or, alternatively, when B is —

NR^6′

R<sup>6″

+</sup>, R⁵ may be taken together with R^6″

to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^6″

, when present, is selected from (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups or, alternatively R^6″

may be taken together with R⁵ to form a 5- or 6-membered ring which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^6′

, when present, is selected from hydrogen, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R^6′

may be taken together with R⁷ to form a 5- or 6-membered ring optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁷ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or R^b groups, or, alternatively, R⁷ may be taken together with R⁸ to form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, when B is —

NR^6′

R<sup>6″

+</sup>, R⁷ may be taken together with R^6′

to form a 5- or 6-membered ring optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R⁸ is selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroaryl alkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups, or, alternatively, R⁸ together with R⁷ may form part of a benzo, naptho or polycyclic aryleno group which is optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R¹¹ and R¹⁵ are each, independently of one another, selected from halo, (C1-C20) alkyl, haloalkyl, —

OR^y, —

SR^y, —

SOR^y, —

SO₂R^y, and nitrile;

R¹², R¹³ and R¹⁴ are each, independently of one another, selected from hydrogen, R^x, (C1-C20) alkyl or heteroalkyl optionally substituted with one or more of the same or different R^b groups, (C5-C20) aryl or heteroaryl optionally substituted with one or more of the same or different R^a or suitable R^b groups and (C6-C40) arylalkyl or heteroarylalkyl optionally substituted with one or more of the same or different R^a or suitable R^b groups;

R^x is selected from —

NR^cR^c, —

OR^d, —

SR^d, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, —

N₃, —

S(O)R^d, —

S(O)₂R^d, —

S(O)₂OR^d, —

S(O)NR^cR^c, —

S(O)₂NR^cR^c, —

OS(O)R^d, —

OS(O)₂R^d, —

OS(O)₂OR^d, —

OS(O)₂NR^cR^c, —

C(O)R^d, —

C(O)OR^d, —

C(O)NR^cR^c, —

C(NH)NR^cR^c, —

OC(O)R^d, —

OC(O)OR^d, —

OC(O)NR^cR^c and —

OC(NH)NR^cR^c;

R^y is selected from (C1-C20) alkyls or heteroalkyls optionally substituted with lipophilic substituents, (C5-C20) aryls or heteroaryls optionally substituted with lipophilic substituents and (C2-C26) arylalkyl or heteroarylalkyls optionally substituted with lipophilic substituents;

R^a is selected from hydrogen, (C1-C8) alkyl or heteroalkyl, (C5-C20) aryl or heteroaryl and (C6-C28) arylalkyl or heteroarylalkyl;

R^b is selected from —

NR^cR^c, ═

O, —

OR^d, ═

S, —

SR^d, ═

NR^d, ═

NOR^d, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, ═

N₂, —

N₃, —

S(O)R^d, —

S(O)₂R^d, —

S(O)₂OR^d, —

S(O)NR^cR^c, —

S(O)₂NR^cR^c, —

OS(O)R^d, —

OS(O)₂R^d, —

OS(O)₂OR^d, —

OS(O)₂NR^cR^c, —

C(O)R^d, —

C(O)OR^d, —

C(O)NR^cR^c, —

C(NH)NR^cR^c, —

OC(O)R^d, —

OC(O)OR^d, —

OC(O)NR^cR^c and —

OC(NH)NR^cR^c;

each R^c is independently hydrogen or R^d, or, alternatively, each R^c is taken together with the nitrogen atom to which it is bonded to form a 5 to 8-membered saturated or unsaturated ring which may optionally include one or more of the same or different additional heteroatoms and which may optionally be substituted with one or more of the same or different R^a or R^d groups;

each R^d is independently R^a or R^a substituted with one or more of the same or different R^a or R^e groups; and

each R^e is selected from —

NR^aR^a, ═

O, —

OR^a, ═

S, —

SR^a, ═

NR^a, ═

NOR^a, halo, haloalkyl, —

CN, —

NC, —

OCN, —

SCN, —

NO, —

NO₂, ═

N₂, —

N₃, —

S(O)R^a, —

S(O)₂R^a, —

S(O)₂OR^a, —

S(O)NR^aR^a, —

S(O)₂NR^aR^a, —

OS(O)R^a, —

OS(O)₂R^a, —

OS(O)₂OR^a, —

OS(O)₂NR^aR^a, —

C(O)R^a, —

C(O)OR^a, —

C(O)NR^aR^a, —

C(NH)NR^aR^a, —

OC(O)R^a, OC(O)OR^a, —

OC(O)NR^aR^a and —

OC(NH)NR^aR^a

or, alternatively, one or more of R², R^3′

, R^3″

, R⁴, R⁵, R^6′

, R^6″

, R⁷, R¹², R¹³ and R¹⁴ are each, independently of one another, selected from the group consisting of —

S-LG and —

S¹-LK-S²—

CS, wherein

each S, which may be the same or different, is a direct bond or linker;

each LG, which may be the same or different, is a linking group;

each S¹ and S², independently, is a direct bond or linker;

each LK is a linkage formed from a reacted linking group, and

each CS, which may be the same or different is a conjugated substance.