Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays

1. A light harvesting array, comprising:

(a) a first substrate comprising a first electrode; and

(b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I:

X 1 X m+1 ) m   (I)

wherein:

m is at least 1;

X 1 is a charge separation group having an excited-state of energy equal to or lower than that of X 2 ;

X 2 through X m+1 are chomophores; and

at least one of X 2 through X m+1 has at least one perylene group coupled thereto, and wherein said perylene group is a perylene (bis)imide group.

2. A light harvesting array according to claim 1 , wherein m is from 2 to 49.

3. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 has at least two perylene groups coupled thereto.

4. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 further has at least one of a perylene group coupled thereto at a perylene N-imide position.

5. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 further has at least one of a perylene group coupled thereto at a perylene 1, 6, 9, or 11 position.

6. A light harvesting array according to claim 1 , wherein:

m is from 2 to 49;

at least one of X 2 through X m+1 further has at least two perylene groups coupled thereto;

said perylene groups are perylene mono-imides; and

said perylene groups are coupled thereto at the perylene 1, 6, 9, 11, or N-imide positions.

7. A light harvesting array according to claim 1 , wherein at least one of X 1 through X m+1 is selected from the group consisting of chlorins, bacteriochlorins, and isobacteriochlorins.

8. A light harvesting array according to claim 1 , wherein X 1 through X m+1 are selected so that, upon injection of either an electron or hole from X 1 into said first electrode, the corresponding hole or electron from X 1 is transferred to at least X 2 .

9. A light harvesting array according to claim 1 , wherein X 1 comprises a porphyrinic macrocycle.

10. A light harvesting array according to claim 1 , wherein X 1 comprises a double-decker sandwich coordination compound.

11. A light harvesting array according to claim 1 , wherein X 2 through X m+1 comprise porphyrinic macrocycles.

12. A light-harvesting array according to claim 1 , wherein X 1 through X m+1 comprise porphyrinic macrocycles.

13. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 comprises a meso-linked porphyrinic macrocycle.

14. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 comprises a trans meso-linked porphyrinic macrocycle.

15. A light harvesting array according to claim 1 , wherein X 2 through X m+1 consist of meso-linked porphyrinic macrocycles.

16. A light harvesting array according to claim 1 , wherein X 2 through X m+1 consist of trans meso-linked porphyrinic macrocycles.

17. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 comprises a β-linked porphyrinic macrocycle.

18. A light harvesting array according to claim 1 , wherein at least one of X 2 through X m+1 comprises a trans β-linked porphyrinic macrocycle.

19. A light harvesting array according to claim 1 , wherein X 2 through X m+1 consist of β-linked porphyrinic macrocycles.

20. A light harvesting array according to claim 1 , wherein X 2 through X m+1 consist of trans β-linked porphyrinic macrocycles.

21. A light harvesting array according to claim 1 , wherein said light harvesting rods are oriented substantially perpendicularly to said first electrode.

22. A light harvesting array according to claim 1 , wherein said substrate is rigid.

23. A light harvesting array according to claim 1 , wherein said substrate is flexible.

24. A light harvesting array according to claim 1 , wherein said substrate is transparent.

25. A light harvesting array according to claim 1 , wherein said substrate is opaque.

26. A light harvesting array according to claim 1 , wherein said substrate is reflective.

27. A light harvesting array according to claim 1 , wherein said substrate is substantially planar in shape.

28. A light harvesting array according to claim 1 , wherein said electrode comprises a metallic conductor.

29. A light harvesting array according to claim 1 , wherein said electrode comprises a nonmetallic conductor.

30. A light harvesting array according to claim 1 , wherein said light-harvesting rods are intrinsic rectifiers of excited-state energy.

31. A light harvesting array according to claim 1 , wherein said light harvesting rods are intrinsic rectifiers of holes.

32. A light harvesting array according to claim 1 , wherein said light harvesting rods are not greater than 500 nanometers in length.

33. A solar cell, comprising:

(a) a light harvesting array according to claim 1 ;

(b) a second substrate comprising a second electrode, with said first and second substrate being positioned to form a space therebetween, and with at least one of (i) said first substrate and said first electrode and (ii) said second substrate and said second electrode being transparent; and

(c) an electrolyte in said space between said first and second substrates.

34. A solar cell according to claim 33 , further comprising a mobile charge carrier in said electrolyte.

35. A solar cell according to claim 33 , wherein said electrolyte comprises an aqueous electrolyte.

36. A solar cell according to claim 33 , wherein said electrolyte comprises a non-aqueous electrolyte.

37. A solar cell according to claim 33 , wherein said electrolyte comprises a polymer electrolyte.

38. A solar cell according to claim 33 , wherein said electrolyte comprises a solid.

39. A solar cell according to claim 33 , wherein said solar cell is devoid of liquid in said space between said first and second substrates.

40. A solar cell according to claim 33 , wherein X 1 is electrically coupled to said first electrode.

41. A solar cell according to claim 33 , wherein X m+1 is electrically coupled to said second electrode.

42. An electrical device, comprising:

(a) a solar cell according to claim 33 ; and

(b) a circuit electrically coupled to said solar cell.

43. An electrical device according to 42 , claim wherein said circuit comprises a resistive load.

44. A composition useful for the manufacture of a light harvesting array, comprising:

(a) a non-polar organic solvent; and

(b) from 2 microMolar to 100 milliMolar of light harvesting rods solubilized in said organic solvent, said light harvesting rods comprising a polymer of Formula I:

X 1 X m+1 ) m   (I)

wherein:

m is at least 1;

X 1 is a charge separation group having an excited-state of energy equal to or lower than that of X 2 ;

X 2 through X m+1 are chromophores; and

at least one of X 2 through X m+1 has at least one perylene group coupled thereto;

wherein said perylene group is a compound of formula IV:

wherein:

R 9 is a link to one of said chromophores;

R 1 and R 6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate and trialkyltin;

Y 2 through Y 6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin; and

wherein either (i) Y 4 is halo, ethynyl, dialkylboronate, or trialkyltin, or (ii) Y 3 is halo, ethynyl, dialkylboronate, or trialkyltin.

45. A composition according to claim 44 , wherein said solvent is selected from the group consisting of tetrahydrofuran, toluene, chloroform, chlorobenzene, xylene, dichloromethane, mesitylene, 1,1,1-trichloroethane, 2-chloronaphthalene, 1,2-dichlorobenzene, 1,1,2,2-tetrachloroethane, and mixtures thereof.

46. A composition according to claim 44 , wherein m is from 2 to 49.

47. A composition according to claim 44 , wherein at least one of X 2 through X m+1 has at least two perylene groups coupled thereto.

48. A composition according to claim 44 , wherein at least one of X 2 through X m+1 further has at least one of a perylene group coupled thereto at a perylene N-imide position.

49. A composition according to claim 44 , wherein at least one of X 2 through X m+1 further has at least one of a perylene group coupled thereto at a perylene 1, 6, 9, or 11 position.

50. A composition according to claim 44 , wherein:

m is from 2 to 49;

at least one of X 2 through X m+1 further has at least two perylene groups coupled thereto;

said perylene groups are perylene mono-imides; and

said perylene groups are coupled thereto at the perylene 1, 6, 9, 11, or N-imide positions.

51. A method of making a composition useful for the manufacture of light harvesting arrays, said composition comprising a non-polar organic solvent and from 2 microMolar to 100 milliMolar of light harvesting rods solubilized in said organic solvent, said light harvesting rods comprising a polymer of Formula I:

X 1 X m+1 ) m   (I)

wherein:

m is at least 1;

X 1 is a charge separation group having an excited-state of energy equal to or lower than that of X 2 ;

X 2 through X m+1 are chromophores; and

at least one of X 2 through X m+1 has at least one perylene group coupled thereto;

wherein said perylene group is a compound of formula IV:

wherein:

R 9 is a link to one of said chromophores;

R 1 and R 6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate and trialkyltin; and

Y 2 through Y 6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin;

wherein either (i) Y 4 is halo, ethynyl, dialkylboronate, or trialkyltin, or (ii) Y 3 is halo, ethynyl, dialkylboronate, or trialkyltin;

said method comprising the steps of:

(a) providing a mixture of X 1 through X m+1 as monomers in said organic solvent with an amine and a catalyst;

(b) polymerizing said monomers in said mixture to produce a polymer of Formula I; and then

(c) separating amine and catalyst from said mixture to provide said composition having said polymer of Formula I solubilized therein.

52. A method according to claim 51 , wherein said polymerizing step is carried out by a Glaser or Sonogashira reaction.

53. A method according to claim 51 , wherein said solvent is selected from the group consisting of tetrahydrofuran, toluene, chloroform, chlorobenzene, xylene, dichloromethane, mesitylene, 1,1,1-trichloroethane, 2-chloronaphthalene, 1,2-dichlorobenzene, 1,1,2,2-tetrachloroethane, and mixtures thereof.

54. A method according to claim 51 , wherein m is from 2 to 49.

55. A method according to claim 51 , wherein at least one of X 2 through X m+1 has at least two perylene groups coupled thereto.

56. A method according to claim 51 , wherein at least one of X 2 through X m+1 further has at least one of a perylene group coupled thereto at a perylene N-imide position.

57. A method according to claim 51 , wherein at least one of X 2 through X m+1 further has at least one of a perylene group coupled thereto at a perylene 1, 6, 9, or 11 position.

58. A method according to claim 51 , wherein:

m is from 2 to 49;

at least one of X 2 through X m+1 further has at least two perylene groups coupled thereto;

said perylene groups are perylene mono-imides; and

said perylene groups are coupled at the perylene 1, 6, 9, 11, or N-imide positions.

59. A compound according to Formula II:

wherein:

Ar is an aromatic group;

Porph is a porphyrinic macrocycle;

Peryl 1 is a first perylene group; and

Peryl 2 is a second perylene group.

60. A compound according to claim 59 , wherein Ar is selected from the group consisting of benzene, thiophene, furan, pyrrole, pyridine, naphthalene, anthracene, phenanthrene, biphenyl, indene, quinoline, pyridazine, pyrimidine, fluorene, and pyrazine.

61. A compound according to claim 59 , wherein Ar is benzene.

62. A compound according to claim 59 , wherein said perylene groups are perylene mono-imides.

63. A compound according to claim 59 , wherein said perylene groups are perylene (bis)imides.

64. A compound according to claim 59 , wherein said perylene groups are coupled to said aromatic group at the perylene N-imide position.

65. A compound according to claim 59 , wherein said perylene groups are coupled to said aromatic group at the perylene 1, 6, 9, or 11 position.

66. A compound according to claim 59 , wherein said porphyrinic macrocycle comprises a porphyrin group substituted with Ar at the 5-position, X at the 10-position, Y at the 15-position, and Z at the 20-position; wherein Y is an alkyl or aryl group; and wherein X and Z are independently selected substituents selected from the group consisting of iodo, bromo, ethynyl, 2-(trimethylsilyl)ethynyl, 4-ethynylphenyl, 4-[2-(trimethylsilyl)ethynyl]phenyl, 4-iodophenyl, 4-bromophenyl, 4,4,5 ,5-tetramethyl-1,3,2-dioxaborolan-2-yl, and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl.

67. A compound according to Formula III:

wherein:

Ar 1 is a first aromatic group;

Ar 2 is a second aromatic group;

Porph is a porphyrinic macrocycle;

Peryl 1 is a perylene group;

Peryl 2 is a second perylene group;

m is from 1 to 3; and

n is from 1 to 3.

68. A compound according to claim 67 , wherein Ar 1 and Ar 2 are each independently selected from the group consisting of benzene, thiophene, furan, pyrrole, pyridine, naphthalene, anthracene, phenanthrene, biphenyl, indene, quinoline, pyridazine, pyrimidine, fluorene, and pyrazine.

69. A compound according to claim 67 , wherein Ar 1 and Ar 2 are benzene.

70. A compound according to claim 67 , wherein said perylene groups are perylene mono-imides.

71. A compound according to claim 67 , wherein said perylene groups are perylene (bis)imides.

72. A compound according to claim 67 , wherein said perylene groups are coupled to said aromatic groups at the perylene N-imide position.

73. A compound according to claim 67 , wherein said perylene groups are coupled to said aromatic groups at the perylene 1, 6, 9, or 11 position.

74. A compound according to claim 67 , where said porphyrinic macrocycle comprises a porphyrin substituted with Ar 1 at the 5-position, X at the 10-position, Ar 2 at the 15-position, and Z at the 20-position; and wherein X and Z are independently selected substituents selected from the group consisting of iodo, bromo, ethynyl, 2-(trimethylsilyl)ethynyl, 4-ethynylphenyl, 4-[2-(trimethylsilyl)ethynyl]phenyl, 4-iodophenyl, 4-bromophenyl, 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl.

75. A compound of formula IV:

wherein:

R 1 , R 6 , and R 9 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate and trialkyltin; and

Y 2 through Y 6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin;

wherein either (i) Y 4 is halo, ethynyl, dialkylboronate, or trialkyltin, or (ii) Y 3 is halo, ethynyl, dialkylboronate, or trialkyltin.

76. The compound according to claim 75 , wherein:

Y 2 and Y 6 are H or alkyl;

Y 4 is halo, ethynyl, dialkylboronate, or trialkyltin; and

Y 3 and Y 5 are H.

77. The compound according to claim 75 , wherein Y 2 , Y 4 and Y 5 are H, Y 3 is halo, ethynyl, dialkylboronate, or trialkyltin and Y 6 is alkyl.

78. A compound of formula V:

wherein:

R 1 and R 6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin; and

R 9 is selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin.

79. A compound of formula VI:

wherein

Ar is an aromatic group; and

Y 1 and Y 2 are independently selected perylene mono-imide groups; and

X is selected from the group consisting of formyl, halo, or 5-dipyrromethane.

80. A compound according to claim 79 , wherein Ar is selected from the group consisting of benzene, thiophene, furan, pyrrole, pyridine, naphthalene, anthracene, phenanthrene, biphenyl, indene, quinoline, pyridazine, pyrimidine, fluorene, and pyrazine.

81. A compound according to claim 79 , wherein Ar is benzene.