Organoboron Compounds and Methods of Making Same

• US 20160046652A1
• Filed: 03/25/2014
• Published: 02/18/2016
• Est. Priority Date: 03/25/2013
• Status: Active Grant

• Current Assignee: Jiasheng Lu, Suning Wang
• Original Assignee: Jiasheng Lu
• Inventors: Wang, Suning, Lu, Jiasheng, Ko, Soo-Bying, McDonald, Sean Michael, Yang, Dengtao
• Granted Patent: US 10,301,328 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C07F 15/0086 Platinum compounds
• CPC Class Codes: C07F 5/02 Boron compounds
• CPC Class Codes: C07F 5/022 without C-boron linkages
• CPC Class Codes: C09K 11/025 non-luminescent particle coatings or suspension media
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1033 with oxygen
• CPC Class Codes: C09K 2211/1037 with sulfur
• CPC Class Codes: C09K 2211/104 with other heteroatoms
• CPC Class Codes: C09K 2211/1044 containing two nitrogen atoms as heteroatoms
• CPC Class Codes: C09K 2211/1048 with oxygen
• CPC Class Codes: C09K 2211/1055 with other heteroatoms
• CPC Class Codes: C09K 2211/107 with other heteroatoms
• CPC Class Codes: C09K 2211/1085 with other heteroatoms
• CPC Class Codes: C09K 2211/1096 containing other heteroatoms
• CPC Class Codes: C09K 2211/185 of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: G03F 7/20 Exposure; Apparatus therefor photographic printing apparatus for making copies G03B27/00
• CPC Class Codes: G03G 5/0653 containing five relevant rings
• CPC Class Codes: G03G 5/0659 containing more than seven relevant rings
• CPC Class Codes: H10K 2101/10 Triplet emission
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/322 : comprising boron
• CPC Class Codes: H10K 85/346 : comprising platinum
• CPC Class Codes: H10K 85/657 : Polycyclic condensed heteroaromatic hydrocarbons
• CPC Class Codes: H10K 85/6572 : comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
• CPC Class Codes: H10K 85/658 : Organoboranes
• CPC Class Codes: Y02E 10/549 : Organic PV cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides organoboron precursors and facile photoirradiation and/or heating methods of making corresponding elimination products. Some elimination products are polycyclic aromatic molecules wherein a number of aromatic C—C moieties have been replaced by a B—N moiety to form azaborine compounds with interesting properties such as electronic, photophysical, luminescent, as well as chemical properties. Examples of polymer films that were doped with such compounds are shown wherein irradiated portions of the polymer film luminesce. The invention further provides methods of producing photoluminescence and electroluminescence, and uses of the compounds of the invention in luminescent probes, sensors, electroluminescent devices, hydrogen storage materials, optoelectronic materials, and bioactive molecules.

Claims

1. A method of making organoboron compounds, comprising:

photoirradiating and/or heating a reactant; and

obtaining an elimination product;

wherein the reactant comprises;

(i) a boron atom that is bonded at least to a first moiety and a second moiety, the first moiety being a terminal moiety, and the second moiety being a Lewis base, and

(ii) a carbon atom that is proximal to the boron and that is bonded to at least one hydrogen atom;

wherein the elimination product differs from the reactant such that the elimination product;

(a) has a bond between the boron and the carbon, which may be a single bond or an additional bond between the boron and the carbon; and

(b) does not include the first moiety.

2. The method of claim 1, wherein the reactant is photoirradiated or heated in solid state, or in a polymer matrix.

3. The method of claim 1 or 2, wherein the terminal moiety is a hydrogen atom, substituted or unsubstituted aliphatic, or substituted or unsubstituted aryl.

4. The method of claim 3, wherein the terminal moiety is methyl, unsubstituted phenyl, substituted phenyl, or mesityl.

5. The method of any one of claims 1 to 4, wherein the second moiety is an aryl (which includes heteroaryl) moiety, an N-heterocyclic carbene, or comprises a heteroatom.

6. The method of claim 5, wherein the aryl moiety is substituted or unsubstituted pyridyl.

7. The method of claim 6, wherein the N of the pyridyl ring is bonded to the boron.

8. The method of any one of claims 1 to 7, comprising a reaction:

9. The method of claim 8, wherein the ring comprising X is an N-heterocyclic carbene.

10. The method of claim 9, wherein the ring comprising X is pyridyl and wherein the N of the pyridyl ring is bonded to B.

11. The method of any one of claims 1 to 10, wherein Y is carbon, X is nitrogen, and at least one G of the ring comprising X is a heteroatom.

12. The method of any one of claims 1 to 11, wherein R′

is further substituted by a transition metal or a main group metal.

13. The method of claim 12, wherein the transition metal is platinum or zinc.

14. The method of claim 12, wherein the main group metal is aluminum or boron.

15. The method of claim 2, wherein the polymer is poly(methyl methacrylate) or poly(N-vinylcarbazole).

16. The method of any one of claims 1 to 15, wherein the elimination product is photoluminescent or electroluminescent.

17. The method of any one of claims 1 to 15, wherein the elimination product is an electron transport material.

18. The method of any one of claims 1 to 15, wherein the elimination product is a hydrogen storage material.

19. The method of any one of claims 1 to 15, wherein the elimination product is a solar cell material.

20. The method of any one of claims 1 to 19, wherein R′

is a fused aromatic ring that bridges the ring comprising X and the ring comprising Y.

21. The method of claim 13 or 14, wherein the elimination product is photoluminescent and/or is an electron transport material.

22. The method of claim 8, wherein the reactant is:

BN-1, BN-2, BN-3, BN-4, BN-7, (BN2)-1, (BN2)-2, BC-1, BC-2, BC-3, BC-4, BN-bpy1, SM1, DT1, or BN-Bpy-Pt1.

23. The method of claim 14, wherein the elimination product is a diboron molecule.

24. The method of claim 23, wherein the elimination product is BN-5 or BN-6.

25. The method of any one of claims 1 to 21, wherein the elimination product is:

BN-1a, BN-2a, BN-3a, BN-4a, (BN2)-1a, SM1-aza, DT1-aza, or BN-5b.

26. The method of any one of claims 1 to 22, wherein a final product is a triboron compound or a conjugated polycyclic compound comprising B—

N moieties.

27. The method of claim 26, wherein the product is a conjugated aromatic triboron compound or a 2D conjugated polyaromatic system comprising boron.

28. The method of claim 26 or 27, wherein the triboron compound is BN-5b, (BN)2-2a, BN-5c, BN-6c, BC-1b, BN-7b, BN-bpy1a, BN-bpy-Pt1a, or BC-1.

29. The method of any one of claims 1 to 21, wherein the elimination product has bound to the boron:

a carbene ring;

a mesityl;

a pyridyl ring;

a pyridyl that is part of a fused ring system;

an unsaturated five-membered heterocycle comprising both S and N ring atoms;

or

an unsaturated five-membered heterocycle comprising both S and N ring atoms that is part of a fused ring system.

30. The method of any one of claims 1 to 29, wherein the photoirradiation is UV-irradiation.

31. The method of any one of claims 1 to 29, wherein R′

is further substituted by a metal, wherein the photoirradiation is exposing to visible light.

32. The method any one of claims 1 to 31, wherein a reactant is doped into polymeric film.

33. The method of claim 32, where the polymeric film'"'"'s polymer comprises PMMA or PVK.

34. The method of claim 32 or 33, wherein the photoirradiation or heat is used to create patterns in solid state or in a polymer matrix.

35. The method of any one of claims 1 to 34, wherein the elimination product is used in an optoelectronic device.

36. The method of any one of claims 1 to 35, wherein the elimination product is a polycyclic π

-conjugated compound.

37. A method of producing electroluminescence, comprising the steps of:

providing the electroluminescent elimination product of any one of claims 1 to 36 and applying a voltage across the compound so that the compound electroluminesces.

38. A method of harvesting photons, comprising the steps of:

providing the elimination product of any one of claims 1 to 36, and providing light such that photons strike the elimination product and charge separation occurs in the elimination product.

39. The method of claim 38, wherein the separated charges recombine and photons are released.

40. A method of separating charges, comprising the steps of:

providing the elimination product of any one of claims 1 to 36, and providing light such that photons strike the elimination product and charge separation occurs in the elimination product, optionally wherein the separated charges recombine and photons are released.

41. The method of claim 40, wherein the separated charges migrate to respective electrodes to produce a potential difference.

42. The method of any one of claims 1 to 41, wherein the Lewis base comprises a pyridyl, a pyrimidinyl, a benzothiazolyl, or an imidazolyl.

43. The method of any one of claims 1 to 42, wherein the reactant comprises a chelated metal.

44. The method of claim 43, wherein the chelated metal is a transition metal, rare earth metal, or main group metal.

45. The method of claim 44, wherein the elimination product is BN-bpy-Pt1, or BN-bpy-Pt1a.

46. The method of any one of claims 1 to 44, wherein the reactant'"'"'s boron is bound to three hydrogens and undergoes eliminations so that the final elimination product is a triboron compound.

47. The method of any one of claims 1 to 44, wherein the elimination product is a polycyclic compound.

48. The method of claim 47, wherein the elimination product is an aromatic polycyclic compound.

49. The method of claim 48, wherein the elimination product is a graphene wherein at least one C—

C moiety has been replaced by a B—

N moiety.

50. A method of making a patterned fluorescent film, comprising:

casting a polymer doped with the reactant of claim 1 to form a polymeric film;

positioning a patterned mask having solid areas and open areas between the film and a source of light; and

exposing the mask-positioned film to the light; and

obtaining a patterned film with non-luminescent areas corresponding to the solid areas of the mask, and luminescent areas corresponding to the open areas of the mask that allowed the light to strike the film.

51. The method of claim 50, wherein the reactant comprises a reactant structure of claim 8.

52. The method of claim 50 or 51, wherein the light is UV light.

53. A photocopier employing the method of any one of claims 38 to 41.

54. A photovoltaic device employing the method of any one of claims 38 to 41.

55. A photoreceptor employing the method of any one of claims 38 to 41.

56. A solar cell employing the method of any one of claims 38 to 41.

57. A semiconductor employing the method of any one of claims 38 to 41.

58. A patterned fluorescent polymer film made by the method of claim 50, optionally wherein the film is used in an optoelectronic device.

59. An article that comprises a elimination product made by the method of any one of claims 1 to 49, wherein the elimination product is doped in a polymer film, optionally wherein the doped film is fluorescent, phosphorescent, and/or electroluminescent.

60. The film of claim 58 or 59, wherein the film is patterned with luminescent and non-luminescent areas.

61. An electroluminescent device for use with an applied voltage, comprising:

a first electrode,

an emitter which is an electroluminescent elimination product of claim 1 or claim 8, optionally in a host layer, and

a second, transparent electrode,

wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.

62. An electroluminescent device for use with an applied voltage, comprising:

a first electrode,

a second, transparent electrode,

an electron transport layer adjacent the first electrode,

a hole transport layer adjacent the second electrode, and

an emitter which is an electroluminescent elimination product of claim 1 or 8, optionally in a host layer, interposed between the electron transport layer and the hole transport layer,

wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.

63. A light emitting device comprising:

an anode;

a cathode; and

an emissive layer disposed between the anode and the cathode, wherein the emissive layer comprises the elimination product of claim 1 or claim 8.

64. The device of claim 63, wherein the emissive layer further comprises a host.

65. A consumer product comprising the device of claim 63 or 64.

66. An optoelectronic device comprising the elimination product made by the method of any one of claims 1 to 36.

67. A compound made by the method of any one of claims 1 to 49.

75. A compound which comprises a structure of a general formula:

76. A compound which comprises a structure of a general formula:

77. A compound which comprises a structure of general formula:

78. A compound which comprises a structure of general formula:

79. A compound which comprises a structure of general formula:

80. The compound of any one of claims 75 to 79, wherein the compound is (BN)2-2, BN-5b, (BN)2-2a, BN-5c, BN-6c, BC-1b, BN-7b, BN-bpy1a, BN-bpy-Pt1a, BC-1, (BN)2-2b, BN-5, BN-6, BN-1a, BN-2a, BN-3a, BN-4a, (BN2)-1a, BN-5b, BN-5b, (BN)2-2a, BN-5c, BN-6c, BC-1b, BN-7b, BN-bpy1a, BN-bpy-Pt1a, BC-1, SM1-aza, or DT1-aza.

81. The method of claim 1, wherein the carbon atom of the elimination product is bonded to at least one less hydrogen than the carbon of the reactant.

82. The method of claim 1, wherein the elimination product'"'"'s boron atom can undergo one or more subsequent elimination reaction(s) involving the same carbon atom or a different carbon atom.

68. A compound of general formula:

69. The compound of claim 68, wherein for the ring comprising X, t is zero and at least one ring atom is a heteroatom, so that ring is a five-membered heterocycle.

70. The compound of claim 68 or 69, wherein X is nitrogen and Y is carbon.

71. The compound of any one of claims 68 to 70, wherein the ring comprising Y is substituted phenyl.

72. The compound any one of claims 68 to 71, wherein the R substituent on B is mesityl.

73. The compound of claim 68, wherein the compound is BN-1a, BN-2a, BN-3a, BN-4a, (BN2)-1a, or BN-5b, SM1-aza, or DT1-aza.

74. The compound of any one of claims 68 to 73, wherein the compound is a hydrogen storage material, optoelectronic material, sensor, bioactive molecule, and/or electroluminescent material.