TRIPHENYLENE DERIVATIVES FOR USE IN IMAGING BIOLOGICAL TISSUE OR FLUID
20220357332 · 2022-11-10
Inventors
- Jon PREECE (Birmingham, West Midlands, GB)
- Alex ROBINSON (Birmingham, West Midlands, GB)
- Owen JONES (Birmingham, West Midlands, GB)
- Michael BUTLIN (Birmingham, West Midlands, GB)
- Parvez IQBAL (Birmingham, West Midlands, GB)
- Sareena SUND (Birmingham, West Midlands, GB)
Cpc classification
C07D277/66
CHEMISTRY; METALLURGY
C07D277/60
CHEMISTRY; METALLURGY
A61K49/006
HUMAN NECESSITIES
C07D413/04
CHEMISTRY; METALLURGY
C07D263/52
CHEMISTRY; METALLURGY
A61K49/0021
HUMAN NECESSITIES
C07D413/12
CHEMISTRY; METALLURGY
International classification
Abstract
A composition for imaging a biological tissue or fluid comprising a compound of formula (A) and a biologically acceptable diluent or carrier, (A) wherein X represents one of a nitrogen atom, an oxygen atom, a sulphur atom, a phosphorus atom, or a selenium atom; R represents an aromatic group and/or an aliphatic group; p is an integer of 1 to 2; q and s are independently integers of 1, 2, 3, or 4; Y.sup.1, Y.sup.2, and Y.sup.3 independently represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a polyglycol group, an oxygen atom, a nitrogen atom, a cyano group, a nitro group; and/or wherein two or more of Y.sup.1, Y.sup.2, and Y.sup.3 may combine together to form a condensed ring.
##STR00001##
Claims
1-25. (canceled)
26. A composition for imaging a biological tissue or fluid comprising a compound of formula (A) and a biologically acceptable diluent or carrier, ##STR00013## wherein X represents one of a nitrogen atom, an oxygen atom, a sulphur atom, a phosphorus atom, or a selenium atom; R represents an aromatic group and/or an aliphatic group; p is an integer of 1 to 2; q and s are independently integers of 1, 2, 3, or 4; Y.sup.1, Y.sup.2, and Y.sup.3 independently represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a polyglycol group, an oxygen, a nitrogen atom, a cyano group, a nitro group; and/or wherein two or more of Y.sup.1, Y.sup.2, and Y.sup.3 may combine together to form a condensed ring.
27. The composition of claim 26, wherein the luminescent compound is capable of crossing a cell membrane.
28. The composition of claim 26, wherein the luminescent compound is capable of being retained with cells for at least 10 minutes.
29. The composition of claim 26, wherein the luminescent compound preferentially accumulates in T cells.
30. The composition of claim 26, wherein the biologically acceptable diluent or carrier is selected from phosphate-buffered saline, saline, deionized water, blood, cell culture medium or plasma.
31. The composition of claim 26, wherein the luminescent compound is present in the composition at a concentration of from 0.1 to 20 μg/ml.
32. The composition of claim 26, wherein the composition comprises two or more different luminescent compounds, at least one of which has the general formula (A).
33. The composition of claim 26, wherein the composition comprises a first luminescent compound of formula (A) which emits light at a first wavelength and a second luminescent compound of formula (A) which emits light at a second wavelength, wherein the second wavelength which is longer than the first wavelength, wherein both the first and second compounds are capable of absorbing light at a third wavelength which is shorter than both the first and second wavelengths.
34. The composition of claim 26, wherein the luminescent compound of formula (A) is conjugated to a further molecule.
35. The composition of claim 26, wherein the composition comprises cells which have been dyed with the luminescent compound.
36. The use of a compound of formula (A), in a method of obtaining an image of a biological tissue or fluid using fluorescence microscopy.
37. The use of claim 36, wherein the biological tissue or fluid is in vivo, in vitro or ex vivo.
38. A method of obtaining an image of a biological tissue or fluid in vivo in a subject, the method comprising administering the composition of claim 26 to the subject and obtaining an image of the subject using fluorescence microscopy.
39. The method of claim 38, wherein the composition is administered topically, orally or parenterally.
40. A method of obtaining an image of a biological tissue or fluid previously obtained from a subject, the method comprising: administering to, or contacting with, the biological tissue or fluid a luminescent compound of formula (A) ##STR00014## wherein X represents one of a nitrogen atom, an oxygen atom, a sulphur atom, a phosphorus atom, or a selenium atom; R represents an aromatic group and/or an aliphatic group; p is an integer of 1 to 2; q and s are independently integers of 1, 2, 3, or 4; Y.sup.1, Y.sup.2, and Y.sup.3 independently represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a polyglycol group, an oxygen, a nitrogen atom, a cyano group, a nitro group; and/or wherein two or more of Y.sup.1, Y.sup.2, and Y.sup.3 may combine together to form a condensed ring; and obtaining an image of the biological tissue or fluid using fluorescence microscopy.
41. The method of claim 40, wherein the fluorescence microscopy is multiphoton fluorescence microscopy.
42. The method of claim 40, wherein the biological tissue is selected from blood, connective tissue, muscle tissue, nervous tissue, epithelial tissue, vasculature tissue, lymphoid tissue, tissues of the endocrine system, a gland or an organ.
43. The method of claim 38, for use in a diagnosis of a disease or condition in a subject, wherein the disease or condition is selected from: cancer, inflammation, oedema, cardiovascular disorders, ischemia, autoimmune disease, infection, skin disease, eye disease, neurological disorders or injury.
44. The method of claim 38, comprising subsequently determining the effectiveness of a treatment or therapy received by the subject.
45. The method of claim 40, comprising subsequently determining the effectiveness of a treatment or therapy received by the subject.
Description
[0167]
[0168]
[0169]
[0170]
[0171] Compounds for use in the invention were synthesised according to the following protocols. All compound names were generated using ChemDraw (RTM) software.
[0172] Synthetic Methods
[0173] Method of Synthesising Compound 1
[0174] Compound 1 was synthesised using the following method from Precursor 1.
[0175] Precursor 1 was fabricated according to the method described in N. Boden et. al. J. Mater. Chem., 1995, 5, 2275.
[0176] A solution of Precursor 1 (100 mg; 0.13 mmol) in o-xylene (8 mL) was added to a flask. This was then heated and held at 175° C. for 16 h to afford Compound 1 (51% yield).
[0177] In the alternative, Compound 1 was synthesised using the following method. A solution of Precursor 1 (100 mg; 0.13 mmol) in dry PhMe (8 mL) was added to a flask containing rhodium octanoate dimer (8 mg; 0.01 mmol), under a N.sub.2 atmosphere. This was then heated and held at reflux for 20 h. The reaction was cooled to room temperature and then evaporated to dryness in vacuo, the solid was then purified via flash column chromatography (silica; 95% n-hexane: 5% ethyl acetate) to afford Compound 1 as a white solid (96 mg, 99%).
[0178] The name for Compound 1 is 8-butyl-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0179] Compound 1 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.01 (1 H, s), 7.94 (1H, s), 7.90 (1H, s), 7.88 (1 H, s), 7.85 (1H, s), 4.42 (2H, t, J 6.7 Hz), 4.37 (2H, t, J 6.7 Hz) 4.29-4.23 (6H, m), 3.09 (2H, t, J 7.5 Hz), 2.05-1.92 (10H, m), 1.62-1.43 (24H, m), 1.06-0.96 (18H, m) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3) δ.sub.c: 165.6, 149.5, 149.1, 148.7, 148.3, 142.9, 140.1, 139.8, 124.6, 123.9, 123.5, 123.3, 116.3, 111.0, 108.3, 106.9, 106.8, 102.6, 69.9, 69.6, 69.5, 68.8, 29.2, 29.0, 28.8, 28.4, 28.3, 22.6, 22.4, 14.2, 13.9 ppm. ES+MS m/z: 756.5 ([M.sup.+ H].sup.+15%), 778.5 ([M.sup.+ Na].sup.+100%). IR λ.sup.−1 (neat): 3112w (C—H), 2953m (C—H), 1617w (C═N), 1517w (benzene ring), 1259s (C—O)), 1177s (C—O)), 1159s (C—O)) cm-1. Elemental analysis Found: C, 76.09; H, 9.17; N, 1.95%. C.sub.48H.sub.69NO.sub.6 requires C, 76.25; H, 9.20; N, 1.85%.
[0180] Method of Synthesising Compound 2
[0181] Compound 2 was synthesised using the following method from Precursor 2.
[0182] Precursor 2 was fabricated according to the method described in N. Boden et. al. J. Mater. Chem., 1995, 5, 2275.
[0183] A slurry of benzoic acid (160 mg; 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.16 mmol) in PhMe (5 mL) was heated at 70° C. under N.sub.2 for 20 min. Precursor 2 (100 mg, 0.13 mmol) in PhMe (2 mL) was added and the reaction was heated and held at reflux for 72 h. The mixture was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The mixture was washed with 1M NaOH (2×20 mL) and the organic phase was dried in vacuo. The crude black solid was purified via flash column chromatography (40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 2 as a white solid (35 mg, 34%).
[0184] The name for Compound 2 is 2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]oxazole.
[0185] Compound 2 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.13 (1H, s), 8.40-8.37 (2H, m), 7.92 (1H, s), 7.88 (1H, s), 7.87 (1H, s), 7.77 (1H, s), 7.57-7.55 (1H, m), 4.48-4.43 (4H, m), 4.30-4.23 (6H, m), 2.12-1.92 (10H, m), 1.69-1.54 (12H, m), 1.53-1.45 (12H, m), 1.04-0.96 (18H, m) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3) δ.sub.c: 161.4, 149.5, 149.0, 148.7, 148.3, 142.9, 140.5, 140.2, 131.2, 128.9, 127.5, 127.1, 124.7, 123.8, 123.4, 123.3, 116.4, 110.9, 108.2, 106.8, 106.6, 103.8, 69.8, 69.5, 68.9, 29.2, 29.0, 28.4, 28.3, 22.6, 22.6, 14.1 ppm. ES+MS m/z: 775.5 ([M].sup.+22%), 776.5 ([M+H].sup.+37%), 798.5 ([M+Na]+100%). Elemental analysis Found: C, 77.46; H, 8.44; N, 1.75%. C.sub.50H.sub.65NO.sub.6 requires C, 77.38; H, 8.44; N, 1.80%.
[0186] Method of Synthesising Compound 3
[0187] Compound 3 was synthesised using the following method. A solution of 2-naphthalene carboxylic acid (225 mg, 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in PhMe (5 mL) was heated at 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg; 0.131 mmol) in PhMe (2 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 3 as a yellow solid (35 mg, 32%).
[0188] The name for Compound 3 is 8-(naphthalen-2-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0189] Compound 3 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.22 (1 H, s), 8.89 (1H, s), 8.49 (1H, dd, J 8.6, 1.7 Hz), 8.05-7.99 (2H, m), 7.96-7.91 (5H, m), 7.62-7.59 (2H, m), 4.54 (2H, t, J 6.8 Hz), 4.51 (2H, t, J 6.8 Hz), 4.32-4.25 (6H, m), 2.17-1.93 (10H, m), 1.76-1.42 (20H, m), 1.06-0.97 (15H, m) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3) δ.sub.c: 161.7, 149.8, 149.3, 149.0, 148.6, 143.2, 140.9, 140.6, 135.0, 133.4, 129.3, 128.9, 128.3, 128.0, 127.9, 127.4, 127.2, 125.0, 125.0, 124.4, 124.2, 123.7, 123.6, 116.7, 111.2, 108.5, 107.1, 107.0, 103.9, 70.2, 70.1, 69.8, 69.2, 29.6, 29.5, 28.9, 28.8, 28.7, 23.1, 23.0, 14.6, 14.5 ppm. MALDI+m/z: 825.5 ([M].sup.+100%). IR λ-1 (neat): Elemental analysis Found: C, 78.95; H, 8.02; N, 1.83%. C.sub.54H.sub.87NO.sub.6 requires C, 78.51; H, 8.17; N, 1.70%.
[0190] Method of Synthesising Compound 4 Compound 4 was synthesised using the following method. A solution of 1-naphthalene carboxylic acid (225 mg, 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in PhMe (5 mL) was heated at 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg; 0.131 mmol) in PhMe (2 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 4 as a yellow solid (24 mg, 22%).
[0191] The name for Compound 4 is 8-(naphthalen-1-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0192] Compound 4 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.15 (1H, s), 9.82 (1H, d, J 8.3 Hz), 8.59 (1H, dd, J 7.3, 1.2 Hz), 8.08 (1H, d, J 8.3 Hz), 8.01-7.98 (3H, m), 7.94 (2H, m), 7.71-7.61 (3H, m), 4.54-4.45 (4H, m), 4.32-4.26 (6H, m), 2.10-1.94 (10H, m), 1.70-1.35 (20H, m), 1.04-0.87 (15H, m) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3) δ.sub.c: 161.3, 149.9, 149.6, 149.1, 148.8, 143.2, 141.0, 139.9, 134.5, 132.4, 131.0, 129.6, 129.2, 127.8, 127.5, 126.9, 126.7, 125.5, 125.0, 124.2, 124.1, 123.8, 117.0, 111.0, 108.6, 107.3, 107.2, 104.4, 70.2, 69.9, 69.1, 29.6, 29.5, 29.0, 28.8, 28.7, 23.0, 14.5 ppm. MALDI+m/z: 826.7 ([M+H].sup.+ 100%). Elemental analysis Found: C, 78.49; H, 8.23; N, 1.73%. C.sub.54H.sub.67NO.sub.6 requires C, 78.51; H, 8.17; N, 1.70%.
[0193] Method of Synthesising Compound 5
[0194] Compound 5 was synthesised using the following method. A solution of 2-anthracene carboxylic acid (290 mg, 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in PhMe (5 mL) was heated at 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg; 0.131 mmol) in PhMe (2 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 5 as a yellow solid (22 mg, 20%).
[0195] The name for Compound 5 is 8-(anthracen-2-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0196] Compound 5 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.20 (1H, s), 9.00 (1H, s), 8.58 (1H, s), 8.47 (1H, s), 8.39 (1H, dd, J 8.9, 1.6 Hz), 8.13-8.10 (2H, m), 8.07-8.02 (2H, m), 7.93 (1H, s), 7.90-7.89 (3H, m), 4.57-4.47 (4H, m), 4.31-4.24 (6H, m), 2.19-1.96 (10H, m), 1.76, 1.44 (20H, m), 1.08-0.97 (15H, m) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3) δ.sub.c: 161.8, 149.8, 149.4, 149.0, 148.6, 143.2, 141.0, 140.6, 133.1, 132.6, 132.3, 131.2, 129.2, 128.7, 128.6, 128.2 127.4, 126.8, 126.6, 126.3, 125.0, 124.4, 124.2, 123.8, 123.6, 116.7, 111.3, 108.5, 107.1, 107.0, 104.0, 70.2, 70.1, 69.8, 69.2, 30.1, 29.6, 29.5, 28.9, 28.8, 28.7, 23.1, 23.0, 14.7, 14.5 ppm. MALDI+m/z: 876.5 ([M+H].sup.+100%). Elemental analysis Found: C, 79.49; H, 7.88; N, 1.51%. C.sub.58H.sub.69NO.sub.6 requires C, 79.51; H, 7.94; N, 1.60%.
[0197] Method of Synthesising Compound 6
[0198] Compound 6 was synthesised using the following method. A solution of 9-anthracene carboxylic acid (290 mg; 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added and heated to 140° C. for 72 h. The mixture was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The mixture was washed with 1M NaOH (2×20 mL) and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 6 as a yellow solid (13 mg, 11%).
[0199] The name for Compound 6 is 8-(anthracen-9-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0200] Compound 6 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.18 (1 H, s), 8.70 (1H, s), 8.49-8.44 (2H, m), 8.15-8.09 (2H, m), 8.03 (1H, s), 8.02 (1H, s) 7.95 (1H, s), 7.94 (1H, s) 7.58-7.52 (4H, m), 4.50 (2H, t, J 6.7 Hz), 4.33-4.27 (6H, m), 4.17 (2 H, t, J 6.7 Hz), 2.05-1.93 (8H, m), 1.79 (2H, p, J 6.7, 1.0 Hz), 1.66-1.37 (20H, m), 1.03-0.92 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 160.6, 150.0, 149.6, 149.2, 148.8, 143.5, 141.0, 140.7, 131.9, 131.7, 131.3, 129.1, 127.7, 127.6, 126.4, 125.9, 124.2, 123.8, 121.1, 117.1, 111.3, 108.7, 107.3, 107.2, 104.6, 70.4, 70.3, 69.9, 69.2, 29.6, 29.5, 29.0, 28.8, 28.7, 28.6, 28.5, 23.0, 22.9, 22.6, 14.5, 14.4, 14.3 ppm. MALDI.sup.+ m/z: 876.5 ([M+H].sup.+ 100%). Elemental analysis Found: C, 79.13; H, 7.83; N, 1.77%. C.sub.58H.sub.69NO.sub.6 requires C, 79.51; H, 7.94; N, 1.60%.
[0201] Method of Synthesising Compound 7
[0202] Compound 7 was synthesised using the following method. A solution of 4-fluorobenzoic acid (187 mg; 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added and heated to 140° C. for 72 h. The mixture was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The mixture was washed with 1M NaOH (2×20 mL) and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 7 as a yellow solid (13 mg, 9%).
[0203] The name for Compound 7 is 8-(4-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0204] Compound 7 had the following characterisation data: .sup.1H NMR (300 MHz; CDCl.sub.3) δ.sub.H: 10.03 (1H, s), 8.36-8.30 (2H, m), 7.97-7.75 (4H, m), 7.28-7.15 (3H, m), 4.41 (4H, t, J 6.6 Hz), 4.26 (6H, m), 2.06-1.90 (9H, m), 1.55 (22H, m), 1.05-0.95 (15H, m) ppm. .sup.13C NMR (100 MHz; CDCl.sub.3) δ.sub.c: 166.0, 163.5, 160.6, 149.7, 149.1, 148.9, 148.5, 143.0, 140.5, 140.3, 129.8, 129.7, 127.3, 124.8, 123.9, 123.8, 123.5, 116.5, 116.3, 116.1, 111.1, 108.4, 107.0, 106.8, 103.7, 69.9, 69.8, 69.7, 69.5, 68.9, 29.7, 29.2, 29.0, 28.5, 28.4, 28.3, 22.6, 14.2, 14.1 ppm. .sup.19F NMR (282 MHz, CDCl.sub.3) δ.sub.F: −108.0 ppm. MALDI+m/z: 793.6 ([M].sup.+ 100%), 794.6 ([M+H].sup.+ 55%), 795.6 ([M+H+1].sup.+15%). IR λ.sup.−1 (neat): 2952m (C—H), 2926m (C—H), 2858m (C—H), 1616w (C═N), 1517s (benzene ring), 1499m (benzene ring), 1433m (benzene ring), 1261m (C—O)), 1174s (C—O)) cm.sup.−1.
[0205] Method of Synthesising Compound 8
[0206] Compound 8 was synthesised using the following method. A solution of 3-fluorobenzoic acid (182 mg; 1.30 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added and heated to 140° C. for 72 h. The mixture was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The mixture was washed with 1M NaOH (2×20 mL) and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 8 as a yellow solid (13 mg, 11%).
[0207] The name for Compound 8 is 8-(3-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0208] Compound 8 had the following characterisation data: .sup.1H NMR (300 MHz; CDCl.sub.3) δ.sub.H: 10.06 (1H, s), 8.15 (1H, d, J 7.9 Hz), 8.05 (1H, dd, J 9.0, 1.9 Hz, 7.89 (4H, m), 7.53 (m, 1H), 7.36-7.16 (4H, m), 4.45 (4H, m), 4.33-4.21 (6H, m), 2.16-1.90 (11H, m), 1.71-1.39 (24H, m), 1.06-0.93 (15H, m ppm. .sup.13C NMR (100 MHz; CDCl.sub.3) δ.sub.c: 164.3, 161.8, 160.1, 160.1, 149.6, 149.1, 148.8, 148.4, 142.9, 140.3, 140.3, 130.6, 130.5, 129.6, 129.6, 127.3, 124.8, 123.7, 123.4, 123.4, 123.2, 123.2, 118.3, 118.1, 116.4, 114.6, 114.3, 110.9, 108.2, 106.8, 106.7, 103.9, 69.9, 69.8, 69.6, 69.0, 29.4, 29.3, 29.2, 28.6, 28.5, 28.4, 22.8, 14.3 ppm. 19F NMR (282 MHz; CDCl.sub.3) δ.sub.F: −111.8 ppm. ES+MS m/z: 794.5 ([M].sup.+ 55%), 816.5 ([M+Na].sup.+100%), 817.5 ([M+H*Na].sup.+50%). IR λ-1 (neat): 2952m (C—H), 2925m (C—H), 2856m (C—H), 1617w (C═N), 1518s (benzene ring), 1434s (benzene ring), 1262s (C—O), 1174s (C—O)) cm-1. Elemental analysis Found: C, 75.62; H, 8.25; N, 1.78%. C.sub.50H.sub.64FNO.sub.6 requires C, 75.63; H, 8.12; N, 1.76%.
[0209] Method of Synthesising Compound 9
[0210] Compound 9 was synthesised using the following method. A solution of 2-fluorobenzoic acid (41.86 mg; 0.26 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added and heated to 140° C. for 72 h. The mixture was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The mixture was washed with 1M NaOH (2×20 mL) and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 9 as a yellow solid (7 mg, 10%).
[0211] The name for Compound 9 is 8-(2-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0212] Compound 9 had the following characterisation data: .sup.1H NMR (300 MHz; CDCl.sub.3) δ.sub.H: 10.16 (1H, s), 8.38 (1H, m), 7.92 (4H, m), 7.63-7.47 (1H, m), 7.43-7.28 (2H, m), 4.47 (4H, m), 4.27 (5H, m), 2.13-1.91 (9H, m), 1.69-1.39 (21H, m), 1.00 (14H, m) ppm. 13C NMR (100 MHz; CDCl.sub.3) δ.sub.c: 162.4, 159.8, 157.6, 157.5, 149.7, 149.3, 148.8, 148.4, 142.9, 140.6, 140.5, 139.9, 132.9, 132.8, 130.3, 127.3, 124.8, 124.5, 123.9, 123.4, 123.4, 117.4, 117.2, 116.7, 116.0, 115.9, 110.9, 108.3, 107.0, 106.9, 104.4, 69.8, 69.5, 68.9, 29.2, 29.0, 28.4, 28.3, 22.6, 22.6, 14.1 ppm. 19F NMR (282 MHz; CDCl.sub.3) δ.sub.F: −109.1 ppm. MALDI+m/z: 793.6 ([M].sup.+ 100%), 794.6 ([M+H].sup.+ 65%), 795.6 ([M+1+H].sup.+ 20%). IR λ-1 (neat): 2952m (C—H), 2925m (C— H), 2856m (C—H), 1617w (C═N), 1518m (benzene ring), 1434m (benzene ring), 1261s (C—O)), 1176s (C—O)) cm-1. Elemental analysis Found: C, 75.92; H, 8.26; N, 1.74%. C.sub.50H.sub.64FNO.sub.6 requires C, 75.63; H, 8.12; N, 1.76%.
[0213] Method of Synthesising Compound 10
[0214] Compound 10 was synthesised using the following method. A slurry of Precursor 2 (100 mg; 0.01 mmol), iodobenzene diacetate (51 mg; 0.16 mmol) and palladium diacetate (1 mg; 0.005 mmol) in a mixture of PhMe (5 mL) and acetic acid (1 mL) in PhMe (5 mL) under an N.sub.2 atmosphere was heated and held at reflux for 72 h. The reaction was then cooled to room temperature and washed with 1M NaOH (1M; 2×10 mL). The organic phase was evaporated to dryness in vacuo. The solid was then purified via flash column chromatography (40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 10 as a white solid (64 mg; 66%).
[0215] The name for Compound 10 is 8-methyl-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0216] Compound 10 had the following characterisation data: .sup.1H NMR δ.sub.H: (400 MHz, CDCl.sub.3) 9.94 (1H, s), 7.94 (1H, s), 7.90 (1H, s), 7.89 (1H, s), 7.85 (1H, s), 4.42 (2H, t, J 6.7 Hz), 4.38 (2H, t, J 6.8), 4.30-4.24 (6H, m), 2.81 (3H, s), 1.99 (10H, m), 1.65-1.53 (10H, m), 1.52-1.44 (10H, m), 1.03-0.96 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 162.4, 149.9, 149.4, 149.1, 148.8, 143.2, 140.8, 140.2, 127.2, 125.0, 124.2, 123.9, 123.7, 116.7, 111.6, 108.8, 107.3, 107.2, 102.9, 70.3, 70.2, 69.88, 69.40, 29.60, 29.5, 29.3, 28.8, 28.8, 28.6, 23.0, 15.2, 14.5 ppm. MALDI m/z: 714.5 ([M].sup.+ 100%).
[0217] Method of Synthesising Compound 11
[0218] Compound 11 was synthesised using the following method. A solution of Precursor 2 (200 mg, 0.263 mmol) and trimethylamine (0.2 mL, 1.44 mmol) in PhMe (7 mL) was heated at reflux under N.sub.2 for 10 min. 2-Thiophenecarbonyl chloride (0.3 mL, 2.62 mmol) was added and heated under reflux for 90 min. The solution was cooled to room temperature and washed with 1M HCl (30 mL) and the organic phase extracted with EtOAc (2×30 mL). The organic phase was dried in vacuo and the resultant black solid was heated at 240° C. for 10 min before being cooled to room temperature. The crude 55 black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 11 as a yellow solid (136 mg; 64%).
[0219] The name for Compound 11 is 2,3,6,11,12-pentakis(pentyloxy)-8-(thiophen-2-yl)triphenyleno[1,2-d]oxazole.
[0220] Compound 11 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.03 (1H, s), 7.99 (1H, dd, J 3.7, 1.2 Hz), 7.92 (1H, s), 7.89 (1H, s), 7.88 (1H, s), 7.88 (1H, s), 7.58 (1H, dd, J 5.0, 1.2), 7.25-7.22 (1H, dd, J 5.0, 3.7 Hz), 4.48-4.43 (4H, m), 4.31-4.23 (6H, m), 2.14-1.93 (10H, m), 1.71-1.42 (20H, m), 1.04-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 157.8, 149.8, 149.4, 149.0, 148.6, 143.0, 140.7, 140.1, 130.6, 130.1, 129.7, 128.5, 127.5, 125.0, 124.1, 123.7, 123.6, 116.6, 111.1, 108.5, 107.1, 107.1, 104.0, 70.2, 70.2, 70.1, 69.8, 69.1, 29.6, 29.5, 29.4, 28.9, 28.8, 28.8, 28.6, 23.0, 23.0, 14.6, 14.5 ppm. MALDI m/z: 781.5 ([M].sup.+ 100%).
[0221] Method of Synthesising Compound 12
[0222] Compound 12 was synthesised using the following method. A solution of Precursor 2 (100 mg, 0.132 mmol), 4-Cyanobenzoyl chloride (109 mg, 0.658 mmol) and N,N-Diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 min under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 12 as a yellow solid (40 mg, 38%).
[0223] The name for Compound 12 is 4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)benzonitrile.
[0224] Compound 12 had the following characterisation data: .sup.1H NMR δH: (300 MHz, CDCl.sub.3) 9.96 (1H, s), 8.43-8.40 (2H, d, J 8.55 Hz), 7.90 (1H, s), 7.89 (1H, s), 7.88 (1H, s), 7.87 (1H, s), 7.83-7.80 (2H, d, J 8.55), 4.43-4.38 (4H, m), 4.30-4.23 (6H, m), 2.12-1.93 (10H, m), 1.67-1.42 (20H, m), 1.04-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 159.3, 150.0, 149.3, 149.1, 148.8, 143.1, 140.6, 140.4, 132.7, 131.4, 127.8, 127.6, 125.0, 123.7, 123.7, 123.4, 118.7, 116.6, 114.4, 111.0, 108.4, 106.9, 106.7, 104.4, 70.2, 70.0, 69.9, 69.8, 69.2, 29.6, 29.5, 29.4, 28.8, 28.8, 28.8, 28.7, 23.0, 14.6, 14.5 ppm. MALDI m/z: 800.4 ([M].sup.+ 100%).
[0225] Method of Synthesising Compound 13
[0226] Compound 13 was synthesised using the following method. A solution of 4-(trifluoromethyl)benzoic acid carboxylic acid (248 mg, 1.31 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.157 mmol) in PhMe (5 mL) was heated at 60° C. under N.sub.2 for 30 min. A solution of Precursor 2 (100 mg, 0.132 mmol) in PhMe (2 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 13 as a yellow solid (6 mg; 5%).
[0227] The name for Compound 13 is 2,3,6,11,12-pentakis(pentyloxy)-8-(4-(trifluoromethyl)phenyl)triphenyleno[1,2-d]oxazole.
[0228] Compound 13 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.04 (1H, s), 8.48-8.46 (2H, d, J 8.50), 7.92 (1H, s), 7.90 (1H, s), 7.89 (1H, s), 7.88 (1H, s), 7.83-7.80 (2H, d, J 8.50), 4.47-4.45 (4H, t, J 6.74), 4.31-4.24 (6H, m), 2.14-1.94 (10H, m), 1.70-1.43 (20H, m), 1.05-0.98 (15H, m) ppm. .sup.19F NMR δ.sub.F: (300 MHz, CDCl.sub.3) 62.9 (s) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 159.3, 150.0, 149.3, 149.1, 148.8, 143.1, 140.6, 140.4, 132.7, 131.4, 127.8, 127.6, 125.0, 123.7, 123.7, 123.4, 118.7, 116.6, 114.4, 111.0, 108.4, 106.9, 106.7, 104.4, 70.2, 70.0, 69.9, 69.8, 69.2, 29.6, 29.5, 29.4, 28.8, 28.8, 28.8, 28.7, 23.0, 14.6, 14.5 ppm. MALDI m/z: 844.5 ([M+H].sup.+ 100%).
[0229] Method of Synthesising Compound 14
[0230] Compound 14 was synthesised using the following method. A solution of Precursor 2 (100 mg, 0.132 mmol), 2-iodobenzoyl chloride (175 mg, 0.658 mmol) and N,N-Diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 min under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 14 as a yellow solid (39.9 mg, 35%).
[0231] The name for Compound 14 is 8-(2-iodophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0232] Compound 14 had the following characterisation data: .sup.1H NMR δH: (300 MHz, CDCl.sub.3) 10.07 (1H, s), 8.20-8.16 (1H, dd, J 7.90, 1.60 Hz), 8.18-8.15 (1H, dd, J 7.90, 1.25 Hz), 7.95 (1H, s), 7.94 (1H, s), 7.91 (2H, m), 7.58-7.53 (1H, td, J 7.66, 7.63, 1.25 Hz), 7.26-7.20 (1H, td, J 7.66, 7.63, 1.60 Hz), 4.52-4.44 (4H, m), 4.31-4.25 (6H, m), 2.06-1.94 (10H, m), 1.67-1.41 (20H, m), 1.03-0.92 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 160.9, 149.9, 149.6, 149.2, 149.1, 143.3, 142.0, 140.6, 140.4, 132.5, 132.1, 132.1, 128.5, 127.6, 125.1, 124.1, 124.0, 123.7, 117.2, 111.9, 108.6, 107.3, 107.1, 104.9, 95.0, 70.4, 70.2, 70.2, 70.1, 69.9, 29.6, 29.6, 29.5, 29.4, 28.9, 28.8, 28.7, 23.0, 23.0, 14.5 ppm. MALDI m/z: 901.6 ([M].sup.+ 14%).
[0233] Method of Synthesising Compound 15
[0234] Compound 15 was synthesised using the following method. A solution of Precursor 2 (100 mg, 0.132 mmol), 2-chlorobenzoyl chloride (175 mg, 0.658 mmol) and N,N-Diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 min under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 15 as a yellow solid (52.4 mg, 49%).
[0235] The name for Compound 15 is 8-(2-chlorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0236] Compound 15 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.06 (1H, s), 8.39-8.34 (1H, m), 7.92-7.90 (4H, m), 7.66 (1H, m), 7.51-7.44 (2H, m), 4.49-4.41 (4H, m), 4.30-4.25 (6H, m), 2.06-1.95 (10H, m), 1.67-1.43 (20H, m), 1.03-0.92 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 158.8, 149.6, 149.4, 148.9, 148.5, 142.9, 140.4, 139.9, 133.5, 131.7, 131.6, 127.3, 127.0, 126.2, 124.8, 123.9, 123.4, 116.8, 110.9, 108.2, 106.9, 104.6, 70.1, 70.0, 69.9, 69.6, 69.1, 29.8, 29.3, 29.3, 29.2, 28.5, 28.4, 22.7, 14.3 ppm. MALDI m/z: 809.7 ([M].sup.+ 95%).
[0237] Method of Synthesising Compound 16
[0238] Compound 16 was synthesised using the following method. A solution of Precursor 2 (100 mg, 0.132 mmol), 2-bromobenzoyl chloride (144 mg, 0.658 mmol) and N,N-Diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 min under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 16 as a yellow solid (25.8 mg, 21%).
[0239] The name for Compound 16 is 8-(2-bromophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0240] Compound 16 had the following characterisation data: .sup.1H NMR δH: (300 MHz, CDCl.sub.3) 10.03 (1H, s), 8.31-8.28 (1H, dd, J 7.91, 1.75 Hz), 7.91-7.89 (4H, m), 7.86-7.83 (1H, dd, J 7.91, 1.23 Hz), 7.54-7.49 (1H, td, J 7.70, 7.60, 1.23 Hz), 7.42-7.37 (1H, td, J 7.70, 7.57, 1.75 Hz) 4.49-4.39 (4H, m), 4.31-4.23 (6H, m), 2.06-1.95 (10H, m), 1.64-1.43 (20H, m), 1.03-0.95 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3): 159.5, 149.7, 149.4, 148.9, 148.6, 142.9, 140.3, 135.0, 132.2, 131.8, 128.3, 127.6, 127.4, 124.8, 123.9, 123.6, 123.5, 122.0, 116.9, 111.1, 108.2, 107.0, 104.7, 70.1, 70.0, 69.9, 69.6, 69.4, 29.3, 29.3, 29.2, 28.6, 28.5, 28.4, 22.7, 14.3 ppm. MALDI m/z: 855.7 ([M].sup.+ 31%)
[0241] Method of Synthesisinq Compound 17
[0242] Compound 17 was synthesised using the following method. A solution of 5-bromovaleric acid (773 mg, 4.27 mmol), palladium diacetate (0.005 mmol) and iodobenzene diacetate (0.512 mmol) in PhMe (10 mL) was heated at 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (325 mg; 0.428 mmol) in PhMe (10 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 17 as a white solid (109 mg, 31%).
[0243] The name for Compound 17 is 8-(4-bromobutyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0244] Compound 17 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 9.95 (1H, s), 7.92 (1H, s), 7.90 (1H, s), 7.89 (1H, s), 7.84 (1H, s), 4.43-4.34 (4H, m), 4.30-4.24 (6H, m), 3.55-3.50 (2H, t, J 6.29 Hz), 3.15-3.10 (2H, t, J 7.05 Hz), 2.35 (3H, s), 2.25-1.94 (12H, m), 1.64-1.45 (24H, m), 1.03-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 164.6, 149.6, 149.1, 148.8, 148.4, 142.9, 140.1, 139.7, 127.0, 124.7, 123.8, 123.5, 123.4, 116.3, 111.0, 108.4, 107.0, 102.7, 70.0, 69.9, 69.6, 69.6, 68.9, 33.0, 31.9, 29.3, 29.2, 29.2, 29.1, 28.6, 28.5, 28.4, 28.3, 22.7, 25.3, 22.7, 22.6, 14.3, 14.2, 14.1 ppm. ES+m/z: 834.4 ([M+H].sup.+ 95%), 836.4 ([M+H].sup.+ 100%).
[0245] Method of Synthesisinq Compound 18
[0246] Compound 18 was synthesised using the following method. A solution of Compound 17 (66 mg, 0.079 mmol) in acetone (10 mL) was heated to 50° C. and stirred under N.sub.2, to this was added a solution of sodium azide (7 mg, 0.111 mmol) in H.sub.2O (5 mL) and left stirring under N.sub.2 for 4 h. After this time a precipitate had formed and the solvent was removed under reduced pressure, the precipitate was then filtered under vacuum and dried to give Compound 18 as an off white solid (59 mg, 94%).
[0247] The name for Compound 18 is 8-(4-azidobutyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0248] Compound 18 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 9.96 (1H, s), 7.94 (1H, s), 7.90 (1H, s), 7.90 (1H, s), 7.87 (1H, s), 4.45-4.40 (2H, t, J 6.70 Hz), 4.39-4.35 (2H, t, J 6.67 Hz), 4.30-4.24 (6H, m), 3.55-3.51 (2H, t, J 6.31 Hz), 3.17-3.12 (2H, t, J 7.11 Hz), 2.28-1.93 (12H, m), 1.65-1.41 (24H, m), 1.03-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 165.0, 149.6, 149.9, 149.4, 149.1, 148.7, 143.2, 140.4, 140.0, 127.3, 125.0, 124.1, 123.8, 123.7, 116.7, 111.3, 108.7, 107.3, 103.0, 70.3, 70.3, 69.9, 69.9, 69.2, 33.3, 32.3, 29.6, 29.5, 29.5, 29.4, 28.9, 28.8, 28.7, 28.6, 28.0, 25.6, 23.1, 23.0, 14.6, 14.5, 14.5 ppm. ES+m/z: 819.5 ([M+Na].sup.+100%).
[0249] Method of Synthesisinq Compound 19
[0250] Compound 19 was synthesised using the following method. Compound 17 (21 mg, 0.025 mmol) was dissolved in anhydrous THF (4 mL) to this mixture potassium thioacetate (12 mg, 0.1 mmol) was added and stirred under N.sub.2 for 6 h. The organic phase was then extracted with DCM (10 mL) and washed with water (2×10 mL). The organic phase was then dried in vacuo and the solid recrystalised with DCM:MeOH (1 mL: 5 mL). The resultant precipitate was filtered under suction and the solid washed with methanol to give Compound 19 as an off white solid (4 mg, 19%).
[0251] The name for Compound 19 is S-(4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)butyl) ethanethioate.
[0252] Compound 19 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 9.97 (1H, s), 7.94 (1H, s), 7.90 (1H, s), 7.89 (1H, s), 7.86 (1H, s), 4.45-4.35 (4H, m), 4.30-4.24 (6H, m), 3.14-3.09 (2H, t, J 7.44 Hz), 3.02-2.97 (2H, t, J 7.21 Hz), 2.35 (3H, s), 2.18-1.80 (12H, m), 1.65-1.42 (24H, m), 1.03-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 196.0, 165.2, 149.9, 149.4, 149.1, 148.7, 143.2, 140.4, 140.0, 127.2, 125.0, 124.2, 123.8, 123.6, 116.7, 111.4, 108.7, 107.3, 103.1, 70.3, 70.2, 69.9, 69.9, 69.2, 31.0, 30.1, 29.6, 29.5, 29.5, 29.4, 29.4, 29.1, 28.9, 28.8, 28.7, 28.6, 28.5, 26.2, 23.0, 23.0, 14.6, 14.5, 14.5, 14.5 ppm. MALDI m/z: 829.5 ([M].sup.+ 100%).
[0253] Method of Synthesisinq Compound 20
[0254] Compound 22 was synthesised using the following method. A solution of Compound 17 (260 mg, 0.311 mmol), Sodium Tert-butoxide (90 mg, 0.934 mmol), Potassium Iodide (40 mg, 0.311 mmol) and Ethylene Glycol (193 mg, 3.11 mmol) in MeCN (15 mL) was heated to and held at reflux for 48 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The crude solid was dissolved with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL) and then HCl (1M, 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 16 as a yellow solid (84 mg, 36%).
[0255] The name for Compound 20 is 8-(but-3-en-1-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0256] Compound 20 had the following characterisation data: .sup.1H NMR δH: (300 MHz, CDCl.sub.3) 10.00 (1H, s), 7.92 (1H, s), 7.90 (1H, s), 7.89 (1H, s), 7.84 (1H, s), 6.14-6.00 (1H, ddt, J 16.95, 10.20, 6.45 Hz), 5.22 (1H, dd, J 16.95, 1.60 Hz), 5.10 (1H, dd, J 10.20, 1.60 Hz), 4.43-4.35 (4H, m), 4.30-4.24 (6H, m), 3.22-3.17 (2H, t, J 7.55 Hz), 3.17-3.12 (2H, t, J 7.11 Hz), 2.86-2.78 (2H, m), 2.08-1.94 (10H, m), 1.62-1.45 (20H, m), 1.03-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 165.0, 149.8, 149.4, 149.1, 148.7, 143.2, 140.4, 140.0, 137.0, 127.2, 125.0, 124.2, 123.8, 123.6, 116.7, 116.3, 111.4, 108.7, 107.3, 107.2, 103.0, 70.3, 70.2, 69.9, 69.8, 69.2, 30.9, 29.6, 29.5, 29.4, 29.3, 28.9, 28.8, 28.7, 28.6, 28.5, 23.0, 22.9, 14.6, 14.5, 14.5 ppm. ES+m/z: 754.5 ([M+H].sup.+ 100%).
[0257] Method of Synthesisinq Compound 21
[0258] Compound 21 was synthesised using the following method. A solution of decanoic acid (0.132 mg, 0.236 mmol), palladium diacetate (0.005 mmol) and iodobenzene didecanoate (0.235 mmol) in PhMe (10 mL) was heated at 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg; 0.132 mmol) in PhMe (10 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 21 as a white solid (42 mg, 39%).
[0259] The name for Compound 21 is 8-nonyl-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0260] Compound 21 had the following characterisation data: .sup.1H NMR δH: (300 MHz, CDCl.sub.3) 10.02 (1H, s), 7.93 (1H, s), 7.90 (1H, s), 7.89 (1H, s), 7.84 (1H, s), 4.43-4.36 (4H, m), 4.30-4.24 (6H, m), 3.11-3.06 (2H, t, J 7.52 Hz), 2.10-1.94 (12H, m), 1.63-1.29 (32H, m), 1.02-0.97 (15H, m) 0.91-0.87 (3H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 165.9, 149.8, 149.3, 149.0, 148.6, 143.2, 140.4, 140.1, 127.1, 124.9, 124.2, 123.8, 123.6, 123.6, 116.6, 111.3, 108.6, 107.2, 107.1, 102.9, 70.2, 69.9, 69.8, 69.1, 32.3, 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.0 28.9, 28.8, 28.6, 27.1, 23.1, 23.0, 14.6, 14.5 ppm. ES+m/z: 826.6 ([M+H].sup.+ 100%).
[0261] Method of Synthesisinq Compound 22 Compound 22 was synthesised using the following method. A solution of Precursor 2 (100 mg, 0.132 mmol), 4-(dimethylamino)benzoyl chloride (175 mg, 0.658 mmol) and N,N-Diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 mins under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 22 as a yellow solid (19 mg, 18%).
[0262] The name for Compound 22 is N,N-dimethyl-4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)aniline.
[0263] Compound 22 had the following characterisation data: .sup.1H NMR δH: (300 MHz, CDCl.sub.3) 10.20 (1H, s), 8.27-8.24 (2H, d, J 8.60 Hz), 7.94 (1H, s), 7.90-7.85 (3H, m), 6.89-6.86 (2H, d, J 8.60 Hz), 4.56-4.45 (4H, m), 4.31-4.24 (6H, m), 3.11 (6H, s), 2.16-1.94 (10H, m), 1.71-1.42 (20H, m), 1.04-0.97 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 162.8, 152.2, 149.7, 149.3, 148.5, 143.1, 141.4, 140.2, 129.3, 127.4, 124.9, 124.5, 124.0, 123.6, 116.5, 112.4, 111.5, 108.6, 107.3, 107.2, 103.4, 70.2, 70.2, 69.9, 69.2, 40.9, 29.6, 29.6, 29.5, 29.4, 29.0, 28.9, 28.8, 28.7, 23.0, 23.0, 14.7, 14.5 ppm. ES+m/z: 819.7 ([M].sup.+ 100%).
[0264] Method of Synthesisinq Compound 23
[0265] Compound 23 was synthesised using the following method. A solution of 4-nitrobenzoic acid (1 g, 6 mmol), palladium diacetate (0.005 mmol) and (diacetoxyiodo)benzene (51 mg, 0.157 mmol) in PhMe (10 mL) was heated at 70° C. under N.sub.2 for 20 min. A solution of Precursor 2 (100 mg; 0.132 mmol) in PhMe (10 mL) was added and heated under reflux for 48-72 h, whilst stirring. The solution was cooled to room temperature and diluted with CH.sub.2Cl.sub.2 (20 mL). The organic phase was washed with aqueous NaOH (1M; 2×20 mL), separated and the organic phase was dried in vacuo. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 23 as an off-white solid (74 mg, 69%).
[0266] The name for Compound 23 is 8-(4-nitrophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0267] Compound 23 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 9.66 (1H, s), 8.14-8.05 (4H, m), 7.74 (1H, s), 7.73 (1H, s), 7.70 (1H, s), 7.67 (1H, s), 4.30-4.19 (10H, m), 2.04-1.94 (10H, m), 1.63-1.47 (20H, m), 1.05-1.00 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 158.9, 150.0, 149.3, 149.1, 148.8, 143.0, 140.6, 140.4, 132.8, 127.8, 127.5, 125.0, 124.0, 123.6, 123.5, 123.3, 116.5, 110.8, 108.3, 106.8, 106.4, 104.3, 70.2, 69.9, 69.8, 69.7, 69.1, 29.7, 29.6, 29.5, 29.4, 28.9, 28.8, 28.8, 28.7, 23.0, 14.6, 14.5 ppm. MALDI m/z: 820.5 ([M].sup.+ 100%).
[0268] Method of Synthesisinq Compound 24
[0269] Compound 24 was synthesised using the following method. A solution of (diacetoxyiodo)benzene (51 mg, 0.157 mmol) and acetylsalicylic acid (550 mg, 3.031 mmol) in toluene (4 mL) was heated to 80° C. and stirred for 10 min under N.sub.2. Then Precursor 2 (100 mg, 0.131 mmol) was added to form a black solution which was then stirred for a further 10 mins. A solution of palladium diacetate (1 mg, 5 mol %) and acetylsalicyclic acid (553 mg, 3.197 mmol) in toluene (4 mL) was heated to 110° C. and stirred for 10 mins under N.sub.2 before being combined with the black solution. The resultant solution was left stirring at 110° C. for 72 h under N.sub.2. The crude black solution was dried in vaccuo and purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane). The crude material was then evaporated to dryness in vacuo and then dissolved in a mixture of MeCN (10 mL) and 1M NaOH (10 mL). The solution was heated to 80° C. for 2 h. After cooling to room temperature the product was acidified using 1M HCl (20 mL) and extracted into CH.sub.2Cl.sub.2 (3×10 mL). The combined organic layer was evaporated to dryness in vacuo to afford Compound 24 as a white solid (2 mg. 2%).
[0270] The name for Compound 24 is 2-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)phenol.
[0271] Compound 24 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 11.42 (1H, s), 9.35 (1H, s), 8.20-8.17 (1H, dd, J 8.01, 1.67 Hz), 7.90 (1H, s), 7.89 (1H, s), 7.88 (1H, s), 7.87 (1H, s), 7.52-7.46 (1H, ddd, J 8.51, 7.22, 1.67 Hz), 7.18-7.14 (1H, dd, J 8.51, 1.08 Hz), 7.08-7.05 (1H, ddd, J 8.01, 7.22, 1.08 Hz), 4.47-4.42 (2H, t, J 6.65 Hz), 4.39-4.35 (2H, t, J 6.71 Hz), 4.30-4.19 (6H, m), 2.09-1.94 (10H, m), 1.71-1.43 (20H, m), 1.05-0.98 (15H, m) ppm. MALDI m/z: 791 ([M].sup.+ 100%).
[0272] Method of Synthesisinq Compound 25
[0273] Compound 25 was synthesised using the following method from Precursor 3.
[0274] Precursor 3 was fabricated according to the method described in N. Boden et. al. J. Mater. Chem., 1995, 5, 2275. A solution of 2,3,6,7,10,11-hexabutoxy-1-nitrotriphenylene (1.70 g, 2.79 mmol), sodium borohydride (1.70 g, 45.1. mmol) and nickel(II) chloride hexahydrate (4.45 g, 18.7 mmol) in a 50/50 mix of MeOH and THF (40 mL) was stirred at room temperature for 5 h under N.sub.2. The crude black solid was then filtered and washed with CHCl.sub.3 and the filtrate evaporated to dryness in vacuo to afford Precursor 3 as a brown solid (1.6 g, 85%).
[0275] The name for Precursor 3 is 2,3,6,7,10,11-hexabutoxytriphenylen-1-amine.
[0276] Precursor 3 had the following characterization data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 8.82 (1H, s), 7.83 (1H, s), 7.80 (1H, s), 7.78 (1H, s), 7.37 (1H, s), 4.57 (2H, s), 4.29-4.09 (12H, m), 2.01-1.81 (12H, m), 1.67-1.52 (12H, m), 1.13-0.94 (18H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 151.0, 149.5, 148.9, 148.0, 147.6, 138.4, 135.6, 127.0, 124.7, 124.5, 124.1, 124.0, 114.0, 110.3, 108.5, 108.2, 107.1, 97.4, 72.9, 69.7, 69.4, 69.1, 68.4, 32.7, 31.8, 31.7, 31.6, 31.5, 19.7, 19.6, 19.5, 19.4, 14.1 ppm. MALDI m/z: 675.8 ([M].sup.+ 100%).
[0277] A solution of Precursor 3 (100 mg, 0.148 mmol), 2-napthoyl chloride (141 mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo.
[0278] The solid was then heated and held at 240° C. for 15 mins under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 25 as a yellow solid (21 mg, 19%).
[0279] The name for Compound 25 is 2,3,6,11,12-pentabutoxy-8-(naphthalen-2-yl)triphenyleno[1,2-d]oxazole.
[0280] Compound 25 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.01 (1H, s), 8.68 (1H, s), 8.31-8.27 (1H, dd, J 8.57, 1.65 Hz), 7.96-7.87 (3H, m), 7.80-7.79 (3H, m), 7.70 (1H, s), 7.58-7.55 (2H, m), 4.45-4.40 (2H, t, J 7.01 Hz), 4.38-4.34 (2H, t, J 6.67 Hz), 4.28-4.19 (6H, m), 2.15-1.91 (10H, m), 1.79-1.59 (10H, m), 1.18-1.07 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 161.6, 149.7, 149.3, 149.0, 148.5, 143.1, 140.8, 140.4, 134.9, 133.4, 129.2, 128.3, 127.8, 127.3, 127.1, 125.0, 124.9, 124.4, 124.1, 123.7, 123.6, 116.6, 111.3, 108.4, 107.1, 106.9, 103.7, 69.8, 69.6, 69.5, 68.9, 31.9, 31.8, 19.9, 19.8, 19.7, 14.5, 14.4, 14.3 ppm. MALDI m/z: 755.1 ([M].sup.+ 100%).
[0281] Method of Synthesisinq Compound 26
[0282] Compound 26 was synthesised using the following method from Precursor 4 (2,3,6,7,10,11-hexakis(pentyloxy)-1,8-triphenylenediamine).
[0283] Precursor 4 is synthesised using the method described in N. Boden et. al. J. Mater. Chem., 1995, 5, 2275 from the di-nitro triphenylene derivative, which is formed as a side product in the method that was used to synthesis the mono-nitro triphenylene derivative. The di-nitro triphenylene derivative may be isolated using flash column chromatography in an earlier fraction than the mono-nitro intermediate.
[0284] A solution of Precursor 4 (135 mg, 0.174 mmol) and palladium diacetate (0.0005 mmol) in PhMe (7 mL) was heated at reflux under N.sub.2 for 10 min. 2-flourobenzoyl chloride (0.02 mL, 0.174 mmol) was added and heated under reflux for 40 h. The solution was cooled to room temperature and dried in vacuo and the resultant black solid was heated at 240° C. for 10 minutes before being cooled to room temperature. The crude black solid was purified by flash column chromatography (silica; 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 26 as an off-white solid (6 mg, 4%).
[0285] The name for Compound 26 is 2,9-bis(2-fluorophenyl)-4,7,12,13-tetrakis(pentyloxy)triphenyleno[1,2-d:8,7-d′]bis(oxazole).
[0286] Compound 26 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.09 (2H, s), 8.38-8.32 (2H, td, J 7.56, 7.52, 1.78 Hz), 7.82 (2H, m), 7.58 (2H, m), 7.36-7.31 (2H, m), 7.29-7.25 (2H, m), 4.48-4.39 (8H, m), 2.16-1.96 (8H, m), 1.70-1.44 (16H, m), 1.05-1.00 (12H, m) ppm. .sup.19F NMR δ.sub.F: (300 MHz, CDCl.sub.3) 108.9 (s) ppm. MALDI m/z: 842.5 ([M].sup.+ 100%).
[0287] Method of Synthesisinq Compound 27
[0288] Compound 27 was synthesised using the following method. A solution of 4′-Carboxybenzo-15-crown-5 (600 mg, 1.92 mmol), Oxalyl chloride (2.0 mL, 23.6 mmol) and Dimethylformamide (0.01 ml, 0.129 mmol) was heated and held at reflux for 10 minutes under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. A solution of Precursor 2 (100 mg, 0.132 mmol) and N,N-Diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was added. The reaction was then heated and held at reflux for 72 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 mins under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 10% EtOAc: 90% n-hexane) to afford compound 27 as a brown solid (22 mg, 17%).
[0289] The name for Compound 27 is 8-(2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecin-15-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0290] Compound 27 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.10 (1H, s), 8.04-7.80 (6H, m), 6.99 (1H, d, J 8.35 Hz), 4.53-4.38 (4H, m), 4.33-4.17 (10H, m), 4.06-3.90 (4H, m), 3.89-3.73 (8H, m), 2.10-1.88 (10H, m), 1.69-1.44 (20H, m), 1.07 0.92 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 161.6, 152.1, 149.6, 149.1, 148.9, 148.4, 142.9, 140.7, 140.1, 127.2, 124.7, 124.0, 123.6, 123.4, 121.7, 120.5, 116.4, 113.2, 112.9, 111.1, 108.3, 107.0, 103.4, 71.3, 70.6, 70.5, 70.0, 70.0, 69.9, 69.6, 69.5, 69.2, 68.9, 68.7, 29.8, 29.4, 29.3, 29.2, 28.7, 28.5, 28.4, 22.8, 22.7, 14.4, 14.3 ppm. MALDI m/z: 965.9 ([M].sup.+ 100%).
[0291] Method of Synthesisinq Compound 28
[0292] Compound 28 was synthesised using the following method. A solution of Compound 2 (60 mg, 0.077 mmol) in degassed dichloromethane (5 mL) was stirred in a nitrogen purged 2 neck flask under nitrogen atmosphere at −20° C. Boron tribromide (1M solution in CH.sub.2Cl.sub.2, 387 μL, 0.385 mmol, 5 eq) was added via syringe through a Suba-Seal(RTM) and the dark yellow solution was stirred for at room temperature for 24 h. Water (40 mL) was added to quench the reaction and the product was extracted with dichloromethane (10 mL), washed with water (2×20 mL) and dried over MgSO.sub.4. The organic phase was evaporated to dryness and purified by column chromatography (Silica: 5% Ethyl acetate: Hexane) to afford Compound 28 as a brown solid (10 mg, 6%).
[0293] The name for Compound 28 is 2,3,11,12-tetrakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]oxazol-6-ol.
[0294] Compound 28 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.09 (1H, s), 8.48 (2H, dd, J 6.86, 2.85 Hz), 7.94 (1H, s), 7.90 (1H, s), 7.88 (1H, s), 7.83 (1H, s), 7.59-7.56 (3H, m), 5.95 (1H, s br), 4.48 (2H, t, J 6.60 Hz), 4.33 (2H, t, J 6.51 Hz), 4.26-4.24 (4H, m), 2.06-1.93 (8H, m), 1.64-1.43 (16H, m), 1.01-0.97 (12H, m) ppm. ES.sup.+MS m/z: 728.4 ([M+Na].sup.+ 25%), 707.4 ([M+H+1].sup.+ 30%), 706.4 ([M+H].sup.+ 85%).
[0295] Method of Synthesisinq Compound 29
[0296] Compound 29 was synthesised using the following method. Compound 2 (250 mg, 0.322 mmol) was dissolved in dry CH.sub.2Cl.sub.2 (10 mL) and stirred at 0° C. under a N.sub.2 atmosphere. 0.01M solution of Br.sub.2 in CH.sub.2Cl.sub.2 (144 mL, 1.449 mmol) was then added over 2 h (4×36 mL) and monitered by TLC. The reaction was quenched by addition of saturated sodium metabisulfate solution (100 mL). The product was extracted with dichloromethane (30 mL) washed with water (3×30 mL), dried over MgSO.sub.4 and evaporated to dryness. The crude product was then purified by column chromatography (Silica 40% CH.sub.2Cl.sub.2: n-hexane) to yield Compound 29 as a yellow solid (170 mg, 62%).
[0297] The name for Compound 29 is 1-bromo-2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]oxazole.
[0298] Compound 29 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H: 10.06 (1H, s), 8.71 (1H, s), 8.56 (1H, s), 8.34-8.31 (2H, m), 7.60-7.58 (4H, m), 4.59 (2H, t, J 6.5 Hz), 4.41 (2H, t, J 6.8 Hz), 4.26-4.20 (6H, m), 2.06-1.90 (10H, m), 1.64-1.42 (20H, m), 1.02-0.94 (15H, m) ppm.
[0299] Method of Synthesisinq Compound 30
[0300] Compound 30 was synthesised using the following method. Compound 29 (170 mg, 0.199 mmol), K.sub.2CO.sub.3 (410 mg, 2.97 mmol) and Pd(PPh.sub.3).sub.4 (30 mg, 0.026 mmol) were dissolved in degassed 5: 1 THF:H.sub.2O mix (4 mL) under nitrogen atmosphere. (4-hydroxyphenyl)boronic acid (140 mg, 1.02 mmol) was then added and the reaction was heated to reflux under N.sub.2 for 24 h. The product was extracted with dichloromethane (30 mL), washed with water (3×30 mL) and evaporated to dryness. The crude product was purified by column cromatography (Silica CH.sub.2Cl.sub.2: n-hexane) to yield impure Compound 30 as a brown solid.
[0301] The name for Compound 30 is 4-(2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]oxazol-1-yl)phenol.
[0302] Compound 30 had the following characterisation data: TOF LD*.sup.+ m/z: 869.49 ([M+1].sup.+ 70%), 868.52 ([M].sup.+ 70%).
[0303] Method of Synthesisinq Compound 31
[0304] Compound 31 was synthesised using the following method. Compound 10 (50.7 mg, 0.071 mmol) was added to a 2 neck round bottom flask, which was purged with N.sub.2 for 15 min. Dry CH.sub.2Cl.sub.2 (20 mL) was then added via syringe through a Suba-Seal(RTM) and the brown stirring solution was cooled to −78° C. Boron tribromide (1M solution in CH.sub.2Cl.sub.2, 391 μL, 0.391 mmol, 5.5 eq) was added via syringe through a Suba-Seal(RTM) and the reaction was stirred for 4 h. The reaction mixture was poured over crushed ice and stirred until the ice had fully melted, 4 drops of hydrochloric acid (1M) were added and the product was extracted with ethyl acetate, washed with water (2×20 mL), and dried over MgSO.sub.4 and evaporated to dryness. The crude product was used without further purification.
[0305] The name for Compound 31 is 8-methyltriphenyleno[1,2-d]oxazole-2,3,6,11,12-pentaol.
[0306] Compound 31 had the following characterisation data: ES.sup.+*MS m/z: 503.26 ([M+2(OC.sub.5H.sub.11)].sup.+ 50%), 433.17 ([M+(OC.sub.5H.sub.11)].sup.+ 100%), 363.08 ([M].sup.+ 10%).
[0307] Method of Synthesisinq Compound 32
[0308] Crude Compound 31 (26 mg, 0.071 mmol), potassium carbonate (74 mg, 0.533 mmol), potassium iodide (6 mg, 0.036 mmol) was dissolved in dry MeCN (35 mL). 1(-2-Bromoethoxy)-2-(2-methoxyethoxy)ethane (132 μL, 0.533 mmol) was then added via pipette and the reaction was heated to reflux and stirred under a CaCl.sub.2 drying tube for 20 h. The reaction was cooled to room temperature and the product was extracted with ethyl acetate (20 mL), washed with water (3×20 mL), brine (2×20 mL) and dried over MgSO.sub.4 to yield crude Compound 32 as a brown solid.
[0309] The name for Compound 32 is 2,3,6,12-tetrakis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-8-methyl-11-(pentyloxy)triphenyleno[1,2-d]oxazole.
[0310] Compound 32 had the following characterisation data: ES.sup.+MS m/z: 1017.5 ([M].sup.+ 100%).
[0311] Advantageously, Compound 32 is water soluble.
[0312] Method of Synthesisinq Compound 33
[0313] Compound 33 was synthesised from Precursor 5 in the following method. The starting material to form Precursor 5 was obtained using the method described in J. Mater. Chem. C, 2017, 5, 669-682 (DOI: 10.1039/C6TC04530H).
[0314] 5,6-Dimethoxy-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracene (681 mg, 0.775 mmol) was dissolved in diethyl ether (20 ml) and then acetic acid (1.33 ml, 23.24 mmol, 30 eqiv) was added and the mixture stirred at room temperature in a nitrogen atmosphere for 10 minutes before the addition of fuming nitric acid (65 μL, 1.55 mmol, 2 equiv) was added. The reaction mixture was stirred under nitrogen for 20 min before the further addition of nitric acid (30 μL, 0.715 mmol, 0.92 eq) and the reaction mixture was left for 20 min stirring at room temperature. The mixture was then quenched with water (10 ml) and the organic phase was washed with NaOH (1M, 2×30 mL) and then dried in vacuo to provide Precursor 5 as a black solid (680 mg, 95%). This was used in the next step with no further purification.
[0315] The name for Precursor 5 is 5,6-dimethoxy-1-nitro-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracene.
[0316] Precursor 5 had the following characterisation data: .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H 9.16 (1H, s), 9.01 (1H, s), 7.95 (1H, s), 7.84 (1H, s), 7.58 (1H, s), 4.53 (2H, t, J 6.7 Hz), 4.32 (2H, t, J 5.1 Hz), 4.29 (2H, t, J 5.3 Hz), 4.18-4.14 (2H, m), 4.14 (3H, s), 4.13 (3H, s), 3.95 (2H, t, J 6.8 Hz), 3.95 (2H, t, J 7.0 Hz), 2.11-1.82 (12H, m), 1.69-1.29 (24H, m), 1.08-0.84 (18H, m). .sup.13C NMR (101 MHz, CDCl.sub.3) δ.sub.c 151.9, 149.6, 149.3, 148.7, 148.1, 147.9, 144.4, 143.2, 141.5, 124.9, 124.8, 124.7, 124.4, 123.1, 123.1, 122.3, 119.4, 118.6, 116.0, 109.5, 109.3, 107.6, 107.3, 104.9, 76.3, 74.5, 74.0, 69.5, 68.9, 68.8, 55.8, 30.3, 30.3, 29.9, 29.2, 29.0, 28.8, 28.4, 28.3, 28.2, 28.1, 22.6, 22.6, 22.6, 14.1, 14.0, 14.0. MALDI.sub.+ m/z: 924.82 ([M+H].sup.+ 30%).
[0317] Precursor 6 was synthesised in the following method. Precursor 5 (680 mg, 0.736 mmol) and NiCl.sub.2.6H.sub.2O (552 mg, 2.33 mmol, 3 equivalents) were dissolved in THF:MeOH (20 mL, 5:4 ratio), to make a yellow solution, and then NaBH.sub.4 (586 mg, 15.5 mmol, 20 equivalents) was added over 15 minutes. The black reaction mixture was left stirring under a N.sub.2 atmosphere for 40 min after which time it was diluted with chloroform and the precipitate was gravity filters to leave a brown organic phase, which was then dried in vacuo to provide Precursor 6 as brown solid (614 mg, 93%).
[0318] The name for Precursor 6 is 5,6-dimethoxy-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracen-1-amine.
[0319] Precursor 6 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H 9.09 (1H, s), 8.98 (1H, s), 8.67 (1H, s), 7.97 (1H, s), 7.90 (1H, s), 4.76 (2H, s), 4.40 (2H, t, J 6.8 Hz), 4.34 (2H, t, J 6.5 Hz), 4.28 (2H, t, J 6.6 Hz), 4.20 (2H, t, J 6.6 Hz), 4.11 (3H, s), 4.08 (3H, s), 3.99 (2H, t, J 7.0 Hz), 3.93 (2H, t, J 7.0 Hz), 2.07-1.88 (12H, m), 1.66-1.34 (24H, m), 1.06-0.88 (18H, m, J 22.0, 12.0, 7.1 Hz). .sup.13C NMR (101 MHz, CDCl.sub.3) δ.sub.c 151.2, 148.5, 148.2, 148.0, 146.8, 143.8, 139.8, 136.9, 125.4, 125.0, 124.5, 124.4, 123.6, 123.5, 122.6, 120.5, 113.9, 111.8, 110.0, 109.4, 108.6, 108.4, 104.3, 73.9, 73.8, 69.7, 69.2, 69.0, 55.7, 30.4, 30.3, 29.7, 29.3, 29.1, 29.0, 28.5, 28.4, 28.3, 22.7, 22.6, 22.6, 14.1, 14.0. MALDI.sup.+ m/z: 893.8 ([M+H].sup.+ 100%).
[0320] Precursor 7 was synthesised in the following method. Precursor 6 (147 mg, 0.181 mmol) was dissolved in dry CH.sub.2Cl.sub.2 (20 mL) and dry MeCN (20 mL). The solution was cooled to 0° C. under a N.sub.2 atmosphere then tert-butyl nitrite (34 μL, 0.309 mmol, 1.7 equivalents) and TMSN.sub.3 (36 μL, 0.273 mmol, 1.5 equivalents) were added and the reaction mixture stirred 0° C. for 10 min and then at room temperature for 20 min. The solution was then dried in vacuo and purified via flash column chromatography (silica, 30% DCM, 70% n-hexane) to provide Precursor 7 as a while solid (120 mg, 72%).
[0321] The name for Precursor 7 is 1-azido-5,6-dimethoxy-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracene.
[0322] Precursor 7 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H 9.12 (1H, s), 9.03 (1H, s), 8.98 (1H, s), 8.01 (1H, s), 7.89 (1H, s), 4.45 (2H, t, J 6.7 Hz), 4.38-4.32 (2H, m), 4.29 (2H, t, J=6.0 Hz), 4.11 (3H, s), 4.09 (3H, s), 4.01 (2H, m), 3.94 (2H, t, J 6.6 Hz), 2.13-1.84 (12H, m), 1.69-1.32 (24H, m), 1.04-0.87 (18H, m). .sup.13C NMR (101 MHz, CDCl.sub.3) δ.sub.c 151.6, 148.9, 148.0, 148.0, 147.9, 147.9, 146.3, 144.1, 127.3, 125.4, 124.8, 124.0, 123.9, 123.3, 123.2, 122.8, 120.2, 119.4, 117.6, 112.6, 109.4, 109.1, 107.5, 104.7, 75.3, 74.4, 74.0, 69.6, 69.1, 69.0, 55.8, 30.4, 30.3, 29.5, 29.3, 29.1, 28.9, 28.5, 28.3, 28.2, 28.1, 22.7, 22.6, 22.5, 14.1, 14.0.
[0323] Compound 33 was synthesised using the following method. Precursor 7 (100 mg; 0.13 mmol) was dissolved in dry PhMe (5 mL) was added to a flask containing rhodium octanoate dimer (5 mg; 0.01 mmol), under a N.sub.2 atmosphere. This mixture was then heated to reflux and stirred for 20 hours. The reaction was cooled to room temperature and then dried in vacuo, the solid was then purified via flash column chromatography (silica; 95% n-hexane: 5% ethyl acetate) to provide Compound 33 as a white solid (58 mg, 50%).
[0324] The name of Compound 33 is 2-butyl-12,13-dimethoxy-5,6,9,10,15-pentakis(pentyloxy)dibenzo[4,5:9,10]pyreno[1,2-d]oxazole.
[0325] Compound 33 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H 10.08 (1H, s), 9.28 (1H, s), 9.15 (1H, s), 8.16 (1H, s), 8.02 (1H, s), 4.42 (2H, t, J 6.0 Hz), 4.37 (2H, d, J=5.8 Hz), 4.35-4.29 (4H, m, J 6.7, 3.3 Hz), 4.12 (3H, s), 4.11 (3H, s), 3.98 (2H, t, J=6.9 Hz), 3.18 (2H, t, J=7.5 Hz), 2.09-1.92 (10H, m), 1.67-1.36 (24H, m), 1.07-0.90 (18H, m). .sup.13C NMR (101 MHz, CDCl.sub.3) δ.sub.c 166.1, 151.3, 149.5, 148.8, 147.8, 147.7, 144.0, 142.4, 138.4, 137.1, 125.5, 124.9, 124.1, 124.0, 123.7, 123.5, 123.0, 119.9, 118.8, 116.1, 111.3, 109.6, 109.4, 107.1, 104.8, 74.5, 74.0, 69.8, 69.0, 68.8, 55.8, 55.7, 30.3, 30.1, 29.3, 29.1, 28.9, 28.7, 28.5, 28.4, 28.3, 28.2, 22.6, 22.5, 22.3, 14.1, 14.0, 13.8. MALDI.sup.+ m/z: 889.2 ([M+H].sup.+ 100%).
[0326] Method of Synthesisinq Compound 34
[0327] Precursor 6 (47 mg; 0.053 mmol), benzoyl chloride (30 μL, 0.265 mmol, 5 equivalents), and diisopropylethylamine (46 μL, 0.265 mmol, 5 equiv) were dissolved in dry PhMe (5 mL) and the mixture was heated to reflux under a N.sub.2 atmosphere. The reaction mixture was stirred for 1 h at which point the mixture was dried in vacuo then the solid was heated to 240° C. for 10 min. The reaction was cooled to room temperature and the solid was then purified via flash column chromatography (silica; 40% CH.sub.2Cl.sub.2, 60% n-hexane) to afford Compound 34 a white solid (16 mg, 33%).
[0328] The name of Compound 34 is12,13-dimethoxy-5,6,9,10,15-pentakis(pentyloxy)-2-phenyldibenzo[4,5:9,10]pyreno[1,2-d]oxazole.
[0329] Compound 34 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ.sub.H 9.29 (1H, s), 9.19 (1H, s), 8.48-8.43 (2H, m), 8.17 (1H, s), 8.03 (1H, s), 7.65-7.59 (3H, m), 4.53 (2H, t, J=6.9 Hz), 4.44-4.33 (6H, m), 4.14 (3H, s), 4.12 (3H, s), 3.99 (2H, t, J=6.9 Hz), 2.15-1.90 (10H, m), 1.71-1.36 (24H, m), 1.06-0.80 (18H, m). .sup.13C NMR (101 MHz, CDCl.sub.3) δ.sub.c 166.6, 161.8, 151.4, 149.5, 148.9, 147.9, 147.9, 144.1, 142.5, 138.5, 137.7, 132.9, 131.5, 129.5, 129.0, 128.4, 127.6, 127.4, 125.6, 124.8, 124.3, 124.0, 123.8, 123.5, 123.3, 119.8, 119.7, 116.4, 111.3, 109.7, 109.4, 106.9, 104.8, 74.7, 74.1, 69.8, 69.0, 64.5, 55.8, 55.7, 30.4, 30.2, 29.7, 29.3, 29.1, 28.9, 28.5, 28.5, 28.4, 25.6, 22.6, 22.5, 14.2, 14.1, 14.1, 14.1, 14.0. ES.sup.+ m/z: 910.5 ([M+H].sup.+ 100%).
[0330] Method of Synthesisinq Compound 35
[0331] Precursor 6 (100 mg; 0.111 mmol) 4-cyanobenzoyl chloride (92 mg, 0.555 mmol, 5 equiv), and diisopropylethylamine (90 μL, 0.555 mmol, 5 equiv) were dissolved in dry toluene (5 mL) and the mixture was heated reflux under a nitrogen atmosphere. The reaction mixture was stirred for 1 hour at which point the mixture was dried in vaccuo then the solid was heated to 240° C. for 10 minutes. The reaction was cooled to room temperature and the solid was then purified via flash column chromatography (silica; 40% DCM, 60% n-hexane) to afford Compound 35 as a white solid (17 mg, 16%).
[0332] The name of Compound 35 is 4-(12,13-dimethoxy-5,6,9,10,15-pentakis(pentyloxy)dibenzo[4,5:9,10]pyreno[1,2-d]oxazol-2-yl)benzonitrile.
[0333] Compound 35 had the following characterisation data: .sup.1H NMR (300 MHz, CDCl.sub.3) δ 10.02 (s, 1H), 9.27 (s, 1H), 9.15 (s, 1H), 8.43 (d, J=8.3 Hz, 2H), 8.13 (s, 1H), 7.99 (s, 1H), 7.84 (d, J=8.3 Hz, 2H), 4.45 (t, J=6.8 Hz, 2H), 4.36 (dt, J=13.0, 6.4 Hz, 6H), 4.14 (s, 3H), 4.12 (s, 3H), 3.97 (t, J=6.9 Hz, 2H), 2.12-1.90 (m, 10H), 1.65-1.38 (m, 24H), 1.06-0.88 (m, 18H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 159.8, 151.9, 149.9, 149.5, 148.5, 148.3, 144.6, 143.0, 138.6, 137.6, 133.0, 131.5, 128.0, 125.8, 124.8, 124.4, 123.9, 123.8, 123.8, 121.1, 119.9, 118.6, 117.0, 114.7, 111.5, 110.1, 109.8, 107.1, 105.2, 75.1, 74.4, 70.1, 69.3, 56.2, 56.1, 30.7, 30.5, 30.0, 29.6, 29.5, 29.3, 28.9, 28.8, 28.7, 28.7, 23.0, 22.9, 22.9, 14.6, 14.5, 14.4. MALDI.sup.+ m/z: 934.55 ([M+H].sup.+ 100%).
[0334] Method of Synthesisinq Compound 36
[0335] Compound 1 was synthesised using the following method. A solution of Precursor 1 (100 mg, 0.132 mmol), benzoyl chloride (92 mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo purified via flash column chromatography (silica, 60% CH.sub.2Cl.sub.2: 40% n-hexane) to afford an intermediate as a brown solid (19 mg, 18%).
[0336] The intermediate had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 8.55 (1H, s), 8.45 (1H, s), 8.07 (2H, d, J 7.5 Hz), 7.78 (1H, s), 7.74 (1H, s), 7.72 (1H, s), 7.71 (1H, s), 7.59 (1H, d, J 7.0 Hz), 7.54 (2H, t, J 7.4 Hz), 4.28-4.12 (10H, m), 3.67-3.54 (2H, m), 2.00-1.85 (8H, m), 1.70-1.37 (20H, m), 1.34-1.06 (8H, m), 1.02-0.90 (12H, m), 0.83 (3H, t, J 7.0), 0.75 (3H, t, J 7.1) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 174.6, 151.0, 149.7, 148.7, 148.4, 148.4, 144.0, 135.1, 131.7, 130.9, 128.5, 127.9, 126.6, 124.7, 124.2, 123.0, 122.6, 122.0, 110.3, 108.1, 107.7, 106.8, 106.7, 73.4, 70.1, 70.0, 69.5, 69.3, 68.8, 32.1, 30.1, 29.9, 29.6, 29.4, 29.3, 28.7, 28.5, 28.5, 28.1, 22.9, 22.7, 22.6, 14.3, 14.3, 14.1 ppm. MALDI m/z: 863.3 ([M]+100%).
[0337] A solution of the intermediate (100 mg, 0.116 mmol) and Lawesson's Reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was heated to and held at reflux for 48 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 min under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 36 as a green solid (17 mg, 19%).
[0338] The name for Compound 36 is 2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]thiazole.
[0339] Compound 36 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.51 (1H, s), 8.24-8.22 (2H, m), 7.92-7.89 (3H, m), 7.76 (1H, s), 7.53-7.52 (3H, m), 4.43-4.26 (10H, m), 2.10-1.95 (10H, m), 1.66-1.57 (10H, m), 1.53-1.47 (10H, m), 1.03-1.00 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 166.4, 152.5, 151.5, 150.2, 149.3, 148.3, 134.7, 130.9, 130.0, 129.3, 127.6, 125.7, 125.4, 124.7, 123.8, 119.0, 112.4, 108.9, 107.2, 106.9, 100.9, 70.3, 70.2, 69.7, 69.2, 69.1, 29.7, 29.6, 29.6, 29.5, 29.4, 28.8, 28.8, 28.8, 23.1, 23.0, 23.0, 23.0 23.0, 14.5, 14.5, 14.5, 14.5 ppm. MALDI m/z: 791.6 ([M]+100%).
[0340] Method of Synthesisinq Compound 37
[0341] Compound 37 was synthesised using the following method. A solution of Precursor 1 (100 mg, 0.132 mmol), 4-cyanobenzoyl chloride (109 mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The crude brown solid was added to a solution of Lawesson's Reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was heated to and held at reflux for 48 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 min under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 37 as a yellow solid (5 mg, 5%).
[0342] The name for Compound 37 is 4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]thiazol-8-yl)benzonitrile.
[0343] Compound 37 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.38 (1H, s), 8.31 (2H, d, J 8.4), 7.97-7.88 (4H, m), 7.79 (1H, d, J 8.5), 4.41-4.26 (10H, m), 2.06-1.95 (10H, m), 1.61-1.55 (10H, m), 1.51-1.44 (10H, m), 1.03-0.97 (15H, m) ppm. MALDI m/z: 816.9 ([M]+90%), 817.9 ([M+H].sup.+ 100%).
[0344] Method of Synthesisinq Compound 38
[0345] Compound 38 was synthesised from Precursor 8 in the following method.
[0346] Precursor 8 was synthesised using the following method. Compound 3 (8-(naphthalen-2-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole) (150 mg, 0.18 mmol, 1 eq) was dissolved in CH.sub.2Cl.sub.2 (10 mL) which had been dried and degassed for 10 min in a 2 necked flask fitted with a Subaseal(RTM) and had been purged with N.sub.2 for 10 min. The green solution was stirred at −10° C. under N.sub.2 for 10 min and boron tribromide (1M in CH.sub.2Cl.sub.2 solution) (0.2 mmol, 1.1 eq) was added via syringe through the Subaseal(RTM). The black solution was stirred under N.sub.2 for 2 h at −10° C. and then poured over crushed ice and stirred until all the ice had melted. The product was then extracted with ethyl acetate (20 mL), washed with water (3×50 mL) and evaporated to dryness yielding a brown solid. The product was then purified by flash column chromatography (20% EtOAc: n-hexane, silica) yielding 8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenyleno[1,2-d]oxazol-11-ol as a yellow solid (31 mg, 23%).
[0347] The name for Precursor 8 is 8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenyleno[1,2-d]oxazol-11-ol.
[0348] Precursor 8 had the following characterisation data-.sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.06 (1H, s), 8.83 (1H, s), 8.50 (1H, dd, J 8.6, 1.7), 8.05-8.03 (1H, m), 7.79 (1H, d, J 8.7), 7.91-7.89 (1H, m), 7.84 (1H, s), 7.79 (1H, s), 7.78 (1H, s), 7.74 (1H, s), 7.58-7.56 (2H, m), 5.97 (1H, s), 4.42 (2H, t, J 6.7), 4.29-4.20 (6H, m), 2.05-1.93 (8H, m), 1.63-1.45 (16H, m), 1.05-0.98 (12H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 161.7, 149.4, 148.9, 146.0, 145.3, 143.0, 140.9, 140.2, 134.8, 133.2, 129.1, 128.66, 128.0, 127.9, 127.6, 127.2, 126.8, 124.8, 124.7, 124.7, 124.0, 123.6, 123.4, 116.4, 112.7, 108.1, 107.1, 103.7, 103.6, 69.9, 69.8, 69.7, 69.1, 29.3, 29.3, 29.2, 28.6, 28.5, 28.4, 22.8, 22.7, 14.3, 14.2 ppm. MALDI m/z: 755.65 ([M].sup.+ 100%), 756.66 ([M+H].sup.+ 70%), 757.67 ([M+1+H].sup.+ 25%).
[0349] A slurry of Precursor 8 (100 mg, 0.13 mmol) and K.sub.2CO.sub.3 (114 mg, 0.83 mmol) in DMF (5 mL) was heated at reflux with a CaCl.sub.2 drying tube for 0.5 h, followed by addition of methyl 2-(2-(2-chloroethoxy)ethoxy)acetate (114 mg, 0.40 mmol) and KI (75 mg, 0.5 mmol). The resultant slurry was further heated at reflux for 3 h. The reaction mixture was allowed to cool to room temperature and the precipitate filtered off via suction filtration. The solvent was evaporated from the filtrate to dryness in vacuo and the crude solid was purified by purified via flash column chromatography (silica, 25% EtOAc: 75% n-hexane) to afford Compound 38 as a yellow solid (36 mg, 30%).
[0350] The name for Compound 38 is methyl 2-(2-(2-((8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenyleno[1,2-d]oxazol-11-yl)oxy)ethoxy)ethoxy)acetate.
[0351] Compound 38 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.16 (1H, s), 8.83 (1H, s), 8.50 (1H, dd, J 8.6, 1.7), 8.05-8.03 (2H, m), 7.91-7.81 (5H, m), 7.58-7.56 (2H, m), 4.60 (2H, t, J 5.5), 4.42 (2H, t, J 6.7), 4.29-4.21 (6H, m), 4.20 (3H, s), 3.85-3.65 (8H, m), 2.05-1.93 (8H, m), 1.63-1.45 (16H, m), 1.05-0.98 (12H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 173.9, 161.7, 149.4, 148.9, 145.9, 145.3, 142.0, 140.8, 140.4, 134.8, 133.1, 129.1, 128.7, 128.0, 127.9, 127.6, 127.2, 126.8, 124.8, 124.7, 124.6, 124.0, 123.6, 123.3, 116.5, 112.7, 108.1, 107.1, 103.7, 103.6, 71.8, 71.4, 71.2, 70.4, 69.8, 69.8, 69.7, 69.0, 68.5, 29.4, 29.3, 29.2, 28.6, 28.5, 28.4, 22.8, 22.7, 14.3, 14.2 ppm. MALDI m/z: 915.7 ([M].sup.+ 100%), 916.7 ([M+H].sup.+ 90%). Elemental analysis Found: C, 73.41; H, 7.56; N, 1.54%. C.sub.56H.sub.69NO.sub.10 requires C, 73.42; H, 7.59; N, 1.53%.
[0352] Method of Synthesisinq Compound 39
[0353] Compound 39 was synthesised using the following method. A solution of NaOH (3 mg, 0.08 mmol) in H.sub.2O (1 mL) was added to a solution of Compound 38 (35 mg, 0.04 mmol in MeOH (5 mL). The resultant solution was heated at reflux for 5 h. The reaction mixture was allowed to cool to room temperature and aliquots of 1M HCl aqueous solution was added until no further precipitate was 55 formed. The precipitate was collected through suction filtration affording a yellow solid (24 mg, 70%).
[0354] The name for Compound 39 is 2-(2-(2-((8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenyleno[1,2-d]oxazol-11-yl)oxy)ethoxy)ethoxy)acetic acid.
[0355] Compound 39 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.16 (1H, s), 8.83 (1H, s), 8.50 (1H, dd, J 8.6, 1.6), 8.05-8.03 (2H, m), 7.91-7.81 (5H, m), 7.58-7.56 (2H, m), 4.60 (2H, t, J 5.5 Hz), 4.42 (2H, t, J 6.7 Hz), 4.29-4.21 (6H, m), 3.85-3.65 (8H, m), 2.05-1.93 (8H, m), 1.63-1.45 (16H, m), 1.05-0.98 (12H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 175.7, 149.4, 148.9, 145.9, 145.3, 142.0, 140.8, 140.4, 134.8, 133.1, 129.1, 128.7, 128.0, 127.9, 127.6, 127.2, 126.8, 124.8, 124.7, 124.6, 124.0, 123.6, 123.3, 116.5, 112.7, 108.1, 107.1, 103.7, 103.6, 71.8, 71.4, 71.2, 70.4, 69.8, 69.8, 69.7, 69.0, 68.5, 29.4, 29.3, 29.2, 28.6, 28.5, 28.4, 22.8, 22.7, 14.3, 14.2 ppm. MALDI m/z: 901.5 ([M].sup.+ 100%), 902.5 ([M+H].sup.+ 70%). Elemental analysis Found: C, 73.24; H, 7.52; N, 1.54%. C.sub.55H.sub.67NO.sub.10 requires C, 73.23; H, 7.55; N, 1.55%.
[0356] Method of Synthesisinq Compound 40
[0357] Compound 40 was synthesised using the following method. A slurry of Precursor 8 (100 mg, 0.13 mmol) and K.sub.2CO.sub.3 (37 mg, 0.26 mmol) in MeCN (5 mL) was heated at reflux with a CaCl.sub.2 drying tube for 0.5 h, followed by addition of 2-(2-(2-azidoethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (87 mg, 0.26 mmol). The resultant slurry was further heated at reflux for 24 h. The reaction mixture was allowed to cool to room temperature and the precipitate filtered off via suction filtration. The solvent was evaporated from the filtrate to dryness in vacuo and the crude solid was purified by purified via flash column chromatography (silica, 25% EtOAc: 75% n-hexane) to afford Compound 38 as a yellow solid (18 mg, 15%).
[0358] The name for Compound 40 is 11-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)-8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0359] Compound 40 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.14 (1H, s), 8.82 (1H, s), 8.51 (1H, dd, J 8.6, 1.7), 8.06-8.03 (2H, m), 7.91-7.80 (5H, m), 7.57-7.55 (2H, m), 4.59 (2H, t, J 5.5 Hz), 4.41 (2H, t, J 6.7 Hz), 4.29-4.20 (6H, m), 4.15-4.10 (2H, m), 3.87-3.82 (2H, m), 3.69-3.57 (4H, m), 3.30-3.21 (2H, m), 2.05-1.93 (8H, m), 1.63-1.45 (16H, m), 1.05-0.98 (12H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 161.7, 149.4, 148.8, 145.9, 145.4, 142.9, 140.8, 140.2, 134.7, 133.2, 129.1, 128.7, 128.0, 127.9, 127.6, 127.1, 126.9, 124.8, 124.7, 124.6, 124.0, 123.6, 123.4, 116.4, 112.7, 108.1, 107.2, 103.7, 103.6, 72.5, 70.7, 70.4, 70.1, 69.9, 69.8, 69.7, 69.0, 50.6, 29.32, 29.30, 29.17, 28.54, 28.46, 28.43, 22.75, 22.71, 14.27, 14.21 ppm. MALDI m/z: 912.9 ([M].sup.+ 100%), 913.9 ([M+H].sup.+ 90%). Elemental analysis Found: C, 73.36; H, 7.55; N, 6.12%. C.sub.55H.sub.68N.sub.4O.sub.8 requires C, 73.34; H, 7.51; N, 6.14%.
[0360] Method of Synthesisinq Compound 41
[0361] Compound 41 was synthesised using the following method. A slurry of Precursor 8 (100 mg, 0.13 mmol) and K.sub.2CO.sub.3 (37 mg, 0.26 mmol) in MeCN (5 mL) was heated at reflux with a CaCl.sub.2 drying tube for 0.5 h followed by addition of 2-(2-(2-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)ethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (101 mg, 0.26 mg). The resultant slurry was further heated at reflux for 24 h. The reaction mixture was allowed to cool to room temperature and the precipitate filtered off via suction filtration. The solvent was evaporated from the filtrate to dryness in vacuo and the crude solid was purified by purified via flash column chromatography (silica, silica, 50% EtOAc: 50% n-hexane) to afford Compound 38 as a yellow solid (15 mg, 13%).
[0362] The name for Compound 41 is 2-(2-(2-((8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenyleno[1,2-d]oxazol-11-yl)oxy)ethoxy)ethoxy)ethan-1-amine.
[0363] Compound 41 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.13 (1H, s), 8.82 (1H, s), 8.50 (1H, dd, J 8.6, 1.7), 8.07-8.03 (2H, m), 7.91-7.81 (5H, m), 7.57-7.57 (2H, m), 4.58 (2H, t, J 5.5 Hz), 4.43 (2H, t, J 6.7 Hz), 4.28-4.20 (6H, m), 4.14-4.10 (2H, m), 3.86-3.82 (2H, m), 3.69-3.57 (4H, m), 3.17-3.19 (2H, m), 2.04-1.92 (8H, m), 1.63-1.44 (16H, m), 1.04-0.97 (12H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 161.7, 149.4, 148.8, 145.9, 145.4, 142.9, 140.8, 140.2, 134.7, 133.2, 129.1, 128.7, 128.0, 127.9, 127.6, 127.1, 126.9, 124.8, 124.7, 124.6, 124.0, 123.6, 123.4, 116.4, 112.7, 108.1, 107.2, 103.7, 103.6, 72.3, 70.6, 70.3, 70.0, 69.9, 69.8, 69.7, 69.0, 42.5, 29.4, 29.3, 29.2, 28.5, 28.5, 28.4, 22.75, 22.7, 14.3, 14.2 ppm. MALDI m/z: 886.5 ([M].sup.+ 100%), 887.6 ([M+H].sup.+ 70%).
[0364] Method of Synthesisinq Compound 44
[0365] Compound 44 was synthesised using the following method. A solution of Precursor 2 (100 mg, 0.132 mmol), 3-fluorobenzoyl chloride (92 mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo purified via flash column chromatography (silica, 60% CH.sub.2Cl.sub.2: 40% n-hexane) to afford an intermediate as a brown solid (19 mg, 18%).
[0366] The intermediate (3-fluoro-N-(2,3,6,7,10,11-hexakis(pentyloxy)triphenylen-1-yl)benzamide) (100 mg, 0.11 mmol) was dissolved in xylenes (10 mL) and Woollins reagent (117.8 mg, 0.22 mmol) was added to the flask. The reaction was stirred at reflux for 24 h before being cooled to room temperature causing the formation of a grey precipitate. The contents of the flask were filtered through filter paper and the filtrate recovered. The filtrate was evaporated to dryness and purified by column chromatography (silica, 40% dichloromethane: hexane) and (silica, 1% acetone: hexane) yielding 8-(3-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d][1,3]selenazole as a yellow solid (1.8 mg).
[0367] The name for Compound 44 is 8-(3-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d][1,3]selenazole.
[0368] Compound 44 had the following characterisation data: .sup.1H NMR δ.sub.H (500 MHz, CDCl.sub.3) 10.40 (1H, s), 8.00 (1H, s), 7.97 (1H, d, J 9.8 Hz), 7.95 (1H, s), 7.92 (1H, s), 7.90 (1H, d, J 7.8 Hz), 7.87 (1H, s), 7.49 (1H, dd, J 14.1, 8.5 Hz), 7.24-7.21 (1H, m), 4.45 (2H, t, J 6.8 Hz), 4.42 (2H, t, J 6.7 Hz), 4.28 (6H, dt, J 13.4, 6.6 Hz), 2.06-1.94 (10H, m), 1.61-1.44 (20H, m), 1.03-0.93 (15H, m) ppm. TOF LD.sup.+ m/z=860.4 ([M+2+H].sup.+ 30%), 859.4 ([M+2].sup.+ 60%), 858.4 ([M+H].sup.+ 90%), 857.4 ([M].sup.+ 100%), 856.4 ([M-2+H].sup.+ 40%), 855.4 ([M-2].sup.+ 60%), 854.4 ([M-3].sup.+30%), 825.5 ([TpOxPhmF+MeOH].sup.+), 793.4 ([TpOxPhmF].sup.+).
[0369] Method of Synthesisinq Compound 45
[0370] Compound 45 was synthesised using the following method. Precursor 2 (190 mg, 0.25 mmol, 1 eq) and 4-methoxybenzoyl chloride (213 mg, 1.25 mmol, 5 eq) were dissolved in dry toluene (7 mL) and N,N-disopropylethylamine (0.2 mL, 1.25 mmol, 5 eq) was added. The solution was stirred and heated to reflux under a CaCl.sub.2 drying tube for 2 h. The solution was then evaporated to dryness and the crude solid was heated to 240° C. for 10 mins. The crude product was recrystalised (dichloromethane: hexane, 1: 5) and then purified by silica plug (60% dichloromethane: hexane) to yield 8-(4-methoxyphenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole as an off white solid (53 mg, 26%).
[0371] The name for Compound 45 is 8-(4-methoxyphenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.
[0372] Compound 45 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.15 (1H, s), 8.32 (2H, d, J 8.9 Hz), 7.93-7.87 (4H, m), 7.06 (2H, d, J 8.9 Hz), 4.46 (4H, t, J 7.0 Hz), 4.28-4.24 (6H, m), 3.93 (3H, s), 2.12-1.94 (10H, m), 1.65-1.43 (20H, m), 1.03-0.96 (15H, m) ppm. MALDI m/z: 804.9 ([M].sup.+ 100%), 805.9 ([M+H].sup.+ 70%), 806.9 ([M+1+H].sup.+ 25%).
[0373] Method of Synthesisinq Compound 46
[0374] Compound 46 was synthesised using the following method. A solution of Precursor 1 (100 mg, 0.132 mmol), benzoyl chloride (92 mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo purified via flash column chromatography 55 (silica, 60% CH.sub.2Cl.sub.2: 40% n-hexane) to afford an intermediate as a brown solid (19 mg, 18%).
[0375] The intermediate had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 8.55 (1H, s), 8.45 (1H, s), 8.07 (2H, d, J 7.5 Hz), 7.78 (1H, s), 7.74 (1H, s), 7.72 (1H, s), 7.71 (1H, s), 7.59 (1H, d, J 7.0 Hz), 7.54 (2H, t, J 7.4 Hz), 4.28-4.12 (10H, m), 3.67-3.54 (2H, m), 2.00-1.85 (8H, m), 1.70-1.37 (20H, m), 1.34-1.06 (8H, m), 1.02-0.90 (12H, m), 0.83 (3H, t, J 7.0 Hz), 0.75 (3H, t, J 7.1 Hz) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 174.6, 151.0, 149.7, 148.7, 148.4, 148.4, 144.0, 135.1, 131.7, 130.9, 128.5, 127.9, 126.6, 124.7, 124.2, 123.0, 122.6, 122.0, 110.3, 108.1, 107.7, 106.8, 106.7, 73.4, 70.1, 70.0, 69.5, 69.3, 68.8, 32.1, 30.1, 29.9, 29.6, 29.4, 29.3, 28.7, 28.5, 28.5, 28.1, 22.9, 22.7, 22.6, 14.3, 14.3, 14.1 ppm. MALDI m/z: 863.3 ([M]+100%).
[0376] A solution of the intermediate (100 mg, 0.116 mmol) and Lawesson's Reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was heated to and held at reflux for 48 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 mins under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 46 as a green solid (17 mg, 19%).
[0377] The name for Compound 46 is 2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]thiazole.
[0378] Compound 46 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.51 (1H, s), 8.24-8.22 (2H, m), 7.92-7.89 (3H, m), 7.76 (1H, s), 7.53-7.52 (3H, m), 4.43-4.26 (10H, m), 2.10-1.95 (10H, m), 1.66-1.57 (10H, m), 1.53-1.47 (10H, m), 1.03-1.00 (15H, m) ppm. .sup.13C NMR δ.sub.c: (100 MHz, CDCl.sub.3) 166.4, 152.5, 151.5, 150.2, 149.3, 148.3, 134.7, 130.9, 130.0, 129.3, 127.6, 125.7, 125.4, 124.7, 123.8, 119.0, 112.4, 108.9, 107.2, 106.9, 100.9, 70.3, 70.2, 69.7, 69.2, 69.1, 29.7, 29.6, 29.6, 29.5, 29.4, 28.8, 28.8, 28.8, 23.1, 23.0, 23.0, 23.0 23.0, 14.5, 14.5, 14.5, 14.5 ppm. MALDI m/z: 791.56 ([M]+100%).
[0379] Method of Synthesisinq Compound 47
[0380] Compound 47 was synthesised using the following method. A solution of Precursor 1 (100 mg, 0.132 mmol), 4-cyanobenzoyl chloride (109 mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was heated to and held at reflux for 18 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The crude brown solid was added to a solution of Lawesson's Reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was heated to and held at reflux for 48 h under N.sub.2. The reaction was cooled to room temperature and then evaporated to dryness in vacuo. The solid was then heated and held at 240° C. for 15 mins under N.sub.2. The crude black solid was then cooled to room temperature and purified via flash column chromatography (silica, 40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 47 as a yellow solid (5 mg, 5%).
[0381] The name for Compound 47 is 4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]thiazol-8-yl)benzonitrile.
[0382] Compound 47 had the following characterisation data: .sup.1H NMR δ.sub.H: (300 MHz, CDCl.sub.3) 10.38 (1H, s), 8.31 (2H, d, J 8.4 Hz), 7.97-7.88 (4H, m), 7.79 (1H, d, J 8.5 Hz), 4.41-4.26 (10H, m), 2.06-1.95 (10H, m), 1.61-1.55 (10H, m), 1.51-1.44 (10H, m), 1.03-0.97 (15H, m) ppm. MALDI m/z: 816.9 ([M]+90%), 817.9 ([M+H]+ 100%).
[0383] Referring now to Table 1, there is shown luminescent data for Compounds 1 to 6.
TABLE-US-00001 TABLE 1 Luminescent data for Compounds 1 to 6 c ϵ.sub.r Viscosity (cP) Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Ethyl acetate 6.0 0.45 Absorption λ.sub.max (nm) 281 270 272 275 272 253 Emission λ.sub.max (nm) 367 467 494 510 536 594 pSS (cm.sup.−1) 8300 15600 16500 16800 18100 22700 Φ 0.18 ± 0.01 0.46 ± 0.04 0.55 ± 0.05 0.48 ± 0.04 0.51 ± 0.04 † Brightness (M.sup.−1 cm.sup.−1) 29 ± 5 51 ± 5 92 ± 9 56 ± 5 53 ± 5 † Octan-1-ol 10.3 7.36 Absorption λ.sub.max (nm) 281 271 272 275 270 255 Emission λ.sub.max (nm) 367 473 497 515 526 384 pSS (cm.sup.−1) 8300 15800 16600 17000 18000 13200 Φ 0.30 ± 0.03 0.61 ± 0.06 0.71 ± 0.07 0.55 ± 0.05 0.56 ± 0.05 † Brightness (M.sup.−1 cm.sup.−1) 36 ± 7 64 ± 6 91 ± 9 67 ± 7 50 ± 5 † Acetonitrile 37.5 0.38 Absorption λ.sub.max (nm) 281 270 273 275 270 253 Emission λ.sub.max (nm) 367 492 524 543 592 630 pSS (cm.sup.−1) 8300 16700 17600 18000 20200 23650 Φ 0.20 ± 0.02 0.46 ± 0.04 0.51 ± 0.05 0.36 ± 0.04 0.21 ± 0.02 † Brightness (M.sup.−1 cm.sup.−1) 12 ± 2 38 ± 4 44 ± 4 30 ± 3 ‡ † † No value could be obtained ‡ No value could be obtained due to poor solubility and therefore no ϵ data.
[0384] Referring now to Tables 2 to 4, there is provided luminescence data for pairs of compounds which are capable of absorbing at the same wavelength and emitting at different wavelengths.
TABLE-US-00002 TABLE 2 Luminescence data for pair 1 ε × 10.sup.3 (M.sup.−1 cm.sup.−1) at Absorption Emission 355 405 λ.sub.Max % Abs at % Abs at λ.sub.Max pSS Compound λ.sub.Max nm nm (nm) 355 nm.sup.a 405 nm.sup.a (nm) (nm) (cm.sup.−1) QY Compound 97 21 0 270 22 0 444 174 14000 0.40 45 Compound 103 13 14 272 12 14 558 286 18800 0.32 12
TABLE-US-00003 TABLE 3 Luminescence data for pair 2 ε × 10.sup.3 (M.sup.−1 cm.sup.−1) at Absorption Emission 355 405 λ.sub.Max % Abs at % Abs at λ.sub.Max pSS Compound λ.sub.Max nm nm (nm) 355 nm.sup.a 405 nm.sup.a (nm) (nm) (cm.sup.−1) QY Compound 97 21 0 270 22 0 444 174 14000 0.40 45 Compound 164 29 13 272 17 7 494 222 16500 0.55 3
TABLE-US-00004 TABLE 4 Luminescence data for pair 3 ε × 10.sup.3 (M.sup.−1 cm.sup.−1) at Absorption Emission 355 405 λ.sub.Max % Abs at % Abs at λ.sub.Max pSS Compound λ.sub.Max nm nm (nm) 355 nm.sup.a 405 nm.sup.a (nm) (nm) (cm.sup.−1) QY Compound 72 39 1.5 271 54 2 421 150 13150 0.70 22 Compound 164 29 13 272 17 7 494 222 16500 0.55 3
EXAMPLE 1: VISUALISING A HUMAN LIVER
[0385] In Vitro Testing
[0386] To test the relative toxicity of tetrahydrofuran (THF) for liver cells, Huh-7 cells (hepatoma cell line used for a model of hepatocytes) were labelled with CMFDA (CellTracker Green, in DMSO, Invitrogen) and then treated with half log concentrations of THF (0.1%, 0.3%, 1%, 3%) for 1 hr. Cells were then imaged live using a Zeiss primovert fluorescence microscope.
[0387] The cell images indicated that at 0.1% and 0.3% THF there were no differences in the cell culture compared to the reference. At 1% and 3% THF an increasing number of dead cells were recorded.
[0388] Ex Vivo Testing
[0389] All fluorophores were testing using donated human tissue which had been previously rejected for transplantation. All reagents were diluted in pre-warmed Dulbecos Modified Eagles Medium (DMEM) or CO.sub.2-independent media (both Invitrogen) to working concentrations and then perfused into pieces of liver for 45 min. Membrane and nuclear dyes were used simultaneously to visualise other cellular structures within the liver. Tissues were then imaged using multiphoton microscopy (825 nm). All fluorophores were used at 1 μg/ml (giving 0.1% of vehicle, being DMSO or THF). Testing of TpOx-2-Nap (green fluorophore) was done using DMSO as a solvent. Although this yielded limited solubility, the green fluorescence was still visible. A commercial red cell membrane dye (CMFDA) was used for comparison, having been perfused through a separate piece of tissue from the same donor. When using TpOx-Ph (blue fluorophore), THF was used as the solvent, which yield brighter and less punctate fluorescence.
[0390]
[0391]
[0392] These results demonstrate that the compounds described herein are suitable for live tissue imaging, since they permeate well into tissues, are capable of crossing the cell membrane, and provide bright emissions.