Triphenylene derivatives for use in imaging biological tissues or fluids

Abstract

A composition for imaging a biological tissue or fluid, comprising a compound of formula (A) and a bioacceptable diluent or carrier, wherein in formula (A), X represents one of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a selenium atom, R represents an aromatic group and / or an aliphatic group, p is an integer from 1 to 2, q and s are independently integers from 1, 2, 3, or 4, and Y 1 , Y 2 , and Y 3 However, independently, each represents 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 Y 1 , Y 2 , and Y 3 A composition in which two or more of these can combine together to form a condensed ring. TIFF2022550486000018.tif50170

Description

Technical Field

[0001] The present invention relates to a composition comprising a luminescent compound and a method of using such compound. In particular, the invention relates to the use of luminescent compounds for the imaging of biological tissues and fluids.

[0002] Optical imaging is used to visualize internal tissues and organs within organisms, including animals and humans. The purpose of tissue imaging can be for laboratory studies to learn about internal structures without using surgery or other invasive techniques. In addition, optical imaging can be used in medicine to detect diseases and other abnormalities in visceral tissues and organs.

[0003] One type of tissue imaging is fluorescence imaging, which uses fluorescent dyes, tags, or probes to label cell or molecular structures. The fluorescent dye, tag, or probe can then be imaged by exciting it with illumination light and causing fluorescence at a wavelength different from that of the illumination light. The emitted light can then be captured by a microscope or camera.

[0004] In some techniques, fluorescent probes that bind to specific targets within an organism are used. For example, immunofluorescence involves the use of fluorescent molecules chemically conjugated to antibodies that are specific for a target antigen. In other techniques, organisms are genetically modified to express proteins tagged with fluorescent markers, of which the green fluorescent protein (GFP) is the most common example. However, there is a need to label structures in living tissues without affecting cell biology and without modifying the organism's genome. There is also a need for combinations of fluorescent dyes that do not cross-talk with each other and can be excited by only a few types of lasers.

[0005] The present invention has been devised with these problems in mind.

[0006] According to a first aspect of the present invention, there is provided a composition for imaging biological tissues or fluids, comprising a luminescent compound of general formula (A) and a biologically acceptable diluent or carrier, [Chemical formula] wherein X represents one of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a selenium atom, R represents an aromatic group and / or an aliphatic group, p is an integer from 1 to 2, q and s are independently an integer of 1, 2, 3, or 4, Y 1 、Y 2 、and Y 3 are independently 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 (e.g., a group containing a polyethylene glycol moiety), an oxygen atom (e.g., a hydroxyl group, or an alkylated oxygen atom forming an alkoxy group), a nitrogen atom (e.g., a primary, secondary, or tertiary amine group), a cyano group, a nitro group, and / or Y 1 、Y 2 、and Y 3 Two or more of which may combine together to form a condensed ring (e.g., a condensed aromatic ring), and a composition is provided.

[0007] The inventors observed that when the compound of general formula (A) was perfused into human liver ex vivo, it was effectively taken up by hepatocytes. Surprisingly, significantly higher uptake by T cells was observed compared to hepatocytes. Without being bound by theory, the preferential accumulation of the compound in T cells is considered to have moderate utility such as enabling the identification and / or monitoring of inflammatory sites.

[0008] Furthermore, it was observed that the compound was retained within hepatocytes and T cells for several hours, enabling visualization of the hepatic vein. This has not been achieved previously as existing fluorophores leak rapidly from cells into the blood. Thus, the compositions of the invention advantageously enable elucidation of tissue structure.

[0009] Thus, in some embodiments, the luminescent compound is capable of crossing the cell membrane. The cells can be animal cells such as human cells.

[0010] In some embodiments, the luminescent compound can be retained within the cell for at least 1 minute, at least 5 minutes, at least 10 minutes, at least 30 minutes, at least 1 hour, or at least 2 hours.

[0011] In some embodiments, the luminescent compound preferentially accumulates in lymphocytes such as T cells. In other words, when a mixture of two or more types of cells including T cells is contacted with the luminescent compound, the compound is taken up by T cells in a greater amount than other cell(s).

[0012] Thus, the compounds, compositions, and methods described herein can be used, for example, for research purposes to determine the structure of biological tissues. The compounds, compositions, and methods described herein can also be used to evaluate the health of biological tissues. For example, the compositions and methods can be used to evaluate the viability of organs ex vivo for transplantation. Alternatively, the compounds, compositions, and methods can be used to detect abnormalities or diseases.

[0013] The inventive composition comprises a luminescent compound of general formula (A) in a biologically acceptable diluent or carrier. Suitable biologically acceptable diluents and carriers include, but are not limited to, physiologically acceptable buffer solutions, buffered saline solutions such as phosphate buffered saline, saline, balanced crystalloid fluids, deionized water, blood, cell culture media (e.g., minimum essential medium, or CO2-independent medium), plasma, and the like. The biologically acceptable diluent or carrier can be physiologically or pharmaceutically acceptable.

[0014] The luminescent compound(s) can be dissolved in the diluent or carrier. Alternatively, the luminescent compound can be dispersed or suspended in, or mixed with, the diluent or carrier.

[0015] The composition can further comprise appropriately selected excipients, fillers, binders, wetting agents, lubricants, surfactants, dispersants, buffer solutions, preservatives, adjuvants, disinfectants, analgesics, stabilizers, and / or isotonic agents.

[0016] The composition can be prepared by mixing the luminescent compound with a biologically acceptable diluent or carrier. Prior to mixing, the luminescent compound can be dissolved in a solvent such as DMSO, THF, or 2-methyl THF.

[0017] In some embodiments, the composition comprises two or more different luminescent compounds, at least one of which has general formula (A). The two or more different luminescent compounds can be present in the composition at different or the same concentrations.

[0018] One (or each) luminescent compound can be present in the composition at a concentration of 0.1 - 20 μg / ml, 0.5 - 10 μg / ml, or 1 - 5 μg / ml.

[0019] For example, the composition can comprise a first luminescent compound of general formula (A) and a second luminescent compound different from the first luminescent compound. In an embodiment, the composition can further comprise a third luminescent compound different from the first and second luminescent compounds.

[0020] In an embodiment, the second and / or third luminescent compound(s) can be a compound different from the luminescent compound represented by general formula (A). In other words, the second and / or third luminescent compound(s) has a structure not according to general formula (A). For example, the second and / or third luminescent compound(s) can be a polycyclic aromatic hydrocarbon compound selected from, for example, one of fluorescein, eosin, rhodamine, or an analog thereof.

[0021] In an alternative embodiment, the second luminescent compound is represented by general formula (A) and is different from the structure of the first luminescent compound. In some embodiments, the third luminescent compound is represented by general formula (A) and is different from the structures of the first and second luminescent compounds.

[0022] Advantageously, customized and / or different absorption and / or emission spectra are provided by using, for example, different combinations and / or concentrations of different first, second, and / or third luminescent compounds represented by general formula (A).

[0023] Conveniently, the composition can contain a plurality of luminescent compounds that absorb light at approximately the same wavelength but emit light at different wavelengths. In other words, the λ of the compounds max is different. This is advantageous as it allows the use of a single laser to excite the compounds.

[0024] In some embodiments, the composition contains a first luminescent compound of formula (A) that emits light at a first wavelength (i.e., has a first λ max ), and a second luminescent compound of formula (A) that emits light at a second wavelength higher than the first wavelength (i.e., has a second λ max ), and both the first and second compounds are capable of absorbing light at a third wavelength lower than both the first and second wavelengths.

[0025] In some embodiments, the second wavelength (the second λ max) is at least 5%, at least 10%, or at least 15% higher than the first wavelength (first λ max ). This enables easy distinction between the emissions of the first and second compounds.

[0026] In some embodiments, both the first and second compounds are capable of absorbing light having a wavelength of 355 nm. In further embodiments, only one of the first and second compounds is capable of absorbing light having a wavelength of 405 nm.

[0027] Examples of pairs of luminescent compounds having the above-described properties are TpOx-Ph-pOMe (Compound No. 45 in Figure 3) and TpOx-Ph-pCN (Compound No. 12); TpOx-Ph-pOMe (Compound No. 45) and TpOx-2-Nap (Compound No. 3); and TpOx-Ph-pNMe2 (Compound No. 22) and TpOx-2-Nap (Compound No. 3).

[0028] In some embodiments, the luminescent compound of formula (A) conjugates to a further molecule such as a protein, chemical moiety, or nucleic acid. Such a molecule, when conjugated to a luminescent label, can then be used as a probe for the detection of a specific target. For example, the composition can include a luminescent compound conjugated to an antibody specific for a target protein. The composition can then be used for the detection of the target protein in a biological tissue or fluid.

[0029] In some embodiments, the composition includes a first luminescent compound conjugated to a first antibody and a second luminescent compound different from the first luminescent compound. The second luminescent compound can conjugate to a second antibody different from the first antibody. For example, the first and second antibodies target different proteins.

[0030] In some embodiments, the composition comprises cells stained with a luminescent compound. By "staining", it will be understood that the luminescent compound can cross the cell membrane and be present within the cytoplasm of the cell, or the luminescent compound can bind to the cell membrane or cell surface receptor, for example, via a conjugated antibody or chemical moiety.

[0031] The cells can include red blood cells and / or white blood cells. The white blood cells can be neutrophils, eosinophils (acidophiles), basophils, lymphocytes (e.g., B cells and / or T cells), and / or monocytes. In some embodiments, the composition comprises T cells stained with a luminescent compound. Such a composition can be used to monitor the location(s) where T cells have accumulated in a subject. The T cells can be obtained from a subject to whom the composition is intended to be administered.

[0032] According to a second aspect of the invention, there is provided the use of a luminescent compound or composition of formula I of the first aspect of the invention in a method of obtaining an image of a biological tissue or fluid.

[0033] The image can be obtained by fluorescence imaging, for example, by a fluorescence microscope.

[0034] In some embodiments, the biological tissue or fluid is in vivo.

[0035] Thus, in a third aspect of the invention, there is provided a method of obtaining an image of a biological tissue or fluid in a subject in vivo, the method comprising: - obtaining an image of the subject using a fluorescence microscope, wherein the subject has been administered a luminescent compound or composition of formula (A) of the first aspect of the invention.

[0036] In some embodiments, the subject has been pre-administered the luminescent compound or composition.

[0037] In some alternative embodiments, the method further comprises administering the luminescent compound or composition of formula (A) of the first aspect of the invention to the subject before obtaining the image.

[0038] In some embodiments, the method is for analyzing healthy biological tissue or fluid in a subject. The luminescent compound or composition can be administered to the subject's body at a location close to the site of interest. For example, in one embodiment where the method is for obtaining an image of the subject's liver, the method can include administering the compound or composition to a blood vessel proximal to the liver.

[0039] In some alternative embodiments, the biological tissue or fluid is in vitro or ex vivo.

[0040] In a fourth aspect of the invention, there is provided a method for obtaining an image of biological tissue or fluid previously obtained from a subject, the method comprising: - administering or contacting the biological tissue or fluid with the luminescent compound or composition of formula (A) of the first aspect of the invention; and - obtaining an image of the biological tissue or fluid using a fluorescence microscope.

[0041] The compound or composition can be administered immediately before obtaining the image. Alternatively, there can be a time delay between the step of administering the compound or composition and the step of obtaining the image. For example, the image can be obtained at least 5 minutes, at least 10 minutes, at least 30 minutes, or at least 1 hour after the compound or composition has been administered. Such a time delay can be beneficial to allow the luminescent compound(s) to be taken up by the cells.

[0042] Obtaining an image using a fluorescence microscope can include irradiating the subject or tissue or fluid with a light source and recording the emission spectrum in the UV, visible, and / or near-infrared range of the electromagnetic spectrum.

[0043] The light source can emit a wavelength suitable for exciting the luminescent compound(s). The wavelength can be in the range of 100 - 700 nm, 200 - 600 nm, or 300 - 500 nm.

[0044] The emission spectrum can be recorded in the range of 100 - 1000 nm, 100 - 700 nm, 200 - 600 nm, or 300 - 500 nm.

[0045] The luminescent compound(s) can emit light in the visible spectrum or near - infrared spectrum, i.e., at 380 nm - 750 nm, and / or have a Stokes shift in the range of 8000 cm -1 ~25,000 cm -1 For example, in the range of 15,000 cm -1 ~25,000 cm -1

[0046] In some embodiments, the luminescent compound(s) can have a conductivity value in the range of 5.0×10 -13 S cm -1 and 1.5×10 -11 S cm -1 For example, in the range of 6×10 -12 S cm -1 ~1.5×10 -11 S cm -1

[0047] When the luminescent compound(s) is irradiated with light at 350 nm in the range of 1.5×10 -10 S cm -1 ~1×10 -3 S cm -1 For example, in the range of 1×10 -8 S cm -1 ~1×10 -3 S cm -1 it can exhibit photoconductivity.

[0048] ​​In some embodiments, the fluorescence microscope is a multiphoton microscope. As is known in the art, in a multiphoton microscope (also known as a two-photon microscope), two photons of light are absorbed at each excitation. This technique is different from conventional fluorescence microscopes where the excitation wavelength is shorter than the emission wavelength. Two-photon excitation microscopy typically uses near-infrared excitation light. In some embodiments, the multiphoton microscope is performed by irradiating a subject, tissue, or fluid using a light source that emits wavelengths in the range of 500-1000 nm, 600-900 nm, or 700-800 nm. The use of a multiphoton microscope is advantageous because it uses lower energy light and thus causes less damage to biological samples. Multiphoton microscopes also have a lower potential for photobleaching dyes and can penetrate tissue more deeply.

[0049] Biological tissue can be any type of tissue such as connective tissue, muscle tissue (including tendons, ligaments, and muscle), nerve tissue, epithelial tissue, vascular tissue (including arteries, veins, and capillaries), lymphatic tissue (including lymphatic vessels and lymph nodes), endocrine tissue, glands, or organs.

[0050] Organs can be the tongue, esophagus, stomach, small intestine (duodenum, jejunum, or ileum), colon, liver, gallbladder, pancreas, heart, lungs, diaphragm, kidneys, bladder, ovaries, uterus, brain, eyes, skin, or spleen.

[0051] Glands can be the thymus, pituitary gland, pineal gland, parathyroid gland, thyroid gland, salivary glands, or adrenal glands.

[0052] In some embodiments, the fluid is blood.

[0053] The compound(s) or composition can be administered locally, orally, or parenterally, for example, by injection or infusion. For oral administration, the compound(s) or composition can be formulated as a capsule, food, or beverage. The capsule can be prepared by filling a capsule shell with the compound(s) or composition, either alone or as a mixture with one or more accessory components, and then sealing them in the usual manner. Formulations for oral administration can be in the form of an aqueous liquid or non-aqueous liquid, or a solution, suspension, or dispersion in a carrier fluid such as an emulsion.

[0054] In some embodiments, the compound or composition is administered by injection, for example, intravenously, intramuscularly, subcutaneously, or intraarterially.

[0055] Formulations suitable for topical administration can be provided, for example, as a gel, solution, suspension, or dispersion (e.g., in the form of drops or sprays), cream, or ointment.

[0056] In some embodiments, the compound(s) or composition is administered by perfusion. "Perfusion" refers to the passage of a fluid through an organ or tissue via the circulatory system (e.g., blood flow) or lymphatic system. For example, in a method of imaging a biological tissue such as an organ ex vivo, the compound can be perfused into the organ in a biologically acceptable carrier fluid, for example, by injecting a carrier fluid containing the compound into the blood vessels associated with the organ.

[0057] In some embodiments, the method includes administering two or more different luminescent compounds to a subject, biological tissue, or fluid. The compounds can be administered simultaneously or sequentially. In some embodiments, the compounds are administered by different modes of administration.

[0058] In a further aspect, the invention provides a kit for imaging a biological tissue or fluid, the kit comprising - a luminescent compound of formula (A), and - instructions for use.

[0059] The kit may further comprise the biologically acceptable diluent or carrier described above. Alternatively or in addition, the kit may comprise one or more further components such as excipients, fillers, binders, wetting agents, lubricants, surfactants, dispersants, buffers, preservatives, adjuvants, disinfectants, analgesics, and / or isotonic agents.

[0060] The kit may contain two or more different luminescent compounds, at least one of which has the general formula (A).

[0061] In the kit, the storage state of the luminescent compound(s) is not limited. For example, the compound(s) may be stored in liquid (e.g., solution, suspension, or dispersion) or solid (e.g., powder, granule, or lyophilized) form. The storage state may be selected by those skilled in the art according to the stability of the compound(s) and the intended use.

[0062] In a further aspect of the invention, there is provided a luminescent compound or composition of formula (A) according to claim 1 for use in a method of diagnosing a disease or condition in a subject.

[0063] The disease or condition is not limited and may be, for example, cancer (including gastrointestinal tract, reproductive organs (e.g., uterine, ovarian, and cervical cancer), liver, kidney, breast, lung, head, mouth, neck, brain, and blood cancers (e.g., leukemia, multiple myeloma)), inflammation, edema, cardiovascular disorders (such as atherosclerosis), ischemia, autoimmune diseases (e.g., rheumatoid arthritis, diabetes, ulcerative colitis, or Crohn's disease), infectious diseases (e.g., bacterial, viral, fungal, or parasitic infections), skin diseases (including skin cancer), eye diseases (e.g., macular degeneration, diabetic retinopathy), neurological disorders (e.g., Alzheimer's, stroke), or injuries.

[0064] The method of diagnosis may include administering to the subject a luminescent compound or composition of formula (A) of the first aspect of the invention and obtaining an image of the subject using a fluorescence microscope.

[0065] Alternatively, in the case of diagnosis, the method may include administering the luminescent compound or composition of formula (A) of the first aspect of the invention to biological tissue or fluid previously obtained from the subject, and obtaining an image of the biological tissue or fluid using a fluorescence microscope.

[0066] In some embodiments, the method of diagnosis further includes referring to or comparing the image of the subject, biological tissue, or fluid. The reference image may be obtained from a healthy subject or may be previously obtained from the subject being diagnosed.

[0067] In yet a further aspect of the invention, a method for determining the effectiveness of a treatment or therapy received by a subject is provided.

[0068] The subject may be receiving a treatment or therapy or may have completed a treatment or therapy.

[0069] The method for determining the effectiveness of a treatment or therapy may include obtaining an image of the subject using a fluorescence microscope, wherein the subject has been administered the luminescent compound or composition of formula (A) of the first aspect of the invention.

[0070] In some embodiments, the subject has been previously administered the luminescent compound or composition. In some alternative embodiments, the method further includes administering the luminescent compound or composition of formula (A) of the first aspect of the invention to the subject before obtaining the image.

[0071] Alternatively, the method may include obtaining an image of biological tissue or fluid obtained from the subject using a fluorescence microscope. The method may further include administering or contacting the biological tissue or fluid with the luminescent compound or composition of formula (A) of the first aspect of the invention.

[0072] The method may further include comparing the obtained image with a reference image. The reference image may have been previously obtained from the subject before or during the treatment or therapy.

[0073] Accordingly, the invention provides a means for monitoring the progression of a disease or treatment.

[0074] The subject can be an animal. The animal can be a mouse, rat, guinea pig, rabbit, dog, cat, sheep, goat, pig, cow, horse, primate, or human. In some embodiments, the subject is a human.

[0075] In an embodiment, the luminescent compound(s) (A) can be represented by the following general formula,

Chemical formula

[0076] In an embodiment, the luminescent compound(s) can be a triphenylene derivative. In an alternative embodiment, the luminescent compound(s) can include a condensed polycyclic aromatic hydrocarbon containing six 6-membered rings.

[0077] In an embodiment, Y 8 represents an oxygen atom, and Y 9 represents a nitrogen atom, and Y 8 and Y 9 combine to form an oxazole moiety containing an R group selected from an aromatic group and / or an aliphatic group.

[0078] In an embodiment, Y 5 and Y 6 together represent carbon atoms that combine to form a condensed ring, for example, a condensed aromatic ring.

[0079] In an embodiment, the luminescent compound(s) can be represented by the following general formula,

Chemical formula

[0080] In an embodiment, the luminescent compound(s) can be represented by the following general formula,

Chemical formula

[0081] In some embodiments, Y 21 represents an oxygen atom, Y 22 represents a nitrogen atom, Y 21 and Y 22combines to form an oxazole moiety containing an R group selected from an aromatic group and / or an aliphatic group.

[0082] In embodiments, the luminescent compound(s) is / are represented by the following general formula,

Chemical formula

[0083] In embodiments, A independently contains or consists of an alkyl group, e.g., a straight-chain alkyl group. In embodiments, A independently is CH3, C2H5, C3H7, C4H9, C5H 11 、C6H 13 、C7H 15 、OC8H 17 、C9H 19 、or C 10 H 21selected from one or more of the bases. In an embodiment, A can independently represent C5H 11 and / or C4H9. In an embodiment, A can independently represent C5H 11 and / or C4H9.

[0084] In an embodiment, A can independently represent a polyethylene glycol (PEG) group (e.g., C2H4OC2H4OC2H4OCH3).

[0085] In an embodiment, A can independently represent an alkyl group containing a reactive functional group FG. For example, A can independently represent an alkyl group or a polyether group containing a carboxylic acid moiety, an ester, an azide, an amine, a maleimide, and / or a thiol moiety. In an embodiment, A can independently represent a (CH2CH2O)2CH2CH2FG moiety, where FG is selected from one of a carboxylic acid moiety, an ester, an azide, an amine, a maleimide, and / or a thiol moiety.

[0086] In an embodiment, X represents an oxygen atom. In an embodiment, X represents a sulfur atom.

[0087] In an embodiment, J 1 , J 2 , J 3 , J 4 , J 5 independently represents a hydrogen atom or a deuterium atom.

[0088] In an embodiment, R represents an aliphatic group or moiety. In an embodiment, R represents an aromatic group or moiety.

[0089] In an embodiment, the triphenylene derivative may not be a compound in which A is C5H 11 , J is H, and R is C4H9.

[0090] In an embodiment, the luminescent compound(s) is represented by the following general formula,

Chemical formula

[0091] In an embodiment, the luminescent compound(s) is represented by the following general formula,

Chemical formula

[0092] In all embodiments, the term "fused ring" is intended to define a group that combines together to form a ring (e.g., an aromatic ring and / or a heterocyclic ring) that forms part of the core of the luminescent compound, i.e., a group that extends the triphenylene core.

[0093] In an embodiment, A can independently represent C5H 11 and / or C4H9. In an embodiment, A can independently represent a polyethylene glycol (PEG) group (e.g., C2H4OC2H4OC2H4OCH3). In an embodiment, A can independently represent an alkyl group containing a reactive functional group FG, e.g., A can independently represent an alkyl group containing a carboxylic acid moiety, an ester, an azide, an amine, a maleimide, and / or a thiol moiety. In an embodiment, A independently represents a -(CH2CH2O)2CH2CH2FG or (CH2CH2O)2CH2FG moiety, where FG is selected from one of a carboxylic acid moiety, an ester, an azide, an amine, a maleimide, and / or a thiol moiety.

[0094] In an embodiment, the luminescent compound(s) is represented by the following general formula

Chemical formula

[0095] In an embodiment, the luminescent compound(s) is represented by the following general formula,

Chemical formula

[0096] In an embodiment, X represents an oxygen atom. In an embodiment, X represents a sulfur atom.

[0097] In an embodiment, A is independently an alkyl group, e.g., including or consisting of a linear alkyl group. In an embodiment, A is independently selected from one or more of CH3, C2H5, C3H7, C4H9, C5H 11 、C6H 13 、C7H 15 、OC8H 17 、C9H 19 、or C 10 H 21 groups.

[0098] In an embodiment, J, J 1 、J 2 、J 3 、J 4 、J 5 independently represent a hydrogen atom.

[0099] In an embodiment, J, J 1 、J 2 、J 3 、J 4 、J 5 independently represent a deuterium atom.

[0100] In an embodiment, J, J 1 、J 2 、J 3 、J 4 、J 5independently represents a heteroatom (e.g., a nitrogen atom, an oxygen atom, a halogen, e.g., F, Cl, Br, I).

[0101] In embodiments, A further comprises a further functional group, e.g., A may further comprise a fluorine atom, a chlorine atom, a cyano group, a nitro group, glycol, alkoxy, thioalkoxy, polyethylene glycol, amino, acetate, carboxylic acid, amide, thioamide, thioester, azo, and / or a silyl group. In embodiments, A comprises a functional group capable of forming a covalent bond with a second molecule, e.g., a biomolecule or a small molecule, e.g., a drug molecule. The functional group may be selected, for example, from carboxylic acid, ester, azide, amine, maleimide, thiol, isothiocyanate, and / or aliphatic alcohol. In embodiments, the functional group may be located at one or more termini of A.

[0102] In embodiments, J comprises or represents an aryl group, e.g., a phenol group. Additionally or alternatively, J comprises a halogen atom, e.g., fluorine, chlorine, bromine, or iodine.

[0103] In embodiments, R, R 1 , R 2 , and / or R 3 may be an alkyl group, e.g., a straight or branched alkyl chain. In embodiments, at least one of R, R 1 , R 2 , R 3 may be a methyl, ethyl, propyl, butyl group.

[0104] R, R 1 , R 2 , and / or R 3 In embodiments where is an aromatic group, the aromatic group is one or a combination of an aromatic hydrocarbon group and / or an aromatic heterocyclic group.

[0105] R, R 1 , R 2 , and / or R 3In embodiments where it is an aromatic hydrocarbon group, the aromatic hydrocarbon group may include one or a combination of a phenyl ring and / or a substituted phenyl ring. One, two, three, four, or five additional substituents may be present on the phenyl ring. The substituents are directly bonded to the phenyl ring and are one or a combination of fluorine, chlorine, bromine, iodine, a hydroxyl group, an amine group, a nitro group, an alkoxy group, a carboxylic acid, an amide, a cyano group, trifluoromethyl, an ester, an alkene, an alkyne, an azide, an azo, an isocyanate, a ketone, an aldehyde, an alkyl group consisting of a hydrocarbon chain or a hydrocarbon ring, an alkyl group consisting of other heteroatoms such as fluorine, chlorine, bromine, iodine, oxygen, nitrogen, and / or sulfur. The alkyl group may include, for example, a hydroxyl group, an amine group, a nitro group, an ether group, a carboxylic acid, an amide, a cyano group, trifluoromethyl, an ester, an alkene, an alkyne, an azide, an azo, an isocyanate, a ketone, an aldehyde. The substituent may be another aromatic group. For example, R may include phenyl substituted with an additional phenyl ring. In embodiments, the R group may be a phenyl ring substituted with a second phenyl ring, and thus the second phenyl ring may be substituted with a third phenyl ring. In embodiments, R, R 1 、R 2 、or R 3 may represent a p-fluorophenyl group, an m-fluorophenyl group, an o-fluorophenyl group, a thiophene group, a cyanophenyl moiety (e.g., a p-cyanophenyl moiety), a trifluoromethylphenyl moiety (e.g., a p-trifluoromethylphenyl moiety), an iodophenyl moiety (e.g., an o-iodophenyl moiety), a chlorophenyl moiety (e.g., an o-chlorophenyl moiety), a bromophenyl moiety (e.g., an o-bromophenyl moiety), an aminophenyl moiety (e.g., a mono-substituted, or di-substituted, or tri-substituted aminophenyl moiety), a nitrophenyl moiety (e.g., a p-nitrophenyl moiety), a phenol moiety.

[0106] R, R 1 、R 2 、and / or R 3In embodiments where the group is an aromatic group, the aromatic group can be a polycyclic aromatic hydrocarbon, such as naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzo[a]pyrene, coronene, benzo[ghi]perylene, ovalene, fullerene, and / or benz[c]fluorene. The R group can be attached to the triphenylene derivative by any isomer of the polycyclic aromatic hydrocarbons described, such as 1-naphthalene, 2-naphthalene, 2-anthracene, 9-anthracene. The polycyclic aromatic hydrocarbon group can be substituted with other moieties such as aryl groups, alkyl groups, heteroatoms, and / or other electron-withdrawing or electron-donating groups.

[0107] R, R 1 、R 2 、またはR 3 In embodiments where the group is an aromatic heterocyclic group, the heterocyclic group can be a 3-membered ring, 4-membered ring, 5-membered ring, 6-membered ring, 7-membered ring, 8-membered ring, 9-membered ring, 10-membered ring, or a fused ring. In embodiments, the heterocyclic group can be furan, benzofuran, isobenzofuran, pyrrole, indole, isoindole, thiophene, benzothiophene, benz[c]thiophene, imidazole, benzimidazole, purine, pyrazole, indazole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, cinnoline, phthalazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, pyridine, or thiophene.

[0108] R, R 1 、R 2 、またはR 3In embodiments where the aliphatic group is an aliphatic group, the aliphatic group can be one of an n-alkyl chain, a branched alkyl chain, an alkyl chain containing an unsaturated moiety, an alkyl chain containing a heteroatom such as fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, or a combination thereof. The alkyl chain can contain an unsaturated moiety including an alkene or an aromatic moiety. The alkyl chain can contain a functional group for further derivatization of a polycyclic aromatic hydrocarbon such as a triphenylene derivative. For example, the functional group can be one or more of an azide, a carbonyl group, an alcohol, a halogen, an alkene, or a thioacetate.

[0109] In embodiments, R, R 1 , R 2 , or R 3 includes a crown ether.

[0110] The luminescent compound can be any one of the structures shown in FIG. 3.

[0111] In some embodiments, the luminescent compound is compound (2) (TpOx-Ph).

Chemical formula

[0112] In some embodiments, the luminescent compound is compound (3) (TpOx-2-Nap).

Chemical formula

[0113] Within the scope of the present application, it is expressly intended that the various aspects, embodiments, examples, and alternatives described in the foregoing paragraphs, claims, and / or the following description and drawings, particularly their individual features, can be made independently or in any combination. That is, all embodiments and / or features of any embodiment may be combined in any manner and / or be in combination, except where such features are incompatible. To avoid doubt, the terms "may", "and / or", "e.g.", "for example", and any similar terms used herein should be construed as non-limiting, so that any feature so described does not necessarily exist. In fact, any combination of optional features is expressly contemplated without departing from the scope of the invention, whether or not they are expressly claimed. The applicant reserves the right to amend any originally filed claim to change any originally filed claim, including the right to make it dependent on and / or incorporate into it any feature of any other claim that was not originally claimed in that form, or to file any new claim accordingly.

[0114] Here, embodiments of the invention will be described by way of example and with reference to the accompanying drawings.

Brief Description of the Drawings

[0115]

Figure 1

Figure 2

Figure 3

Figure 4A

Figure 4B

Mode for Carrying Out the Invention

[0116] The compounds for use in the invention were synthesized according to the following protocol. The names of all compounds were generated using ChemDraw (RTM) software.

[0117] Synthesis Method Method for Synthesizing Compound 1 Compound 1 was synthesized from Precursor 1 using the following method.

[0118] Precursor 1 was prepared according to the method described in N. Boden et.al. J. Mater. Chem., 1995, 5, 2275.

[0119] A solution of Precursor 1 (100 mg; 0.13 mmol) in o-xylene (8 mL) was added to a flask. Then, this was heated and maintained at 175 °C for 16 hours to obtain Compound 1 (yield 51%).

[0120] Alternatively, Compound 1 was synthesized using the following method. Under a N2 atmosphere, 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). Then, this was heated and maintained under reflux for 20 hours. The reaction mixture was cooled to room temperature, then evaporated to dryness under vacuum, and then the solid was purified via flash column chromatography (silica; 95% n-hexane: 5% ethyl acetate) to obtain Compound 1 as a white solid (96 mg, 99%).

[0121] The name of Compound 1 is 8-butyl-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.

[0122] Compound 1 had the following characterization data: 11H NMR (300 MHz, CDCl3) δ Η : 10.01 (1H, s), 7.94 (1H, s), 7.90 (1H, s), 7.88 (1H, 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. 13 13C NMR (100 MHz, CDCl3) δ 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 + H] + 15%), 778.5 ([M + Na] + 100%). IR λ -1 (neat): 3112 w (C - H), 2953 m (C - H), 1617 w (C = N), 1517 w (benzene ring), 1259 s (C - O), 1177 s (C - O), 1159 s (C - O) cm-1. Elemental analysis found: C, 76.09; H, 9.17; N, 1.95%. C 48 H 69 HNO6 requires C, 76.25; H, 9.20; N, 1.85.

[0123] Method for synthesizing Compound 2 Compound 2 was synthesized from Precursor 2 using the following method.

[0124] Precursor 2 was prepared according to the method described in N. Boden et.al. J. Mater. Chem., 1995, 5, 2275.

[0125] A slurry of benzoic acid (160 mg; 1.31 mmol), palladium(II) diacetate (0.005 mmol), and iodo benzene diacetate (0.16 mmol) in PhMe (5 mL) was heated at 70 °C for 20 min under N2. Precursor 2 (100 mg, 0.13 mmol) in PhMe (2 mL) was added and the reaction was heated and maintained at reflux for 72 h. The mixture was cooled to room temperature and diluted with CH2Cl2 (20 mL). The mixture was washed with 1 M aqueous NaOH solution (2 × 20 mL) and the organic phase was dried under vacuum. The black crude solid was purified via flash column chromatography (40% CH2Cl2:60% n-hexane) to afford Compound 2 as a white solid (35 mg; 34%).

[0126] The name of Compound 2 is 2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenylene[1,2-d]oxazole.

[0127] Compound 2 had the following characterization data: 1 Η ΝΜR(300ΜΗz,CDCl3)δ Η : 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. 13 C NMR(100MHz,CDCl3)δ 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] + 22%), 776.5([M+H]+ 37%), 798.5 ([M+Na]+100%). Elemental analysis found: C, 77.46; H, 8.44; N, 1.75%. C 50 H 65 NO6 requires C, 77.38; H, 8.44; N, 1.80.

[0128] Method for synthesizing Compound 3 Compound 3 was synthesized using the following method. A solution of 2-naphthalenecarboxylic acid (225 mg, 1.31 mmol), palladium(II) diacetate (0.005 mmol), and iodo(benzene)diacetate (0.157 mmol) in PhMe (5 mL) was heated at 70 °C for 20 min under N2. A solution of precursor 2 (100 mg; 0.131 mmol) in PhMe (2 mL) was added, and the mixture was heated under reflux for 48 - 72 h with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give Compound 3 as a yellow solid (35 mg; 32%).

[0129] The name of Compound 3 is 8-(naphthalen-2-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0130] Compound 3 had the following characterization data: 1 Η NMR (300 MHz, CDCl3) δ Η : 10.22 (1 H, s), 8.89 (1 H, s), 8.49 (1 H, dd, J 8.6, 1.7 Hz), 8.05 - 7.99 (2 H, m), 7.96 - 7.91 (5 H, m), 7.62 - 7.59 (2 H, m), 4.54 (2 H, t, J 6.8 Hz), 4.51 (2 H, t, J 6.8 Hz), 4.32 - 4.25 (6 H, m), 2.17 - 1.93 (10 H, m), 1.76 - 1.42 (20 H, m), 1.06 - 0.97 (15 H, m) ppm. 13 C NMR (100 MHz, CDCl3) δC : 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] + 100%). IR λ-1 (neat): Elemental analysis found: C, 78.95; H, 8.02; N, 1.83%. C 54 H 67 NO6 requires C, 78.51; H, 8.17; N, 1.70%.

[0131] Method for synthesizing Compound 4 Compound 4 was synthesized using the following method. A solution of 1-naphthalenecarboxylic acid (225 mg, 1.31 mmol), palladium(II) diacetate (0.005 mmol), and iodo(benzene)diacetate (0.157 mmol) in PhMe (5 mL) was heated at 70 °C for 20 min under N2. A solution of precursor 2 (100 mg; 0.131 mmol) in PhMe (2 mL) was added, and the mixture was heated under reflux for 48 - 72 h with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give Compound 4 as a yellow solid (24 mg; 22%).

[0132] The name of Compound 4 is 8-(naphthalen-1-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0133] Compound 4 had the following characterization data: 11H NMR (300 MHz, CDCl3) δ Η : 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. 13 13C NMR (100 MHz, CDCl3) δ 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] + 100%). Elemental analysis found: C, 78.49; H, 8.23; N, 1.73%. C 54 H 67 NO6 requires C, 78.51; H, 8.17; N, 1.70%.

[0134] Method for synthesizing compound 5 Compound 5 was synthesized using the following method. A solution of 2-anthracenecarboxylic acid (290 mg, 1.31 mmol), palladium(II) diacetate (0.005 mmol), and iodobenzene diacetate (0.157 mmol) in PhMe (5 mL) was heated at 70 °C for 20 min under N2. A solution of precursor 2 (100 mg; 0.131 mmol) in PhMe (2 mL) was added, and the mixture was heated under reflux for 48 - 72 h with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give compound 5 as a yellow solid (22 mg; 20%).

[0135] The name of compound 5 is 8-(anthracen-2-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0136] Compound 5 had the following characterization data: 1 Η NMR (300 MHz, CDCl3) δ Η : 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 (10 H, m), 1.76 1.44 (20H, m), 1.08 - 0.97 (15H, m) ppm. 13 C NMR (100 MHz, CDCl3) δ 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] + 100%). Elemental analysis found: C, 79.49; H, 7.88; N, 1.51%. C 58 H 69 NO6 requires C, 79.51; H, 7.94; N, 1.60.

[0137] Method for synthesizing Compound 6 Compound 6 was synthesized using the following method. A solution of 9 - anthracenecarboxylic acid (290 mg; 1.31 mmol), palladium(II) diacetate (0.005 mmol), and diacetoxyiodobenzene (0.157 mmol) in o - xylene (5 mL) was heated to 70 °C for 20 min under N2. A solution of precursor 2 (100 mg, 0.131 mmol) in o - xylene (2 mL) was added, and the mixture was heated to 140 °C for 72 h. The mixture was cooled to room temperature and diluted with CH2Cl2 (20 mL). The mixture was washed with 1 M aqueous NaOH solution (2 × 20 mL), and the organic phase was dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2: 60% n - hexane) to give Compound 6 as a yellow solid (13 mg, 11%).

[0138] The name of Compound 6 is 8 - (anthracen - 9 - yl) - 2,3,6,11,12 - pentakis(pentyloxy)triphenylene[1,2 - d]oxazole.

[0139] Compound 6 had the following characterization data: 11H NMR (300 MHz, CDCl3) δ Η : 10.18 (1H, 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 (2H, 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. 13 13C NMR δ C : (100 MHz, CDCl3) 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 + m / z: 876.5 ([M]+ 100%). Elemental analysis found: C, 79.13; H, 7.83; N, 1.77%. C 58 H 69 NO6 requires C, 79.51; H, 7.94; N, 1.60.

[0140] Method for synthesizing compound 7 Compound 7 was synthesized using the following method. A solution of 4-fluorobenzoic acid (187 mg; 1.31 mmol), palladium(II) diacetate (0.005 mmol), and iodo(benzene)diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70 °C under N2 for 20 minutes. A solution of precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added, and the mixture was heated to 140 °C for 72 hours. The mixture was cooled to room temperature and diluted with CH2Cl2 (20 mL). The mixture was washed with 1 M aqueous NaOH solution (2 × 20 mL), and the organic phase was dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give Compound 7 as a yellow solid (13 mg, 9%).

[0141] The name of Compound 7 is 8-(4-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0142] Compound 7 had the following characterization data: 1 Η ΝΜR(300ΜΗz;CDCl3)δ Η :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 6.6Hz),4.26(6H,m),2.06-1.90(9H,m),1.55(22H,m),1.05-0.95(15H,m)ppm. 13 C NMR(100MHz;CDCl3)δ 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. 1919F NMR (282 MHz, CDCl3) δ F : -108.0 ppm. MALDI+ m / z: 793.6 ([M] + 100%), 794.6 ([M+H] + 55%), 795.6 ([M+H+1] + 15%). IR λ -1 (neat): 2952 m (C-H), 2926 m (C-H), 2858 m (C-H), 1616 w (C=N), 1517 s (benzene ring), 1499 m (benzene ring), 1433 m (benzene ring), 1261 m (C-O), 1174 s (C-O) cm -1 .

[0143] Method for synthesizing Compound 8 Compound 8 was synthesized using the following method. A solution of 3-fluorobenzoic acid (182 mg; 1.30 mmol), palladium(II) diacetate (0.005 mmol), and iodobenzene diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70 °C for 20 minutes under N2. A solution of precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added, and the mixture was heated to 140 °C for 72 hours. The mixture was cooled to room temperature and diluted with CH2Cl2 (20 mL). The mixture was washed with 1 M aqueous NaOH solution (2 × 20 mL), and the organic phase was dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to obtain Compound 8 as a yellow solid (13 mg, 11%).

[0144] The name of Compound 8 is 8-(3-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0145] Compound 8 had the following characterization data: 1 1H NMR (300 MHz; CDCl3) δ Η: 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. 13 13C NMR (100 MHz; CDCl3) δ 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; CDCl3) δ F : -111.8 ppm. ES+MS m / z: 794.5 ([M] + 55%), 816.5 ([M + Na] + 100%), 817.5 ([M + H + Na] + 50%). IR λ-1 (neat): 2952 m (C-H), 2925 m (C-H), 2856 m (C-H), 1617 w (C=N), 1518 s (benzene ring), 1434 s (benzene ring), 1262 s (C-O), 1174 s (C-O) cm-1. Elemental analysis found: C, 75.62; H, 8.25; N, 1.78%. C 50 H 64 FNO6 requires C, 75.63; H, 8.12; N, 1.76.

[0146] Method for synthesizing Compound 9 Compound 9 was synthesized using the following method. A solution of 2-fluorobenzoic acid (41.86 mg; 1.26 mmol), palladium(II) diacetate (0.005 mmol), and iodo(benzene)diacetate (0.157 mmol) in o-xylene (5 mL) was heated to 70 °C under N2 for 20 minutes. A solution of precursor 2 (100 mg, 0.131 mmol) in o-xylene (2 mL) was added and heated to 140 °C for 72 hours. The mixture was cooled to room temperature and diluted with CH2Cl2 (20 mL). The mixture was washed with 1 M aqueous NaOH (2 × 20 mL) and the organic phase was dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford Compound 9 as a yellow solid (7 mg, 10%).

[0147] The name of Compound 9 is 8-(2-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0148] Compound 9 had the following characterization data: 1 Η ΝΜR(300ΜΗz;CDCl3)δ Η : 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(100MHz;CDCl3)δ 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(282MHz;CDCl3)δF :-109.1 ppm. MALDI+ m / z: 793.6([M] + 100%), 794.6([M + H] + 65%), 795.6([M + 1 + H] + 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 50 H 64 FNO6 requires C, 75.63; H, 8.12; N, 1.76.

[0149] Method for synthesizing Compound 10 Compound 10 was synthesized using the following method. Under a N2 atmosphere, a slurry of precursor 2 (100 mg; 0.01 mmol), iodosobenzene 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) was heated and maintained at reflux for 72 hours. The reaction was then cooled to room temperature and washed with 1 M NaOH (1 M; 2 × 10 mL). The organic phase was evaporated to dryness under vacuum. The solid was then purified via flash column chromatography (40% CH2Cl2: 60% n-hexane) to obtain Compound 10 as a white solid (64 mg; 66%).

[0150] The name of Compound 10 is 8-methyl-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0151] Compound 10 had the following characteristic evaluation data: 1 Η NMR δ H:(400 MHz, CDCl3) 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. 13 13C NMR δ C :(100 MHz, CDCl3) 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] + 100%).

[0152] Method for synthesizing Compound 11 Compound 11 was synthesized 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 to reflux under N2 for 10 minutes. 2-Thiophenecarbonyl chloride (0.3 mL, 2.62 mmol) was added and the mixture was heated under reflux for 90 minutes. The solution was cooled to room temperature, washed with 1 M HCl (30 mL), and the organic phase was extracted with EtOAc (2 × 30 mL). The organic phase was dried under vacuum, and the resulting black solid was heated at 240 °C for 10 minutes and then cooled to room temperature. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give Compound 11 as a yellow solid (136 mg; 64%).

[0153] The name of Compound 11 is 2,3,6,11,12-pentakis(pentyloxy)-8-(thiophen-2-yl)triphenylene[1,2-d]oxazole.

[0154] Compound 11 had the following characteristic evaluation data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C :(100 MHz, CDCl3) 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] + 100%).

[0155] Method for synthesizing Compound 12 Compound 12 was synthesized 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 maintained under N2 at reflux with heating for 18 h. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n - hexane) to give Compound 12 as a yellow solid (40 mg, 38%).

[0156] The name of Compound 12 is 4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)benzonitrile.

[0157] Compound 12 had the following characteristic evaluation data: 1 Η NMR δH: (300 MHz, CDCl3) 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. 13 C NMR δ C : (100 MHz, CDCl3) 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] + 100%).

[0158] Method for synthesizing Compound 13 Compound 13 was synthesized using the following method. A solution of 4-(trifluoromethyl)benzoic acid (248 mg, 1.31 mmol), palladium(II) diacetate (0.005 mmol), and iodobenzene diacetate (0.157 mmol) in PhMe (5 mL) was heated at 60 °C for 30 minutes under N2. A solution of precursor 2 (100 mg; 0.1312 mol) in PhMe (2 mL) was added, and the mixture was heated under reflux for 48 - 72 hours with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give Compound 13 as a yellow solid (6 mg; 5%).

[0159] The name of Compound 13 is 2,3,6,11,12-pentakis(pentyloxy)-8-(4-trifluoromethyl)phenyl)triphenylene[1,2-d]oxazole.

[0160] Compound 13 had the following characterization data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 19 F NMR δ F :(300 MHz, CDCl3) 62.9 (s) ppm. 13 C NMR δ C ​:(100 MHz, CDCl3) 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] + 100%).

[0161] Method for synthesizing Compound 14 Compound 14 was synthesized 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 reflux and maintained at reflux for 18 h under N2. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford Compound 14 as a yellow solid (39.9 mg, 35%).

[0162] The name of Compound 14 is 8-(2-iodophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0163] Compound 14 had the following characterization data: 11H NMR δ (300 MHz, CDCl3): 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. 13 13C NMR δ C : (100 MHz, CDCl3) 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 + + 14%).

[0164] Method for synthesizing Compound 15 Compound 15 was synthesized 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 kept under heating reflux and refluxed for 18 h under N2. The reaction mixture was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford Compound 15 as a yellow solid (52.4 mg, 49%).

[0165] The name of Compound 15 is 8-(2-chlorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazole.

[0166] Compound 15 had the following characteristic evaluation data: 1 Η NMR δ H : (300 MHz, CDCl3) 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. 13 C NMR δ C : (100 MHz, CDCl3) 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] + 95%).

[0167] Method for synthesizing Compound 16 Compound 16 was synthesized 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 reflux and maintained at reflux under N2 for 18 h. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford Compound 16 as a yellow solid (25.8 mg, 21%).

[0168] The name of Compound 16 is 8-(2-bromophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0169] Compound 16 had the following characterization data: 1 Η ΝΜR δH: (300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3): 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] + 31%)

[0170] Method for synthesizing Compound 17 Compound 17 was synthesized using the following method. A solution of 5-bromovaleric acid (773 mg, 4.27 mmol), palladium(II) diacetate (0.005 mmol), and iodo benzene diacetate (0.512 mmol) in PhMe (10 mL) was heated at 70 °C for 20 min under N2. A solution of precursor 2 (325 mg; 0.428 mmol) in PhMe (10 mL) was added and the mixture was heated under reflux for 48 - 72 h with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2: 60% n-hexane) to give Compound 17 as a white solid (109 mg; 31%).

[0171] The name of Compound 17 is 8-(4-bromophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0172] Compound 17 had the following characterization data: 1 Η NMR δ H:(300 MHz, CDCl3) 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. 13 13C NMR δ C :(100 MHz, CDCl3) 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] + 95%), 836.4 ([M + H] + 100%).

[0173] Method for synthesizing Compound 18 Compound 18 was synthesized using the following method. A solution of Compound 17 (66 mg, 0.079 mmol) in acetone (10 mL) was heated to 50 °C, stirred under N2, and a solution of sodium azide (7 mg, 0.111 mmol) in H2O (5 mL) was added thereto, and the mixture was left to stir for 4 hours under N2. Thereafter, a precipitate was formed, the solvent was removed under reduced pressure, and then the precipitate was filtered under vacuum and dried to obtain Compound 18 as an off - white solid (59 mg, 94%).

[0174] The name of Compound 18 is 8 - (4 - azidobutyl) - 2,3,6,11,12 - pentakis(pentyloxy)triphenylene[1,2 - d]oxazole.

[0175] Compound 18 had the following characteristic evaluation data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C :(100 MHz, CDCl3) 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] + 100%).

[0176] Method for synthesizing compound 19 Compound 19 was synthesized using the following method. Compound 17 (21 mg, 0.025 mmol) was dissolved in anhydrous THF (4 mL), potassium thioacetate (12 mg, 0.1 mmol) was added to this mixture, and the mixture was stirred under N2 for 6 hours. The organic phase was then extracted with DCM (10 mL) and washed with water (2 × 10 mL). The organic phase was then dried under vacuum, and the solid was recrystallized from DCM:MeOH (1 mL:5 mL). The resulting precipitate was suction filtered, and the solid was washed with methanol to obtain compound 19 as an off - white solid (4 mg, 19%).

[0177] The name of Compound 19 is S-(4-(2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazol-8-yl)butyl)ethanethioate.

[0178] Compound 19 had the following characterization data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C :(100 MHz, CDCl3) 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] + 100%).

[0179] The method for synthesizing Compound 20 Compound 22 was synthesized 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 reflux and maintained at reflux for 48 h under N2. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The crude solid was dissolved in CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), then with HCl (1 M, 2 × 20 mL), separated, and the organic phase was dried under vacuum. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give compound 16 as a yellow solid (84 mg, 36%).

[0180] The name of compound 20 is 8-(but-3-en-1-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0181] Compound 20 had the following characterization data: 1 Η ΝΜR δH: (300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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] + 100%).

[0182] Method for synthesizing Compound 21 Compound 21 was synthesized using the following method. A solution of decanoic acid (0.132 mg, 0.236 mmol), palladium(II) diacetate (0.005 mmol), and iodobenzene diacetate (0.235 mmol) in PhMe (10 mL) was heated at 70 °C for 20 minutes under N2. A solution of precursor 2 (100 mg; 0.132 mmol) in PhMe (10 mL) was added, and the mixture was heated under reflux for 48 - 72 hours with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n - hexane) to obtain Compound 21 as a white solid (42 mg; 39%).

[0183] The name of Compound 21 is 8 - nonyl - 2,3,6,11,12 - pentakis(pentyloxy)triphenyleno[1,2 - d]oxazole.

[0184] Compound 21 had the following characterization data: 11H NMR δ (300 MHz, CDCl3): 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. 13 13C NMR δ C : (100 MHz, CDCl3) 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]+ + 100%).

[0185] Method for synthesizing Compound 22 Compound 22 was synthesized 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 reflux and maintained at reflux for 18 h under N2. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford Compound 22 as a yellow solid (19 mg, 18%).

[0186] The name of Compound 12 is N,N-dimethyl-4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)aniline.

[0187] Compound 22 had the following characteristic evaluation data: 1 Η NMR δ H : (300 MHz, CDCl3) 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. 13 C NMR δ C : (100 MHz, CDCl3) 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] + 100%).

[0188] The method for synthesizing Compound 23 Compound 23 was synthesized 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 for 20 min under N2. A solution of precursor 2 (100 mg; 0.132 mmol) in PhMe (10 mL) was added and the mixture was heated under reflux for 48 - 72 h with stirring. The solution was cooled to room temperature and diluted with CH2Cl2 (20 mL). The organic phase was washed with aqueous NaOH solution (1 M; 2 × 20 mL), separated, and dried under vacuum. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford compound 23 as an off-white solid (74 mg; 69%).

[0189] The name of compound 23 is 8-(4-nitrophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0190] Compound 23 had the following characterization data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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] + 100%).

[0191] Method for synthesizing Compound 24 Compound 24 was synthesized 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 under N2 for 10 minutes. Then, precursor 2 (100 mg, 0.131 mmol) was added to form a black solution, which was then stirred for an additional 10 minutes. A solution of palladium diacetate (1 mg, 5 mol%) and acetylsalicylic acid (553 mg, 3.197 mmol) in toluene (4 mL) was heated to 110 °C and stirred under N2 for 10 minutes, and then combined with the black solution. The resulting solution was left to stir at 110 °C for 72 hours under N2. The black crude solid was dried under vacuum and purified by flash column chromatography (silica; 40% CH2Cl2: 60% n-hexane). The crude material was then evaporated to dryness under vacuum and then dissolved in a mixture of MeCN (10 mL) and 1 M NaOH (10 mL). The solution was heated to 80 °C for 2 hours. After cooling to room temperature, the product was acidified using 1 M HCl (20 mL) and extracted into CH2Cl2 (3 × 10 mL). The combined organic layers were evaporated to dryness under vacuum to obtain Compound 24 as a white solid (2 mg, 2%).

[0192] The name of Compound 24 is 2-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]oxazol-8-yl)phenol.

[0193] Compound 24 had the following characteristic evaluation data: 1 Η NMR δ H :(300 MHz, CDCl3) 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] + 100%).

[0194] Method for synthesizing Compound 25 Compound 25 was synthesized from precursor 3 using the following method.

[0195] Precursor 3 was prepared according to the method described by 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 mixture of MeOH and THF (40 mL) was stirred at room temperature for 5 h under N2. The black crude solid was then filtered, washed with CHCl3, and the filtrate was evaporated to dryness under vacuum to give precursor 3 as a brown solid (1.6 g, 85%).

[0196] The name of precursor 3 is 2,3,6,7,10,11 - hexabutoxytriphenylene - 1 - amine.

[0197] The precursor 3 had the following characteristic evaluation data: 1 Η NMR δ H :(300 MHz, CDCl3) 8.82 (1 H, s), 7.83 (1 H, s), 7.80 (1 H, s), 7.78 (1 H, s), 7.37 (1 H, s), 4.57 (2 H, s), 4.29 - 4.09 (12 H, m), 2.01 - 1.81 (12 H, m), 1.67 - 1.52 (12 H, m), 1.13 - 0.94 (18 H, m) ppm. 13 C NMR δ C :(100 MHz, CDCl3) 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] + 100%).

[0198] A solution of precursor 3 (100 mg, 0.148 mmol), 2-naphthoyl chloride (141 mg, 0.658 mmol), and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL) was maintained under N2 at reflux with heating for 18 h and then at reflux. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give compound 25 as a yellow solid (21 mg, 19%).

[0199] The name of compound 25 is 2,3,6,11,12-pentabutoxy-8-(naphthalen-2-yl)triphenylene[1,2-d]oxazole.

[0200] Compound 25 had the following characteristic evaluation data: 11H NMR δ H :(300 MHz, CDCl3) 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. 13 13C NMR δ C :(100 MHz, CDCl3) 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] + + 100%).

[0201] Method for synthesizing Compound 26 Compound 26 was synthesized from the precursor 4 (2,3,6,7,10,11 - hexakis(pentyloxy)-1,8 - triphenylenediamine) using the following method.

[0202] Precursor 4 was synthesized from a di - nitrotriphenylene derivative, which is formed as a by - product in the method used for the synthesis of mono - nitrotriphenylene derivatives, using the method described by N. Boden et.al. J. Mater. Chem., 1995, 5, 2275. The di - nitrotriphenylene derivative can be isolated by flash column chromatography in a fraction prior to the mono - nitro intermediate.

[0203] A solution of precursor 4 (135 mg, 0.074 mmol) and palladium diacetate (0.0005 mmol) in PhMe (7 mL) was heated to reflux under N2 for 10 minutes. 2-Fluorobenzoyl chloride (0.02 mL, 0.174 mmol) was added and the mixture was heated under reflux for 40 hours. The solution was cooled to room temperature and dried under vacuum. The resulting black solid was heated at 240 °C for 10 minutes and then cooled to room temperature. The black crude solid was purified by flash column chromatography (silica; 40% CH2Cl2: 60% n-hexane) to afford compound 26 as an off-white solid (6 mg; 4%).

[0204] The name of compound 26 is 2,9-bis(2-fluorophenyl)-4,7,12,13-tetrakis(pentyloxy)triphenylene[1,2-d:8,7-d’]bis(oxazole).

[0205] Compound 26 had the following characterization data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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. 19 F NMR δ F :(300 MHz, CDCl3) 108.9 (s) ppm. MALDI m / z: 842.5 ([M] + 100%).

[0206] Method for synthesizing compound 27 Compound 27 was synthesized 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 maintained under reflux for 10 minutes under N2. The reaction mixture was cooled to room temperature and then evaporated to dryness under vacuum. 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 mixture was then heated and maintained under reflux for 72 hours under N2. The reaction mixture was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 minutes under N2. The black crude 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%).

[0207] The name of 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)triphenylene[1,2-d]oxazole.

[0208] Compound 27 had the following characterization data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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] + 100%).

[0209] Method for synthesizing Compound 28 Compound 28 was synthesized using the following method. A solution of Compound 2 (60 mg, 0.077 mmol) in degassed dichloromethane (5 mL) was stirred in a two-necked flask purged with nitrogen at -20 °C under a nitrogen atmosphere. Boron tribromide (1 M solution in CH2Cl2, 387 μL, 0.385 mmol, 5 equivalents) was added via a syringe through a Suba-Sele (RTM), and the resulting yellowish-brown solution at room temperature was stirred for 24 hours. 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 MgSO4. The organic phase was evaporated to dryness and purified by column chromatography (silica: 5% ethyl acetate: hexane) to obtain Compound 28 as a brown solid (10 mg, 6%).

[0210] The name of Compound 28 is 2,3,11,12-tetrakis(pentyloxy)-8-phenyltriphenylene[1,2-d]oxazol-6-ol.

[0211] Compound 28 had the following characterization data: 1 Η NMR (300 MHz, CDCl3) δ Η: 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 + MS m / z: 728.4 ([M + Na] + 25%), 707.4 ([M + H + 1] + 30%), 706.4 ([M + H] + 85%).

[0212] Method for synthesizing Compound 29 Compound 29 was synthesized using the following method. Compound 2 (250 mg, 0.322 mmol) was dissolved in dry CH2Cl2 (10 mL) and stirred at 0 °C under a N2 atmosphere. Then, a 0.01 M solution of Br2 in CH2Cl2 (144 mL, 1.449 mmol) (4 × 36 mL) was added over 2 hours and monitored by TLC. The reaction was quenched by adding saturated sodium metabisulfite solution (100 mL). The product was extracted with dichloromethane (30 mL), washed with water (3 × 30 mL), dried over MgSO4, and evaporated to dryness. The crude product was then purified by column chromatography (silica 40% CH2Cl2:n - hexane) to give Compound 29 as a yellow solid (170 mg, 62%).

[0213] The name of Compound 29 is 1 - bromo - 2,3,6,11,12 - pentakis(pentyloxy) - 8 - phenyltriphenylene[1,2 - d]oxazole.

[0214] Compound 29 had the following characterization data: 1 Η NMR (300 MHz, CDCl3) δ Η: 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.

[0215] Method for synthesizing Compound 30 Compound 30 was synthesized using the following method. Compound 29 (170 mg, 0.199 mmol), K2CO3 (410 mg, 2.97 mmol), and Pd(PPh3)4 (30 mg, 0.026 mmol) were dissolved in a degassed 5:1 THF:H2O mixture (4 mL) under a nitrogen atmosphere. Then, (4-hydroxyphenyl)boronic acid (140 mg, 1.02 mmol) was added, and the reaction mixture was heated to reflux under N2 for 24 hours. 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 chromatography (silica 2Cl2:n-hexane) to obtain impure Compound 30 as a brown solid.

[0216] The name of Compound 30 is 4-(2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenylene[1,2-d]oxazol-1-yl)phenol.

[0217] Compound 30 had the following characterization data: TOF LD + m / z: 869.49 ([M+1] + 70%), 868.52 ([M] + 70%).

[0218] Method for synthesizing Compound 31 Compound 31 was synthesized using the following method. Compound 10 (50.7 mg, 0.071 mmol) was added to a two-necked round-bottom flask and purged with N2 for 15 minutes. Then, dry CH2Cl2 (20 mL) was added via a syringe through a Suba-Seal(RTM), and the brown stirring solution was cooled to -78 °C. Boron tribromide (1 M solution in CH2Cl2, 391 μL, 0.391 mmol, 5.5 eq) was added via a syringe through a Suba-Seal(RTM), and the reaction mixture was stirred for 4 hours. The reaction mixture was poured onto crushed ice, stirred until the ice completely melted, 4 drops of hydrochloric acid (1 M) were added, the product was extracted with ethyl acetate, washed with water (2 × 20 mL), dried over MgSO4, and evaporated to dryness. The crude product was used without further purification.

[0219] The name of Compound 31 is 8-methyltriphenylene[1,2-d]oxazole-2,3,6,11,12-pentaol.

[0220] Compound 31 had the following characterization data: ES + MS m / z: 503.26 ([M+2(OC5H 11 )] + 50%), 433.17 ([M+(OC5H 11 )] + 100%), 363.08 ([M] + 10%).

[0221] Method for synthesizing Compound 32 Crude Compound 31 (26 mg, 0.071 mmol), potassium carbonate (74 mg, 0.533 mmol), and potassium iodide (6 mg, 0.036 mmol) were dissolved in dry MeCN (35 mL). Then, 1(-2-bromoethoxy)-2-(2-methoxyethoxy)ethane (132 μL, 0.533 mmol) was added via a pipette, and the reaction mixture was heated to reflux and stirred with a CaCl2 drying tube for 20 hours. The reaction mixture was cooled to room temperature, the product was extracted with ethyl acetate (20 mL), washed with water (3 × 20 mL) and brine (2 × 20 mL), dried over MgSO4, and crude Compound 32 was obtained as a brown solid.

[0222] The name of Compound 32 is 2,3,6,12-tetrakis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-8-methyl-11-(pentyloxy)triphenylene[1,2-d]oxazole.

[0223] Compound 32 had the following characteristic evaluation data: ES + MS m / z: 1017.5([M] + 100%).

[0224] Advantageously, Compound 32 is water-soluble.

[0225] Method for synthesizing Compound 33 Compound 33 was synthesized from precursor 5 by the following method. The starting materials for forming precursor 5 were obtained using the method described in J. Mater. Chem. C, 2017, 5, 669-682 (DOI: 10.1039 / C6TC04530H).

[0226] 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), then acetic acid (1.33 ml, 23.24 mmol, 30 equivalents) was added, and the mixture was stirred at room temperature for 10 minutes under a nitrogen atmosphere, after which fuming nitric acid (65 μL, 1.55 mmol, 2 equivalents) was added. After the reaction mixture was stirred under nitrogen for 20 minutes, nitric acid (30 μL, 0.715 mmol, 0.92 equivalents) was further added, and the reaction mixture was left to stir at room temperature for 20 minutes. Then, the mixture was quenched with water (10 mL), the organic phase was washed with NaOH (1 M, 2 × 30 mL), and then dried under vacuum to obtain precursor 5 as a black solid (680 mg, 95%). Without further purification, this was used in the next step.

[0227] The name of precursor 5 is 5,6-dimethoxy-1-nitro-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracene.

[0228] The precursor 5 had the following characteristic evaluation data: 1 H NMR (400 MHz, CDCl3) δ 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). 13 C NMR (101 MHz, CDCl3) δ 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 + m / z: 924.82 ([M + H] + 30%).

[0229] The precursor 6 was synthesized by the following method. The precursor 5 (680 mg, 0.736 mmol) and NiCl2·6H2O (552 mg, 2.33 mmol, 3 equivalents) were dissolved in THF:MeOH (20 mL, in a ratio of 5:4) to prepare a yellow solution, and then NaBH4 (586 mg, 15.5 mmol, 20 equivalents) was added over 15 minutes. The black reaction mixture was left to stir for 40 minutes under a N2 atmosphere, then diluted with chloroform, and the precipitate was filtered through a gravity filter, leaving a brown organic phase, which was then dried under vacuum to obtain the precursor 6 as a brown solid (614 mg, 93%).

[0230] The name of precursor 6 is 5,6-dimethoxy-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracen-1-amine.

[0231] Precursor 6 had the following characteristic evaluation data: 1 H NMR (300 MHz, CDCl3) δ 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). 13 C NMR (101 MHz, CDCl3) δ 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 + m / z: 893.8 ([M + H] + 100%).

[0232] The precursor 7 was synthesized by the following method. Precursor 6 (147 mg, 0.181 mmol) was dissolved in dry CH2Cl2 (20 mL) and dry MeCN (20 mL). The solution was cooled to 0 °C under a N2 atmosphere, and then tert-butyl nitrite (34 μL, 0.309 mmol, 1.7 equiv) and TMSN3 (36 μL, 0.273 mmol, 1.5 equiv) were added, and the reaction mixture was stirred at 0 °C for 10 minutes and then at room temperature for 20 minutes. The solution was then dried under vacuum and purified via flash column chromatography (silica, 30% DCM, 70% n-hexane) to give precursor 7 as a white solid (120 mg, 72%).

[0233] The name of precursor 7 is 1-azido-5,6-dimethoxy-2,3,8,9,12,13-hexakis(pentyloxy)dibenzo[fg,op]tetracene.

[0234] Precursor 7 had the following characterization data: 1 H NMR (300 MHz, CDCl3) δ 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). 13 C NMR (101 MHz, CDCl3) δ C151.6, 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。

[0235] Compound 33 was synthesized using the following method. Under an N2 atmosphere, the precursor 7 (100 mg; 0.13 mmol) was dissolved in dry PhMe (5 mL) and added to a flask containing rhodium dimer octanoate (5 mg; 0.01 mmol). The mixture was then heated to reflux and stirred for 20 hours. The reaction was cooled to room temperature and then dried under vacuum, and the solid was purified via flash column chromatography (silica; 95% n - hexane: 5% ethyl acetate) to obtain Compound 33 as a white solid (58 mg, 50%).

[0236] 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.

[0237] Compound 33 had the following characterization data: 1 H NMR (300 MHz, CDCl3) δ H10.08 (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). 13 C NMR (101 MHz, CDCl3) δ 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 + m / z: 889.2 ([M + H] + 100%).

[0238] Method for synthesizing compound 34 Precursor 6 (47 mg; 0.053 mmol), benzoyl chloride (30 μL, 0.265 mmol, 5 equivalents), and diisopropylethylamine (46 μL, 0.265 mmol, 5 equivalents) were dissolved in dry PhMe (5 mL), and the mixture was heated to reflux under an N2 atmosphere. The reaction mixture was stirred for 1 hour, at which point the mixture was dried under vacuum and then the solid was heated to 240 °C for 10 minutes. The reaction was cooled to room temperature and then the solid was purified via flash column chromatography (silica; 40% CH2Cl2, 60% n - hexane) to give compound 34 as a white solid (16 mg, 33%).

[0239] The name of Compound 34 is 12,13-dimethoxy-5,6,9,10,15-pentakis(pentyloxy)-2-phenyldibenzo[4,5:9,10]pyreno[1,2-d]oxazole.

[0240] Compound 34 had the following characteristic evaluation data: 1 H NMR (300 MHz, CDCl3) δ 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). 13 C NMR (101 MHz, CDCl3) δ 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 + m / z: 910.5 ([M + H] + 100%).

[0241] Method for synthesizing Compound 35 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 to reflux under a nitrogen atmosphere. The reaction mixture was stirred for 1 hour, at which point the mixture was dried under vacuum and then the solid was heated to 240 °C for 10 minutes. The reaction was cooled to room temperature and then the solid was purified via flash column chromatography (silica; 40% DCM, 60% n-hexane) to afford Compound 35 as a white solid (17 mg, 16%).

[0242] 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.

[0243] Compound 35 had the following characterization data: 1 H NMR (300 MHz, CDCl3) 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). 1313C NMR (100 MHz, CDCl3) 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 + m / z: 934.55 ([M+H] + 100%).

[0244] Method for synthesizing compound 36 Compound 1 was synthesized 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 maintained under N2 at reflux with heating and reflux for 18 h. The reaction was cooled to room temperature and then evaporated to dryness under vacuum and produced via flash column chromatography (silica, 60% CH2Cl2:40% n-hexane) to give the intermediate as a brown solid (19 mg, 18%).

[0245] The intermediate had the following characterization data: 1 Η NMR δ H:(300 MHz, CDCl3) 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. 13 13C NMR δ C :(100 MHz, CDCl3) 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%).

[0246] A solution of the intermediate (100 mg, 0.116 mmol) and Lawesson's reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was maintained under N2 at reflux with heating for 48 h. The reaction mixture was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n - hexane) to afford Compound 36 as a green solid (17 mg, 19%).

[0247] The name of Compound 36 is 2,3,6,11,12 - pentakis(pentyloxy) - 8 - phenyltriphenylene[1,2 - d]thiazole.

[0248] Compound 36 had the following characteristic evaluation data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C :(100 MHz, CDCl3) 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%).

[0249] Method for synthesizing compound 37 Compound 37 was synthesized 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 under reflux and maintained at reflux for 18 h under N2. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The brown crude solid was added to a solution of Lawesson's reagent (175 mg, 0.658 mmol) in PhMe (5 mL), and the mixture was heated under reflux and maintained at reflux for 48 h under N2. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford compound 37 as a yellow solid (5 mg, 5%).

[0250] The name of compound 37 is 4-(2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]thiazol-8-yl)benzonitrile.

[0251] Compound 37 had the following characterization data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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] + 100%).

[0252] Method for synthesizing compound 38 Compound 38 was synthesized from precursor 8 by the following method.

[0253] The precursor 8 was synthesized using the following method. It was dried, degassed for 10 minutes in a two-necked flask equipped with Subaseal(RTM), and 8-(naphthalen-2-yl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d]oxazole (150 mg, 0.18 mmol, 1 equivalent), which is compound 3, was dissolved in CH2Cl2 (10 mL) purged with N2 for 10 minutes. The green solution was stirred at -10 °C for 10 minutes under N2, and boron tribromide (1 M in CH2Cl2 solution) (0.2 mmol, 1.1 equivalents) was added via a syringe through Subaseal(RTM). The black solution was stirred at -10 °C for 2 hours under N2, then poured onto 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 to obtain a brown solid. The product was then purified by flash column chromatography (20% EtOAc:n-hexane, silica) to obtain 8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenylene[1,2-d]oxazol-11-ol as a yellow solid (31 mg, 23%).

[0254] The name of the precursor 8 is 8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenylene[1,2-d]oxazol-11-ol.

[0255] The precursor 8 had the following characterization data 。1 Η ΝΜR δ H :(300 MHz, CDCl3) 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.13 13C NMR δ C :(100 MHz, CDCl3) 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] + 100%), 756.66 ([M + H] + 70%), 757.67 ([M + 1 + H] + 25%).

[0256] A slurry of precursor 8 (100 mg, 0.13 mmol) and K2CO3 (114 mg, 0.83 mmol) in DMF (5 mL) was heated to reflux for 0.5 h with a CaCl2 drying tube, and then methyl 2-(2-(2-chloroethoxy)ethoxy)acetate (114 mg, 0.40 mmol) and KI (75 mg, 0.5 mmol) were added. The resulting slurry was heated to reflux for an additional 3 h. The reaction mixture was cooled to room temperature and the precipitate was filtered through suction filtration. The solvent was evaporated to dryness under vacuum from the filtrate, and the crude solid was purified via flash column chromatography (silica, 25% EtOAc:75% n-hexane) to afford compound 38 as a yellow solid (36 mg, 30%).

[0257] The name of compound 38 is methyl 2-(2-(2-((8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenylene[1,2-d]oxazol-11-yl)oxy)ethoxy)ethoxy)acetate.

[0258] Compound 38 had the following characterization data: 1 1H NMR δ H:(300 MHz, CDCl3) 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. 13 13C NMR δ C :(100 MHz, CDCl3) 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] + 100%), 916.7 ([M + H] + 90%). Elemental analysis found: C, 73.41; H, 7.56; N, 1.54%. C 56 H 69 NO 10 requires C, 73.42; H, 7.59; N, 1.53%.

[0259] Method for synthesizing Compound 39 Compound 39 was synthesized using the following method. A solution of NaOH (3 mg, 0.08 mmol) in H2O (1 mL) was added to a solution of compound 38 (35 mg, 0.04 mmol) in MeOH (5 mL). The resulting solution was heated to reflux for 5 h. The reaction mixture was cooled to room temperature and an aliquot of 1 M aqueous HCl was added until no further precipitate formed. The precipitate was collected by suction filtration to give a yellow solid (24 mg, 70%).

[0260] The name of compound 39 is 2-(2-(2-((8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenylene[1,2-d]oxazol-11-yl)oxy)ethoxy)ethoxy)acetic acid.

[0261] Compound 39 had the following characterization data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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] + 100%), 902.5 ([M + H] + 70%). Elemental analysis found: C, 73.24; H, 7.52; N, 1.54%. C 55 H 67 NO 10 requires C, 73.23; H, 7.55; N, 1.55%.

[0262] Method for synthesizing Compound 40 Compound 40 was synthesized using the following method. A slurry of precursor 8 (100 mg, 0.13 mmol) and K2CO3 (37 mg, 0.26 mmol) in MeCN (5 mL) was heated to reflux for 0.5 h with a CaCl2 drying tube, followed by the addition of 2-(2-(2-azidoethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (87 mg, 0.26 mmol). The resulting slurry was heated to reflux for an additional 24 h. The reaction mixture was cooled to room temperature and the precipitate was filtered through suction filtration. The solvent was evaporated to dryness under vacuum from the filtrate and the crude solid was purified via flash column chromatography (silica, 25% EtOAc:75% n-hexane) to afford Compound 38 as a yellow solid (18 mg, 15%).

[0263] The name of Compound 40 is 11-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)-8-(naphthalen-2-yl)-2,3,6,12-tetrakis(pentyloxy)triphenylene[1,2-d]oxazole.

[0264] Compound 40 had the following characteristic evaluation data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C :(100 MHz, CDCl3) 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] + 100%), 913.9 ([M + H] + 90%). The measured values of elemental analysis: C, 73.36; H, 7.55; N, 6.12%. C 55 H 68 N4O8 requires C, 73.34; H, 7.51; N, 6.14%.

[0265] Method for synthesizing compound 41 Compound 41 was synthesized using the following method. A slurry of precursor 8 (100 mg, 0.13 mmol) and K2CO3 (37 mg, 0.26 mmol) in MeCN (5 mL) was heated to reflux for 0.5 h in a CaCl2-dried tube, followed by the 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 resulting slurry was heated to reflux for an additional 24 h. The reaction mixture was cooled to room temperature and the precipitate was filtered through suction filtration. The solvent was evaporated to dryness under vacuum from the filtrate and the crude solid was purified via flash column chromatography (silica, silica, 50% EtOAc:50% n-hexane) to afford Compound 38 as a yellow solid (15 mg, 13%).

[0266] The name of 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.

[0267] Compound 41 had the following characterization data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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] + 100%), 887.6 ([M+H] + 70%).

[0268] Method for synthesizing Compound 44 Compound 44 was synthesized 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 reflux and maintained at reflux for 18 h under N2. The reaction was cooled to room temperature and then evaporated to dryness under vacuum, and the intermediate was obtained as a brown solid (19 mg, 18%) via flash column chromatography (silica, 60% CH2Cl2:40% n-hexane).

[0269] The intermediate (3-fluoro-N-(2,3,6,7,10,11-hexakis(pentyloxy)triphenylene-1-yl)benzamide) (100 mg, 0.11 mmol) was dissolved in xylene (10 mL), and Wollins reagent (117.8 mg, 0.22 mmol) was added to the flask. After the reaction mixture was stirred under reflux for 24 hours, it was cooled to room temperature, causing the formation of a gray precipitate. The contents of the flask were filtered through filter paper, and the filtrate was collected. The filtrate was evaporated to dryness and purified by column chromatography (silica, 40% dichloromethane:hexane) and (silica, 1% acetone:hexane) to obtain 8-(3-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d][1,3]selenazole as a yellow solid (1.8 mg).

[0270] The name of Compound 44 is 8-(3-fluorophenyl)-2,3,6,11,12-pentakis(pentyloxy)triphenylene[1,2-d][1,3]selenazole.

[0271] Compound 44 had the following characterization data: 1 H NMR δ H (500 MHz, CDCl3) 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 + m / z = 860.4 ([M + 2 + H] + 30%), 859.4 ([M + 2] + 60%), 858.4 ([M + H] + 90%), 857.4 ([M] + 100%), 856.4 ([M - 2 + H]+ 40%), 855.4 ([M - 2] + 60%), 854.4 ([M - 3] + 30%), 825.5 ([TpOxPhmF + MeOH] + ), 793.4 ([TpOxPhmF] + )。

[0272] Method for synthesizing Compound 45 Compound 45 was synthesized using the following method. Precursor 2 (190 mg, 0.25 mmol, 1 equiv) and 4 - methoxybenzoyl chloride (213 mg, 1.25 mmol, 5 equiv) were dissolved in dry toluene (7 mL), and N,N - diisopropylethylamine (0.2 mL, 1.25 mmol, 5 equiv) was added. The solution was stirred and heated to reflux for 2 hours with a CaCl2 drying tube. Then, the solution was evaporated to dryness, and the crude solid was heated to 240 °C for 10 minutes. The crude product was recrystallized (dichloromethane:hexane, 1:5) and then purified by silica plug (60% dichloromethane:hexane) to obtain 8 - (4 - methoxyphenyl) - 2,3,6,11,12 - pentakis(pentyloxy)triphenyleno[1,2 - d]oxazole as an off - white solid (53 mg, 26%).

[0273] The name of Compound 45 is 8 - (4 - methoxyphenyl) - 2,3,6,11,12 - pentakis(pentyloxy)triphenyleno[1,2 - d]oxazole.

[0274] Compound 45 had the following characteristic evaluation data: 1 Η ΝΜR δ H :(300 MHz, CDCl3) 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] +100%), 805.9 ([M+H] + 70%), 806.9 ([M+1+H] + 25%).

[0275] Method for synthesizing compound 46 Compound 46 was synthesized 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 maintained under N2 at reflux with heating for 18 hours and then at reflux. The reaction was cooled to room temperature and then evaporated to dryness under vacuum and produced via flash column chromatography (silica, 60% CH2Cl2:40% n-hexane) to give the intermediate as a brown solid (19 mg, 18%).

[0276] The intermediate had the following characterization data: 1 Η NMR δ H : (300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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%).

[0277] 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 reflux and maintained at reflux for 48 h under N2. The reaction mixture was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to afford Compound 46 as a green solid (17 mg, 19%).

[0278] The name of Compound 46 is 2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenylene[1,2-d]thiazole.

[0279] Compound 46 had the following characterization data: 1 Η NMR δ H :(300 MHz, CDCl3) 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. 13 C NMR δ C:(100 MHz, CDCl3) 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%).

[0280] Method for synthesizing compound 47 Compound 47 was synthesized 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 maintained under N2 at reflux with heating for 18 h. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The brown crude solid was added to a solution of Lawesson's reagent (175 mg, 0.658 mmol) in PhMe (5 mL), and the mixture was maintained under N2 at reflux with heating for 48 h. The reaction was cooled to room temperature and then evaporated to dryness under vacuum. The solid was then heated and maintained at 240 °C for 15 min under N2. The black crude solid was then cooled to room temperature and purified via flash column chromatography (silica; 40% CH2Cl2:60% n-hexane) to give compound 47 as a yellow solid (5 mg, 5%).

[0281] The name of compound 47 is 4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]thiazol-8-yl)benzonitrile.

[0282] Compound 47 had the following characterization data: 1 Η NMR δ H:(300 MHz, CDCl3) 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%).

[0283] Referring to Table 1 here, the luminescence data of Compounds 1 - 6 are shown.

Table 1

[0284] Referring to Tables 2 - 4 here, the luminescence data of pairs of compounds that can absorb at the same wavelength and emit at different wavelengths are provided.

Table 2

Table 3

Table 4

[0285] Example 1: Visualization of the Human Liver In Vitro Test To test the relative toxicity of tetrahydrofuran (THF) to hepatocytes, Huh-7 cells (a hepatocellular carcinoma cell line used as a model of hepatocytes) were labeled with CMFDA (CellTracker Green, in DMSO, Invitrogen), and then treated with half-log concentrations of THF (0.1%, 0.3%, 1%, 3%) for 1 hour. Subsequently, live cells were imaged using a Zeiss primovert fluorescence microscope.

[0286] Cell images showed no difference in cell culture compared to the reference at 0.1% and 0.3% THF. An increase in the number of dead cells was recorded at 1% and 3% THF.

[0287] Ex vivo test All fluorophores were tested using donated human tissue previously rejected for transplantation. All reagents were diluted to working concentration in pre-warmed Dulbecos Modified Eagles Medium (DMEM) or CO2-independent medium (both from Invitrogen), then perfused through liver slices for 45 minutes. Membrane and nuclear dyes were used simultaneously to visualize other cellular structures within the liver. The tissue was then imaged using a multiphoton microscope (825 nm). All fluorophores were used at 1 μg / mL, providing a vehicle of 0.1% DMSO or THF. The test of TpOx-2-Nap (green fluorophore) was performed using DMSO as the solvent. This resulted in limited solubility, but the green fluorescence was still visible. A commercially available erythrocyte membrane dye (CMFDA) was used for comparison and perfused through separate tissue slices from the same donor. When using TpOx-Ph (blue fluorophore), THF was used as the solvent, resulting in brighter and less punctate fluorescence.

[0288] Figure 1 shows a multiphoton microscopy image (10) of the liver ex vivo perfused with TpOx-2-Nap. The green fluorophore was found to perfuse effectively throughout the human tissue and intracellularly. Diffuse green fluorescence (12) was observed within the cytoplasm of hepatocytes separated by the cell membrane (14) stained red by the commercially available dye. Bright green spots (16) in the image indicated significant uptake of the fluorophore in T cells. The tissue maintained fluorescence over several hours, indicating that the fluorophore did not leak out of the cells.

[0289] Figures 2A and 2B show multiphoton microscopy images of the liver ex vivo perfused with TpOx-Ph (blue fluorophore). The bright regions indicate where the fluorophore has been taken up by hepatocytes. In the center of the image, a black region (22) can be seen. This region (22) is the hepatic vein, which appears as a black region in the image due to the complete absence of the fluorophore within the vein. The retention of the fluorophore within the hepatocytes provides good contrast between the vein and the liver tissue, allowing the vein to be observed over several hours.

[0290] These results demonstrate that the compounds described herein are suitable for live tissue imaging because they can penetrate tissues sufficiently, cross cell membranes, and provide bright emission.

Claims

1. A composition for imaging biological tissue or fluid, comprising a luminescent compound of formula (A) and a biologically acceptable diluent or carrier, 【Chemical 1】 wherein X represents one of an oxygen atom, a sulfur atom, or a selenium atom, R represents an aromatic group and / or an aliphatic group, A independently represents a hydrogen atom or an alkyl group containing 1 to 20 carbons, J １ 、J ２ 、J ３ 、J ４ 、J ５ independently represent a hydrogen atom, said composition.

2. The composition according to claim 1, wherein the luminescent compound of formula (A) is capable of crossing the cell membrane.

3. The composition according to claim 1 or 2, wherein the luminescent compound of formula (A) can be retained with cells for at least 10 minutes.

4. The composition according to any one of claims 1 to 3, wherein the luminescent compound of formula (A) preferentially accumulates in T cells.

5. The composition according to any one of claims 1 to 4, wherein the biologically acceptable diluent or carrier comprises phosphate buffered saline, saline, deionized water, blood, cell culture medium, or plasma.

6. The composition according to any one of claims 1 to 5, wherein the luminescent compound of formula (A) is present in the composition at a concentration of 0.1 to 20 μg / ml.

7. The composition according to any one of claims 1 to 6, wherein the composition contains two or more different luminescent compounds, at least one of which has the general formula (A).

8. The composition according to any one of claims 1 to 7, comprising a first luminescent compound of formula (A) that emits light at a first wavelength and a second luminescent compound of formula (A) that emits light at a second wavelength longer than the first wavelength, wherein both the first and the second compounds are capable of absorbing light at a third wavelength shorter than both the first and the second wavelengths.

9. The composition according to any one of claims 1 to 8, wherein the luminescent compound of formula (A) is conjugated to a further molecule.

10. The composition according to any one of claims 1 to 9, comprising cells stained with a luminescent compound of formula (A).

11. Use of a luminescent compound or composition of formula (A) according to any one of claims 1 to 10 in a method of obtaining an image of a biological tissue or fluid using a fluorescence microscope, wherein the biological tissue or fluid is in vitro or ex vivo.

12. A method of obtaining an image of a biological tissue or fluid previously obtained from a subject, the method comprising: -administering or contacting the biological tissue or fluid with a luminescent compound or composition of formula (A) according to any one of claims 1 to 10; and -obtaining an image of the biological tissue or fluid using a fluorescence microscope.

13. The use according to claim 11 or the method according to claim 12, wherein the fluorescence microscope is a multiphoton microscope.

14. The use according to claim 11 or the method according to claim 12 or 13, wherein the fluid is blood.

15. The use according to claim 11 or the method according to any one of claims 12 to 14, wherein the biological tissue is connective tissue, muscle tissue, nerve tissue, epithelial tissue, vascular tissue, lymphoid tissue, endocrine tissue, gland, or organ.

16. A luminescent compound or composition of formula (A) according to any one of claims 1 to 10 for use in a method for diagnosing a disease or condition in a subject, wherein the disease or the condition is selected from cancer, inflammation, edema, cardiovascular disorder, ischemia, autoimmune disease, infectious disease, skin disease, eye disease, neuropathy or injury, said luminescent compound or said composition.

17. A kit for imaging a biological tissue or fluid, said kit comprising - a luminescent compound or composition of formula (A) according to any one of claims 1 to 10, and - instructions for use, said kit.

18. A composition for imaging a biological tissue or fluid, comprising a compound of formula (A) and a biologically acceptable diluent or carrier, 【Chemical Formula 2】 wherein X represents one of an oxygen atom, a sulfur atom, or a selenium atom, R represents an aromatic group and / or an aliphatic group, p is an integer from 1 to 2, q and s are independently an integer of 1, 2, 3, or 4, Y １ 、Y ２ 、and Y ３ are independently 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, a hydroxyl group, an alkylated oxygen atom forming an alkoxy group, a primary, secondary or tertiary amine group, a cyano group, a nitro group, and / or Y １ 、Y ２ 、and Y ３ two or more of which may combine together to form a condensed ring, composition.

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