Liquid crystal composition containing a reversibly photopolymerizable compound or monomer, a pattern rewritable polymer-dispersed liquid crystal element, and related selectively dimmable devices.

Abstract

This paper describes a photoreactive liquid crystal compound having a reversible photodimerizing functional group, and a device containing the compound. A liquid crystal composition containing a reversibly photodimerizable liquid crystal compound can enable the display content to be changed under the application of an electric field.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims the interests of U.S. Provisional Patent Application No. 63 / 493,132, filed on 30 March 2023, and the entirety of its contents constitutes part of this specification by reference. [Background technology]

[0002] This disclosure relates to a reversibly polymerizable compound or composition, and to an element or device comprising a reversibly polymerizable compound or composition.

[0003] Smart windows could be an attractive alternative to conventional mechanical shutters, blinds, or hydraulic shading methods for window shading. Technologies for smart window applications include suspended particle displays (SPDs), polymer-dispersed liquid crystals (PDLCs), and electrochromics (Non-Patent Documents 1 and 2). With regard to PDLCs, once a PDLC image is created, it is fixed, and changing or replacing the image may require reloading a new image on or within the device.

[0004] Therefore, further contributions are needed in this technological field. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] S. Rudolph, J. Dieckmann, & J. Brodrick, Technologies for Smart Windows, ASHRAE Journal 104 (Jul. 2009) [Non-Patent Document 2] D. Cupelli et al., Reverse Mode Operation Polymer Disperse Liquid Crystal with a Positive Dielectric Anisotropy Liquid Crystal, 49 J. Polymer Sci. Part B: Polymer Physics 257-62 (2011) [Overview of the Initiative]

[0006] In one embodiment, a material that can be used in a rewritable PDLC dimming device is described herein. This material can be integrated into a window or applied as a coating that provides interchangeable images by incorporating the photoreactive compounds described herein, but other applications are also possible and conceivable.

[0007] In one embodiment, a photoreactive liquid crystal composition may become photoreversible by applying irradiation to the composition to bring about selective polymerization and / or depolymerization of crosslinking entities, such as reversibly photodimerizable functional groups. In some embodiments, the photoreactive liquid crystal composition comprises at least one photoreactive compound which may contain at least two photodimerizable functional groups.

[0008] In some embodiments, the photoreactive liquid crystal compound has a structure or substructure that conforms to the following general formula: [ka]

[0009] In this formula, R1, R3, R4, R5 and / or R7 may be independently selected from an anthracenyl group, a coumarinyl group, a cinnamylate group, a stilbenylon group, or a thyminyl group, and R7 may be selected from a bond, hydrogen, or a C1-C3 alkyl group. L1, L3, L4, and L5 are independent of C1~C 10 Diether linker or C1~C 10It can be selected from ether acetate linkers.

[0010] In some embodiments, linkers L1, L3, L4, and L5 are independently, [ka] [ka] or [ka] The following can be selected, where n or m is an integer between 1 and 10.

[0011] In some embodiments, the photoreactive liquid crystal compound or mesogen may contain a reversible photodimerizable R functional group. In some embodiments, the reversible photodimerizable R functional group may contain R groups R1, R3, R4, and / or R5. In some embodiments, the R1 group, R3 group, R4 group, and / or R5 group may be independently [ka] [ka] [ka] [ka] or [ka] It can be selected from the following. In some embodiments, the photoreactive liquid crystal compound has the following structure: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] It may have one of the following.

[0012] In some embodiments, the polymer-dispersed liquid crystal (PDLC) composition may comprise a photoreactive liquid crystal compound as described herein. In some embodiments, the photoreactive compound may comprise at least two reversible photodimerizing functional groups as described herein. In some embodiments, the polymer-dispersed liquid crystal element may comprise a polymer-dispersed liquid crystal composition as described herein.

[0013] In some embodiments, a method for reversibly crosslinking a polymer network includes providing a monomer, oligomer, or polymer comprising a liquid crystal composition. In one embodiment, the liquid crystal composition may comprise one or more photoreactive liquid crystal compounds, each having at least two photodimerizing functional groups. For example, in one embodiment, the liquid crystal composition may comprise two photoreactive liquid crystal compounds described herein. The method further comprises irradiating the oligomer or polymer with ultraviolet light. In one embodiment, the UV rays include a first crosslinking wavelength between about 305 nm and about 395 nm, for example, about 365 nm, to reversibly crosslink and photodimerize terminal R groups located at the ends of linker L, which may be, for example, anthracenyl groups, coumarinyl groups, cinnamylate groups, stilbenylon groups, or thyminyl groups (may be more than one). In some embodiments, the method also comprises irradiating the crosslinked oligomer or polymer with ultraviolet light including a second cleaving wavelength between about 254 nm and about 280 nm. In some embodiments, the liquid crystal element comprises a transparency-changing layer defining two opposing surfaces, a composition described herein, and at least two alignment layers, wherein the transparency-changing layer may be bounded by each of the at least two alignment layers on both opposing surfaces.

[0014] In some embodiments, a selectively dimmable device includes a first conductive substrate and a second conductive substrate, a liquid crystal element described herein disposed between the first conductive substrate and the second conductive substrate, and a voltage source. The first conductive substrate, the second conductive substrate, the liquid crystal element, and the voltage source are all electrically conductive, and therefore, when a voltage is applied from the voltage source, an electric field is applied to the entire element.

[0015] In some embodiments, a selectively dimmable device may be characterized by having a haze of up to 10% when no voltage is applied, but a haze of at least 35% when a voltage of less than 40 volts is applied to the entire device. In some embodiments, the substrate is flexible, and the device is in the form of a flexible sheet.

[0016] These and other embodiments will be described in more detail below. [Brief explanation of the drawing]

[0017] [Figure 1A] This figure shows a liquid crystal element using a liquid crystal with positive dielectric anisotropy. [Figure 1B] This figure shows a liquid crystal element using a liquid crystal with negative dielectric anisotropy. [Figure 2] This figure shows a non-limiting embodiment of a selectively dimmable device using a polymer-dispersed liquid crystal with positive dielectric anisotropy. [Figure 3] This figure shows a non-limiting embodiment of a selectively dimmable device using a negative dielectric anisotropic polymer dispersed liquid crystal. [Figure 4] This figure shows another non-limiting form of a selectively dimmable device. [Figure 5] This is a graph showing the haze results between various selectively dimmable devices. [Figure 6] This is another graphical representation showing the haze results between various selectively dimmable devices. [Figure 7] This graph shows dimerization (molecular weight) as a function of UV365 exposure time. [Figure 8] This graph shows the dimerization (molecular weight) as a function of RM-13 concentration. [Figure 9] This graph shows the cleavage (molecular weight) as a function of UV254 exposure time. [Figure 10] This graph shows the effect of cleavage (molecular weight) as a function of UV365 20-minute exposure time and UV254 60-minute exposure time on the molecular weight measurement. [Modes for carrying out the invention]

[0018] When used herein, "C X~Y The term "carbon chain" refers to a carbon chain having X to Y carbon atoms. For example, C3~8 Alkyl includes alkyl or cycloalkyl groups containing 3, 4, 5, 6, 7, or 8 carbon atoms.

[0019] As used herein, the term "alkyl" refers to a carbon-hydrogen moiety that does not contain double or triple bonds. Alkyls can be linear, branched, cyclic, or a combination thereof, and can contain one to 35 carbon atoms. Examples of alkyl groups include, but are not limited to, C3 alkyls; C4 alkyls, e.g., (CH2)3CH3; C5 alkyls, e.g., -(CH2)3CH3; C6 alkyls; C7 alkyls; C8 alkyls, etc.

[0020] As used herein, the terms “positive dielectric anisotropy,” “negative dielectric anisotropy,” and “neutral dielectric anisotropy” all have meanings known to those skilled in the art. Dielectric anisotropy relates to dielectric and optical properties depending on whether the direction is along the length (or molecular axis) of the molecule or perpendicular to the length (or molecular axis) of the molecule. Dielectric properties depend on the molecular shape and substituent parts and their positions on a given molecule.

[0021] A molecule is said to have positive dielectric anisotropy if the dielectric constant in the direction parallel to the length of the molecule is greater than the dielectric constant in the direction perpendicular to the length of the molecule. In this case, the length of the molecule is defined as the vector between its two furthest parts.

[0022] A molecule is said to have negative dielectric anisotropy if the dielectric constant perpendicular to the molecular length is greater than the dielectric constant parallel to the molecular length. In this case, the molecular length is defined as the vector between the two furthest parts.

[0023] A molecule is said to have neutral dielectric anisotropy if the dielectric constant perpendicular to the molecular length is approximately the same as the dielectric constant parallel to the molecular length (i.e., the difference between the dielectric constants is less than 1%), in which case the molecular length is defined as the vector between the two furthest parts.

[0024] As used herein, the term “opposing faces” refers to a set of two surfaces or sides of a shape or polygon that are opposite each other (e.g., the top and bottom faces of a layer, or the front and back of a shape). When used in the singular, the term “opposing faces” refers to one of two faces.

[0025] The terms nematic, smectic, and isotropic all have the same meaning as those used by those skilled in the art when referring to liquid crystal phases.

[0026] This disclosure relates to reversibly crosslinkable monomers, oligomers and / or polymers, liquid crystal compositions, polymer-dispersed liquid crystal (PDLC) elements, and / or selectively dimmable devices comprising polymer-dispersed liquid crystal (PDLC) elements.

[0027] This disclosure also relates to a display device capable of repeatedly recording (writing) and erasing visible information. For example, in one embodiment, the writing of a pattern can be done by light irradiation by dimerization (photopolymerization) including a crosslinking wavelength of about 305 nm to about 395 nm, and the erasure of the pattern can be achieved by light irradiation of a shorter wavelength (e.g., between about 250 nm and about 280 nm) or by heat.

[0028] This disclosure also relates to electrically switchable and optically rewritable displays based on photopolymerization / photodepolymerization of photoreactive liquid crystal (LC) compounds. In some embodiments, the photoreactive liquid crystal compound comprises one or more reversibly photodimerizable functional groups. Optically rewritable patterns can be generated by using nematic LC as a reaction solvent and applying a spatially heterogeneous electric field, without the use of lithographic or holographic apparatus. A nematic mixture containing 5.0 wt% RM (95% LC) sandwiched between electrodes was exposed to spatially homogeneous reaction-initiating radiation. The spatially heterogeneous electric field induced an optical pattern in the reaction template with spatially varying elastic deformation. The resulting polymerized liquid crystal network patterned both spatially and optically with good fidelity to the electrode pattern and subsequent periodic director profile. This pattern can be erased by dissociating the polymerized liquid crystal network by irradiation with ultraviolet light between approximately 250 nm and 280 nm wavelengths.

[0029] Display devices can repeatedly record (write) and erase visible information. For example, patterns can be written by irradiation, for instance, using light with wavelengths between approximately 305 nm and 395 nm for (photopolymerization) dimerization, and erased by irradiation with light or heat (where the dissociation of the dimer leads to erasure) with shorter wavelengths (between approximately 250 nm and 280 nm). The techniques used here may also be useful for the integration of LED light sources into laminated glass panels or for the repeated generation of characteristic patterns, images, and logos in holographic memory systems, but other applications are also possible and conceivable.

[0030] Liquid crystal composition In some embodiments, a composition may include both liquid and crystalline properties and may be referred to as a liquid crystal composition. In some embodiments, a liquid crystal composition may include one or more compounds described herein. In some embodiments, a liquid crystal composition may exhibit a mesogenic liquid crystal phase. In some embodiments, a liquid crystal composition may include a compound having positive dielectric anisotropy, and in some embodiments, a liquid crystal composition may include a compound having negative dielectric anisotropy. In some embodiments, a liquid crystal composition may include a compound having positive dielectric anisotropy and a compound having negative dielectric anisotropy.

[0031] In some embodiments, the liquid crystal composition may further comprise at least one additional liquid crystal compound. In some forms, the additional liquid crystal compound may be a nematic composition exhibiting positive dielectric anisotropy. In some forms, the additional liquid crystal compound may be a nematic compound exhibiting negative dielectric anisotropy. In some embodiments, a suitable additional liquid crystal compound may include MLC-2132 (EMD Performance Materials, Philadelphia, Pennsylvania).

[0032] Photoreactive liquid crystal compounds In some embodiments, the liquid crystal composition may include a photoreactive liquid crystal compound. In some embodiments, the photoreactive compound may include at least two photoreactive and / or reversible photodimerizing functional groups. In some embodiments, the monomer may be capable of forming a reversibly crosslinked oligomer or polymer, and the monomer may include a substituted benzyl derivative. In some embodiments, the substituted benzyl derivative may include at least two linked functional substituents. In some embodiments, the substituted benzyl derivative may include two linked functional substituent arms, three linked functional substituent arms, four linked functional substituent arms, five linked functional substituent arms, and / or six linked functional substituent arms.

[0033] In some embodiments, the substituted benzyl derivative may have the following general formula: [ka] (In the formula, T1, T2, T3, T4, T5, or T6 may be a bond, hydrogen, a C1-C3 alkyl group and / or an LR functional group, where L is C1-C 10 Diether linker or C1~C 10 It can be an ether acetate linker, where R can be a reversibly photodimerizable functional group, such as an anthracenyl group, a coumarinyl group, a cinnamylate group, a stilbenylon group, and / or a thyminyl group).

[0034] In some embodiments, the substituted benzyl derivative may have the following general formula: [ka]

[0035] In some embodiments, the substituted benzyl derivative may have the following general structure: [ka]

[0036] In some embodiments, the substituted benzyl derivative may have the following general structure: [ka]

[0037] In some embodiments, R7 may be a bond, hydrogen, or a C1-C3 alkyl group. In some embodiments, liquid crystal compounds and / or monomers capable of forming reversibly crosslinked oligomers or polymers may include an R group located at the linker end opposite the benzyl core group. In some embodiments, the R group may include R1, R2, R3, R4, R5, and / or R6. In some embodiments, R1, R2, R3, R4, R5, and / or R6 may be independently selected from anthracenyl, e.g., anthracene; coumarinyl, e.g., coumarin; cinnamylate, e.g., cinnamic acid / ester; stilbenyl, e.g., stilbene; or thyminyl, e.g., thymine. In some embodiments, the anthracenyl group, coumarinyl group, cinnamylate group, stilbenyl group, or thyminyl group may be of the following general formula: [ka] (Anthracenil) [ka] (Cumarinyl group), [ka] (Cinnamic acid ester), [ka] (Stilbenyl group), and, [ka] (Thyminyl group).

[0038] In some embodiments, each R group may contain the same substituent; for example, all R groups may be anthracenyl groups. In some embodiments, each R group may contain any combination of the substituents described above; for example, one arm may be functionalized with one of the substituents described above, and the other arm may be functionalized with another of the substituents described above. Thus, multiple arms may be a mixture of arms functionalized with anthracene, coumarin, cinnamic acid, stilbene, and / or thymine. In some embodiments, at least one of each R group may dimerize, covalently bond, or link with a similar R group; for example, an anthracenyl terminal group may dimerize, covalently bond, or link with another anthracenyl terminal group. In some embodiments, the composition may contain at least two photoreactive liquid crystal compounds having reversibly dimerizable functional groups. Non-limiting examples of reversible dimerization or bonding of at least two dimerizable functional groups include: [ka] TIFF2026512837000034.tif95170 [ka]

[0039] The above-described photoreversible dimerization or covalent bonding is considered one example that enables the formation of links through bonding of each terminal R group. In some embodiments, each structural change can be determined by proton NMR. Photoreversible dimerization is thought to enable the rewriting and erasing properties of this material.

[0040] In some embodiments, a liquid crystal compound and / or monomer capable of forming an oligomer or polymer that is photoreactive and reversibly dimerizes or crosslinks may include a linker L between a benzyl core group and an R group. In some embodiments, the linker L may include L1, L2, L3, L4, L5, and / or L6 and / or any additional similar arms. In some embodiments, the linker L may be selected from a C2-C8 diether linker or a C2-C8 ether acetate linker. In some embodiments, L is a C1-C 10 diether linker (e.g., a C2 diether linker, a C3 diether linker, a C4 diether linker, a C5 diether linker, a C6 diether linker, a C7 diether linker, a C8 diether linker, a C9 diether linker, and / or a C 10 diether linker) or a C1-C 10 ether acetate linker (e.g., a C1 ether acetate linker, a C2 ether acetate linker, a C3 ether acetate linker, a C4 ether acetate linker, a C5 ether acetate linker, a C6 ether acetate linker, a C7 ether acetate linker, a C8 ether acetate linker, a C9 ether acetate linker, and / or a C 10 ether acetate linker). In some embodiments, the linker L may independently be [Chemical formula] [Chemical formula] [Chemical formula] selected from, where n or m can be from 1 to 10, such as 3, 4, 5, and / or 6.

[0041] In some embodiments, a monomer capable of forming a photoreactive reversibly dimerizable oligomer or polymer is ​​​ [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] and or [ka] It may contain one compound selected from, or at least two compounds.

[0042] In some embodiments, the monomer, oligomer, or polymer may have a substructure that may include the above-mentioned monomer and / or photoreactive liquid crystal compound.

[0043] In some embodiments, the polymer-dispersed liquid crystal formulation may include the liquid crystal compounds described herein and / or the monomers, oligomers, and / or polymer-dispersed liquid crystal compositions described herein. In some embodiments, the polymer-dispersed liquid crystal element may include the monomers, oligomers, and / or polymer liquid crystal compositions described herein.

[0044] In some embodiments, a method for reversibly crosslinking a polymer network may include providing an oligomer or polymer comprising a photoreactive monomer, oligomer, and / or polymer described herein. In one embodiment of this method, a crosslinked oligomer or polymer is provided by irradiating the oligomer or polymer with crosslinking ultraviolet light having a crosslinking wavelength between about 305 nm and about 395 nm. In some embodiments, the irradiation of at least R groups may result in covalent bonding between the same R groups. In some embodiments, the bonding may be selected from those described herein. This method may also include irradiating the oligomer or polymer with ultraviolet light having a cleavage wavelength between about 220 nm and about 280 nm, for example, 254 nm. In some embodiments, the irradiation of the R groups, for example, anthracene or coumarin, results in cleavage from the same R groups. In some embodiments, the bonding may be selected from those described herein.

[0045] This method may include repeated irradiation steps of applying crosslinking and dehiscence ultraviolet light.

[0046] Click the LCD button For example, as shown in Figure 1A or Figure 1B, the liquid crystal element 100 includes a transparency-changing layer 110 and at least two alignment layers 120. In the illustrated embodiment, the transparency-changing layer 110 has two opposing surfaces, each of which is bounded by a first and a second alignment layer 120. In some embodiments, any of the above layers may further include a dispersant, a plasticizer, a binder, and / or a solvent.

[0047] In the illustrated embodiment, the transparency-changing layer 110 comprises a liquid crystal composition 111 as described herein. In some embodiments, the liquid crystal composition 111 in the transparency-changing layer 110 may comprise any of the liquid crystal mixed compounds described herein. Those skilled in the art will recognize that additional PDLC materials, including, for example, positive dielectric anisotropy compounds, negative dielectric anisotropy compounds, and / or polymers, may be present in the PDLC matrix. Non-limiting examples of positive dielectric anisotropy compounds are described in detail elsewhere herein or found in International Publication No. 2017 / 180923 and / or International Publication No. 2018 / 152257, the contents of which are incorporated herein by reference in whole. In some embodiments, as shown in Figure 1B, the composition may comprise a negative dielectric anisotropy compound 114, while the embodiment in Figure 1A comprises a positive dielectric anisotropy compound 113. In some embodiments, the composition 111 may comprise both a positive dielectric anisotropy compound and a negative dielectric anisotropy compound. In some embodiments, the transparency-changing layer 110 may further contain a polymer 112, and the composition 111 may be dispersed in the polymer. In the embodiment shown in Figure 1, the composition 111 is dispersed in the transparency-changing layer, so that the composition forms droplets suspended in the polymer 112. The transparency-changing layer 110 can be considered a polymer-dispersed liquid crystal (PDLC). In the embodiments shown in Figures 1A and 1B, the transparency-changing layer 110 includes a spacer 115, but embodiments without the spacer 115 are also conceivable. In some embodiments, the transparency-changing layer 110 may contain one or more photoreactive liquid crystal compounds described herein. In some embodiments, the liquid crystal element 100 may be opaque to visible light but become transparent when an electric field is applied, i.e., it may be a normal-mode PDLC. In some embodiments, the liquid crystal element 100 may be transparent to visible light but become opaque when an electric field is applied, i.e., it may be an inverse-mode element.

[0048] In some embodiments, the transparency-changing layer 110 may be a polymer-dispersed liquid crystal layer, in which case the liquid crystal composition forms droplets within the polymer matrix. In some embodiments, the liquid crystal droplets are formed as suspended precipitates during the polymerization of the polymer precursor. In some embodiments, the droplets may have a uniform, gradient, or random distribution within the polymer matrix. In some embodiments, the transparency-changing layer 110 may further include a substrate having transparent electrode layers disposed on both sides of the polymer-dispersed liquid crystal layer.

[0049] Selectively dimmable devices Referring here to Figures 2 and 3, a selectively dimmable device 200 is shown. The device 200 includes two conductive substrates (or electrode layers) 210, a liquid crystal element 100, and a voltage source. In the illustrated embodiment, the first and second conductive substrates 210 define a gap between them, where the liquid crystal element 100 is positioned between the first and second conductive substrates 210 within this gap. In some embodiments, a polymer matrix containing one or more photoreactive compounds described herein may be placed within a flexible film containing the material described herein. In some embodiments, the polymer matrix containing the photoreactive compounds described herein may be placed within a polymer liquid crystal composition containing the material described herein. In some embodiments, the liquid crystal element 100, the conductive substrates 210, and the voltage source are all electrically connected, so that an electric field is applied to the entire liquid crystal element 100 by applying a voltage from the voltage source. In some embodiments, the application of a voltage from the voltage source provides an identifiable image when the liquid crystal composition and / or device 200 are observed.

[0050] As shown in Figures 2 and 3, the liquid crystal element 100 incorporated into the device 200 includes a polymer matrix 112 in which polymer-dispersed liquid crystal droplets are suspended and bounded by two alignment layers 120. In some embodiments, the polymer-dispersed liquid crystal droplets may include one or more of the photoreactive compounds described herein. For example, as shown in Figure 2, in some embodiments of the device 200, the liquid crystal droplets may include a positive dielectric anisotropy compound 113. In other embodiments of the device 200, as shown in Figure 3, for example, the liquid crystal droplets may include a negative dielectric anisotropy compound 114. In yet another embodiment, the liquid crystal droplets may include a combination of a positive dielectric anisotropy compound and a negative dielectric anisotropy compound.

[0051] In some embodiments of the device 200, the liquid crystal elements 100 are selected such that the refractive indices of the liquid crystal composition 111 and the polymer 112 are similar to each other under conditions where no induced electric field is present in the transparency-changing layer 110, thereby allowing the total transmittance of visible light that can pass through the device 200 to be at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, and / or at least about 95%. In some embodiments, when an electric field is present, for example due to a voltage applied to an electrical circuit, the refractive indices of the liquid crystal composition 111 and the polymer 112 may change relative to each other, thereby scattering the incident light and allowing at most only about 70%, about 65%, about 60%, about 50%, about 30%, about 25%, about 15%, about 10%, or about 5% of visible light to pass through the device 200. In some embodiments, the magnitude of the electric field required to achieve scattering corresponds to applying a voltage of less than 120V, less than 110V, less than 50V, less than 40V, less than 20V, less than 15V, less than 12V, less than 10V, or less than 5V to the entire device 200. In some embodiments, the electric field of the entire device 200 is less than approximately 500kV / m, less than approximately 1000kV / m, less than approximately 5000kV / m, less than approximately 10000kV / m, less than approximately 20000kV / m, less than approximately 40000kV / m, or less than approximately 80000kV / m. The dimming effect of device 200 can also be expressed in terms of haze percentage, generally:

number

[0052] In some embodiments, the device 200 can be semi-rigid or rigid. In some embodiments, the device 200 can be flexible. In some embodiments, as shown in Figure 4, the selectively dimmable device 200 can form a flexible sheet, which can be applied between or on the surface of existing windows. In some embodiments, the conductive substrate 210 can be formed of a flexible material, thereby the aforementioned device can be a flexible film. In some embodiments, the flexible device can be placed between or on one side of existing window panes to provide dimming functionality. In other embodiments, the device can be a rigid body containing a non-flexible material.

[0053] In some embodiments, the conductive substrate 210 may include a base 211, which in some forms may be formed from a conductive material.

[0054] In some embodiments, each conductive substrate 210 may further include an electron conduction layer 212, in which case the layer is physically connected to the base 211. In some embodiments, the electron conduction layer is placed in direct physical communication with the base 211, such as as a layer on top of the base 211. In other embodiments, the electron conduction layer may be directly impregnated into the base (e.g., ITO glass, ITO PET, or ITO PEN) or sandwiched between two bases 211 to form a single conductive substrate. In some embodiments, if an electron conduction layer is present, the base 211 may be formed of a non-conductive material. In some embodiments, the selectively dimmable device 200 may also include a sealant 250, as shown, for example, in Figures 2 and 3. In some embodiments, the sealant 250 may encapsulate the liquid crystal element 110 between the conductive substrates 210 to protect the element 110 from the environment. In some embodiments, the sealant 250 may include 3-Bond 2087, a two-component real-time curing epoxy, or similar. In some embodiments, the sealant 250 may include a UV-curable photopolymer such as NOA-61 or the same. In some embodiments, as shown in Figure 4, the selectively dimmable device 200 may also include an adhesive layer 260. In some embodiments, the adhesive layer 260 allows the flexible sheet embodiment of the device 200 to be installed in an existing window. In some embodiments, the adhesive may include an optically clear adhesive (OCA). In some embodiments, the OCA may include commercially available OCA products known to those skilled in the art (e.g., Nitto OCA tape, Scapa OCA tape). In some embodiments, the selectively dimmable device 200 may include a peelable carrier substrate 261 to protect the adhesive layer 260 from contamination, which is peeled off before application of the device.

[0055] In one or more embodiments, a method using a polymer-dispersed liquid crystal composition or a film containing the same includes a fixation process to generate a liquid crystal polymer by a photodimerization reaction of a photoreactive liquid crystal compound, and a reset process to generate a photoreactive liquid crystal compound by a depolymerization reaction of the liquid crystal polymer. In some embodiments, the fixation process is repeated after the reset process. In some embodiments, the fixation process and / or the reset process are repeated. In some embodiments, the region in which the liquid crystal polymer is generated in the second and subsequent fixation processes is different from the region in which the liquid crystal polymer is generated in the preceding fixation process.

[0056] In one or more embodiments, a method for reversibly crosslinking a polymer network involves preparing an oligomer or polymer containing one or more photoreactive liquid crystal compounds described herein, and applying 0.1 J / cm³ to the oligomer or polymer. 2 ~2500.0 J / cm 2 For example, 32.4 J / cm 2 Or 673.2 J / cm 2 This may include irradiating with ultraviolet light, the UV rays having a first crosslinking wavelength greater than about 350 nm, about 300 nm, about 320 nm, about 270 nm, and / or about 300 nm, and less than about 425 nm, about 420 nm, about 415 nm, about 410 nm, about 405 nm, about 400 nm, and / or about 395 nm. In some embodiments, the first crosslinking wavelength is between about 305 nm and about 395 nm. In some embodiments, the method for reversibly crosslinking a polymer network involves applying 0.1 J / cm² to the crosslinked oligomer or polymer. 2 ~2500.0 J / cm 2 For example, 32.4 J / cm² 2 Or 673.2 J / cm 2The method may further include irradiating with ultraviolet light, the UV rays having second cleavage wavelengths smaller than 300 nm, 260 nm, 280 nm, 249 nm, and / or 280 nm. In one embodiment, the second cleavage wavelengths are between about 200 nm and about 300 nm, about 220 nm and about 300 nm, about 240 nm and about 290 nm, and about 250 nm and about 280 nm. In some embodiments, the crosslinking wavelength is greater than the cleavage wavelength. For example, as explained earlier, the wavelengths for crosslinking various R functional groups may be greater than 350 nm (anthracene), 300 nm (cinnamic acid), 320 nm (coumarin), 270 nm (thymine), and / or 300 nm (stilbene), while the wavelengths for depolymerization may be less than 300 nm (anthracene), 260 nm (cinnamic acid), 280 nm (coumarin), 249 nm (thymine), and / or 280 nm (stilbene). [Examples]

[0057] The following examples are for illustrative purposes only and should not be construed as limiting the subject matter disclosed herein to the embodiments disclosed herein.

[0058] The compounds in the following examples are photoreactive liquid crystal compounds containing at least two reversible photodimerizable functional groups, which were synthesized and evaluated for their PDLC properties.

[0059] Example 1: Synthesis of liquid crystal compounds and / or monomers Generally, the compounds were prepared in a fume hood under an argon atmosphere (Airgas, Inc., San Marcos, California, USA). In addition, where degassing is mentioned, it can be done by blowing argon (Airgas, Inc.) into the compound or by other similar methods.

[0060] Synthesis of RM-1: 2-methyl-1,4-phenylenebis(4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate [ka]

[0061] 4-(3-chloropropoxy)methyl benzoate.Int-1 [ka]

[0062] To a solution of methyl 4-hydroxybenzoate (15.215 g, 0.1 mol) in acetone (230 ml), K2CO3 (molecular weight: 138.21) (20.73 g, 0.15 mol, 1.5 equivalents) was added, followed by the addition of 1-bromo-3-chloropropane (molecular weight: 157.44, density: 1.592 g / ml) (34.62 g, 21.74 ml, 0.11 mol, 1.1 equivalents). The mixture was stirred at 76°C for 8 hours, then at room temperature for 16 hours, and the precipitate was filtered. The filtrate was concentrated to obtain a pale yellowish-green, transparent oily substance (22.5 g, 0.098 mmol) (yield 98%). Product Int-1 was used in the next step without further purification. 1 H NMR (400MHz, chloroform-d) δ8.09~7.87(m, 2H), 7.00~6.84(m, 2H), 4.18(t, J=5.9Hz, 2H), 3.89(s, 3H), 3.75(t, J=6.2Hz, 2H), 2.26(p, J=6.1Hz, 2H). LCMS(APCI-), formula: C 11 H 13 Calculated value (M-) for ClO3: 228.6; Measured value: 228.

[0063] 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)methyl benzoate.Int-2 [ka]

[0064] A mixture of Int-1 (2.285 g, 10.0 mmol), 7-hydroxycoumarin (2.21 g, 13.36 mmol, 1.36 equivalents), anhydrous potassium carbonate (2.75 g, 19.895 mmol, 1.98 equivalents), and anhydrous DMF (20 ml) was stirred at 90°C for 16 hours under an argon atmosphere. The cooled mixture was added to water (100 ml), the precipitate was filtered, washed with water (2 × 50 ml) and methanol (50 mL × 2), and then dried in a vacuum oven to obtain 3.31 g of off-white solid methyl 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate (yield 93.4%). The product Int-2 was stored in an amber vial. 1 H NMR (400MHz, chloroform-d) δ8.06~7.92(m, 2H), 7.63(d, J=9.5Hz, 1H), 7.42~7.33(m, 1H), 6.98~6.90(m, 2H), 6.85(d, J=7.6 Hz, 2H), 6.26(d, J=9.5Hz, 1H), 4.23(td, J=6.0, 1.5Hz, 4H), 3.88(s, 3H), 2.33(p, J=6.0Hz, 2H). LCMS(APCI-), formula: C 20 H 18 Calculated value (M-) for O6:354.36; Measured value: 354.

[0065] 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoic acid.Int-3 [ka]

[0066] A solution of 4N NaOH in H2O (4 mL, 16 mmol, 3.2 equivalents) was added to a mixture of 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)methyl benzoate Int-2 (1.7718 g, 5.0 mmol) and THF (25 mL) and MeOH (4 mL). The resulting mixture was stirred at 53°C for 3 hours. The reaction was monitored by TLC and LC-MS. Once the conversion was complete, the reaction mixture was poured into ice water (100 mL) and 100 mL of EA was added. The aqueous layer was cooled to 0°C, acidified with 6N hydrochloric acid (4 mL), diluted with water (100 mL), the white solid was filtered, washed with water, and then dried in a vacuum oven to obtain 1.701 g of Int-3 as an off-white solid (quantitative yield). 1 H NMR (400MHz, DMSO-d6) δ12.58(s, 1H), 7.99(d, J=9.5Hz, 1H), 7.91~7.85(m, 2H), 7.63(d, J=8.6Hz, 1H), 7.04(dd, J=9.3, 2.4Hz, 3H ), 6.98 (dd, J=8.6, 2.4Hz, 1H), 6.29 (d, J=9.5Hz, 1H), 4.24 (dt, J=13.8, 6.2Hz, 4H), 2.23 (p, J=6.2Hz, 2H). LCMS(APCI-), formula: C 19 H 16 Calculated value for O6 (M-): 340.33; Measured value: 340.

[0067] 2-Methyl-1,4-phenylenebis(4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate)RM-1 [ka]

[0068] A solution of Int-3 (0.628 g, 1.846 mmol), methylhydroquinone (0.114 g, 0.923 mmol), EDC (0.389 g, 2.031 mmol), and DMAP (33.8 mg, 0.277 mmol) in 10.0 mL of anhydrous THF + 5 mL of anhydrous DCM + 5 mL of Me2CO was stirred at room temperature under an argon atmosphere for 48 hours. LC-MS showed that the desired diester product was present in over 60% of the solution and the monoester product in 10% of the solution. An additional 25 mg of 1643-49 and 11 mg of EDC were added, and the mixture was stirred overnight.

[0069] The following day, the mixture was poured into a solution of NH4Cl (0.3 g in 20 mL of water) and extracted twice with CH2Cl2. The combined organic layer was washed with water, dried over MgSO4, filtered, and evaporated under reduced pressure to obtain 660 mg of crude product as an off-white solid after washing with MeOH. The crude product was purified with 80 g of SiO2 and 2.5% EA in DCM as the eluent to obtain 319 mg of colorless solid RM-1 (yield 45%). 1 1H NMR (400MHz, TCE-d8) δ8.15~8.08(m, 2H), 8.08~8.00(m, 2H), 7.59(d, J=9.5Hz, 2H), 7.33(d, J=8. 6Hz, 2H), 7.10(d, J=8.7Hz, 1H), 7.06(d, J=2.7Hz, 1H), 7.01(dd, J=8.6, 2.8H z, 1H), 6.98~6.91(m, 4H), 6.81(dd, J=8.6, 2.4Hz, 2H), 6.77(d, J=2.4Hz, 2H ), 6.16(d, J=9.5Hz, 2H), 4.25~4.11(m, 8H), 2.35~2.22(m, 4H), 2.15(s, 3H). LCMS(APCI-), formula: C 45 H 36 O 12 Calculated value (M-): 768.77; Measured value: 768.

[0070] RM-2: 2-methyl-1,4-phenylenebis(4-(3-(anthracene-9-yloxy)propoxy)benzoate) [ka]

[0071] 4-[3-(anthracene-9-yloxy)propoxy]benzoic acid.Int-4 [ka]

[0072] Step 1: A mixture of methyl Int-1 (4.57 g, 20.0 mmol), anthrone (3.885 g, 20.0 mmol, 1 equivalent), anhydrous potassium carbonate (5.52 g, 40.0 mmol, 2 equivalents), and anhydrous DMF (40 ml) was stirred at 85°C for 16 hours under an argon atmosphere. The cooled mixture was added to water (350 ml), acidified with 4N HCl, extracted into EA (2 × 350 mL), the organic layers were combined, washed with water (2 × 100 ml), and then concentrated to dryness. The crude yellow solid was used in the next step without further purification to obtain 7.5 g (yield 97%). The product was stored in an amber vial.

[0073] Step 2: A solution of 4N NaOH (2 ml, 8 mmol) in H2O (10 mL, 40 mmol) was added to the mixture from the above step (5.28 g, 20.0 mmol) in THF (75 mL) and methanol (25 mL), and the resulting mixture was stirred at 53°C for 3 hours. The reaction was monitored by TLC and LC-MS. Once the conversion was complete, the reaction mixture was poured into ice water (100 mL) and 100 mL of EA was added. The aqueous layer was cooled to 0°C, acidified with 6N HCl (10 mL), and diluted with water (100 mL). The white solid was filtered, washed with water and MeOH, and then dried in a vacuum oven to obtain 2.887 g of Int-4 as an off-white solid (total yield of 38% in the two steps). 1H NMR (400MHz, TCE-d8)) δ8.16(s, 1H), 8.13(d, J=8.8Hz, 2H), 8.03(d, J=8.6Hz, 2H), 7.92(d, J=8.5Hz, 2H), 7.41~7.36(m, 2H), 7.3 5~7.29(m, 2H), 7.02(d, J=8.7Hz, 2H), 4.45(t, J=5.9Hz, 2H), 4.34(t, J=6.0Hz, 2H), 2.46(t, J=6.0Hz, 2H). LCMS(APCI-), formula: C 24 H 20 Calculated value for O4 (M-): 372.4; Measured value: 372.

[0074] 2-Methyl-1,4-phenylenebis(4-(3-(anthracene-9-yloxy)propoxy)benzoate)RM-2: [ka]

[0075] A solution of Int-4 (2.188 g, 5.876 mmol, 2.06 equivalents), methylhydroquinone (0.354 g, 2.851 mmol, 1 equivalent), EDC (1.238 g, 6.463 mmol, 2.26 equivalents), and DMAP (107.6 mg, 0.881 mmol, 0.309 equivalents) was stirred at room temperature under an argon atmosphere for 48 hours in 50.0 mL of anhydrous THF and 30 mL of anhydrous DCM. LC-MS showed that the desired diester product was over 60% and the monoester product was 10%. Additionally, 1643-49 (148.5 mg, 0.436 mmol), EDC (91.9 mg, 0.479 mmol), and DMAP (2.71 mg, 0.022 mmol) were added, and the resulting mixture was stirred overnight. The following day, the mixture was poured into a solution of NH4Cl (0.9 g in 60 mL of water), extracted twice with CH2Cl2 (2 × 250 ml), the combined organic layer was washed with water, dried over MgSO4, filtered, evaporated under reduced pressure, and after washing with MeOH, 2.02 g of off-white crude product was obtained. The crude product was purified with 80 g of SiO2 and 2.5% EA in DCM as the eluent to obtain 0.83 g of RM-2 as a colorless solid (yield 35%). 1 H NMR (400MHz, TCE-d8) δ8.16(dt, J=8.9, 5.2Hz, 10H), 7.93(d, J=8.3Hz, 4H), 7.40(t, J=7.0Hz, 4H), 7.36(dt, J=8.3, 5.1Hz, 4H), 7.15(d, J=8.7 Hz, 1H), 7.08(qd, J=8.7, 7.2, 2.8Hz, 6H), 4.49(t, J=6.0Hz, 4H), 4.36(t, J=6.0Hz, 4H), 2.55~2.43(m, 4H), 2.20(s, 3H). LCMS(APCI-), formula: C 55 H 44 Calculated value for O8 (M-): 832.95; Measured value: 832.

[0076] Synthesis of RM-3: 2-methyl-1,4-phenylenebis(4-(3-(4-((E)-3-butoxy-3-oxopropa-1-en-1-yl)phenoxy)propoxy)benzoate)(1643-59) [ka]

[0077] 4-(3-(4-iodophenoxy)propoxy)benzoic acid.Int-6 [ka]

[0078] Step 1: A mixture of Int-1 (2.285 g, 10.0 mmol, 1 equivalent), 4-iodophenol (2.972 g, 13.51 mmol, 1.31 equivalents), anhydrous potassium carbonate (2.75 g, 19.895 mmol, 1.99 equivalents), and anhydrous DMF (20 ml) was stirred at 90°C for 4 hours under an argon atmosphere. The solid was filtered, and the crude solid product 4-(3-(4-iodophenoxy)propoxy)methyl benzoate was washed with hexane and dried in a vacuum oven at 65°C for 3 hours to obtain 3.8173 g of off-white solid 4-(3-(4-iodophenoxy)propoxy)methyl benzoate (yield 92.6%). 1 H NMR (400MHz, chloroform-d) δ8.01~7.96(m, 2H), 7.57~7.53(m, 2H), 6.94~6.90(m, 2H), 6.71~6.66(m, 2H), 4 .20(t, J=6.1Hz, 2H), 4.12(t, J=6.0Hz, 2H), 3.88(s, 3H), 2.27(p, J=6.1Hz, 2H).

[0079] Step 2: A solution of 4N NaOH in H2O (7.4 mL, 29.63 mmol, 3.2 equivalents) was added to a mixture of the product from the above step (3.8173 g, 9.26 mmol) in THF (50 mL) and methanol (8 mL). The resulting mixture was stirred at 53°C for 3 hours. The reaction was monitored by TLC, and once complete, it was cooled to 0°C, acidified with 6N HCl (approximately 4 mL), and then extracted with 100 mL of EA. The organic layer was separated, dried over MgSO4, concentrated, and the white solid was washed with water, filtered, and then dried in a vacuum oven to obtain 3.68 g of colorless solid Int-6 (quantitative yield). LCMS(APCI-), formula: C 16 H 15 Calculated value for IO4 (M-): 398.2; Measured value: 398.

[0080] 4-((4-(3-((4-iodocyclohexa-1,3-dien-1-yl)oxy)propoxy)benzoyl)oxy)-2-methylphenyl 4-(3-(4-iodophenoxy)propoxy)benzoate.Int-7 [ka]

[0081] A mixture of Int-6 (2.339 g, 5.876 mmol, 2.06 equivalents) and EDC (1.238 g, 6.463 mmol, 2.26 equivalents) in 50.0 mL of anhydrous DCM was stirred at room temperature under an argon atmosphere for 10 minutes. The mixture became a pale yellow solution. A mixture of methylhydroquinone (0.354 g, 2.851 mmol, 1 equivalent) in 10.0 mL of anhydrous THF, EDC, and DMAP (107.6 mg, 0.881 mmol, 0.309 equivalents) was added at room temperature via syringe and needle. The resulting mixture was stirred under an argon atmosphere for 24 hours. LC-MS showed that the desired diester product was present in over 60% of the mixture, and the monoester product in 10% of the mixture. Additionally, 1643-49 (148.5 mg, 0.436 mmol), EDC (91.9 mg, 0.479 mmol), and DMAP (2.71 mg, 0.022 mmol) were added, and the resulting mixture was stirred overnight. The next day, the mixture was poured into NH4Cl solution (0.9 g in 60 mL of water), stirred for 10 minutes, and a white solid was collected by filtration. The filtrate was extracted twice with CHCl3 (150 ml). The crude solid from filtration and the filtrate were combined and purified by 80 g SiO2 column chromatography, with 2.5% EA in DCM as the eluent, yielding 3.5 g of colorless solid Int-7 (yield 85%). 1 H NMR (400MHz, chloroform-d) δ8.23~8.04(m, 4H), 7.60~7.47(m, 4H), 7.17(d, J=8.6Hz, 1H), 7.13(d, J=2.5Hz, 1H), 7.08(dd, J=8.6, 2.7Hz, 1H), 7.04~ 6.92(m, 4H), 6.76~6.65(m, 4H), 4.25(td, J=6.1, 2.2Hz, 4H), 4.15(t, J=6.0Hz, 4H), 2.30(h, J=5.7Hz, 4H), 2.24(s, 3H). LCMS(APCI-), formula: C 39 H 36 Calculated value (M-) for I2O8: 884.5; Measured value: 884.

[0082] 2-Methyl-1,4-phenylenebis(4-(3-(4-((E)-3-butoxy-3-oxopropa-1-en-1-yl)phenoxy)propoxy)benzoate)(1643-59) [ka]

[0083] A mixture of 2-methyl-1,4-phenylenebis(4-(3-(4-iodophenoxy)propoxy)benzoate) (886 mg, 1 mmol, 1 equivalent), n-butyl acrylate (769 mg, 6 mmol, 6 equivalents), Et3N (506 mg, 0.696 mL, 5 mmol, 5 equivalents), Pd(OAc)2 (6.735 mg, 0.003 mmol, 0.03 equivalents), and PPh3 (15.73 mg, 0.06 mmol, 0.06 equivalents) was placed in a sealed vial. The slurry mixture was stirred and heated in degassed 1,4-dioxane (2 mL). When the temperature reached 65°C, the reaction mixture became a clear brown solution, and the mixture was then stirred at 110°C for 16 hours under an argon atmosphere. After cooling to room temperature, the mixture was rapidly cooled with 1 mL of 1 M aqueous HCl solution and extracted to CHCl3 (3 × 10 mL). The organic phase was washed with water, dried over Na2SO4, filtered, and concentrated under vacuum to obtain the crude product. Purification was performed by SiO2 column chromatography using Hex:DCM (1:1) elution to obtain 0.454 g of colorless solid RM-3 (yield 55%). 1H NMR (400MHz, chloroform-d) δ8.21~8.10(m, 4H), 7.63(d, J=15.9Hz, 2H), 7.51~7.42(m, 4H), 7.17(d, J=8.7Hz, 1H), 7 .13(d, J=2.7Hz, 1H), 7.08(dd, J=8.7, 2.8Hz, 1H), 7.04~6.96(m, 4H), 6.95~6.88(m, 4H) , 6.31(d, J=15.9Hz, 2H), 4.26(td, J=6.0, 2.3Hz, 4H), 4.21(dt, J=8.9, 6.3Hz, 8H), 2.33 (p, J=6.0Hz, 4H), 1.68(dq, J=8.6, 6.8Hz, 4H), 1.49~1.38(m, 4H), 0.96(t, J=7.4Hz, 6H). LCMS(APCI-), formula: C 53 H 56 O 12 Calculated value (M-): 885.02; Measured value: 885.

[0084] RM-4: 1,3,5-Tris(3-(anthracene-9-yloxy)propoxy)benzene) [ka]

[0085] 9-(3-chloropropoxy)anthracene.Int-8 [ka]

[0086] To a solution of anthrone (7.768 g, 40 mmol) in 50.0 mL of acetone, 1-bromo-3-chloropropane (12.58 g, 80 mmol) was added under a nitrogen atmosphere at ambient temperature, followed by the addition of K2CO3 (molecular weight: 138.21) (8.312 g, 60.0 mmol). The mixture was stirred at 75°C for 8 hours, then cooled to room temperature and filtered. The filtrate was concentrated to obtain 14.69 g of a dark yellow semi-solid, which was washed with hexane to obtain 11.7 g of a pale yellow solid (yield 48%). The product Int-8 was used in the next step without further purification. 1 H NMR (400MHz, chloroform-d) δ8.30~8.23(m, 2H), 8.21(s, 1H), 8.01~7.95(m, 2H), 7.46(tt, J=6.6, 5.0H z, 4H), 4.33(t, J=5.9Hz, 2H), 4.03(t, J=6.3Hz, 2H), 2.47(p, J=6.1Hz, 2H). LCMS(APCI-), formula: C 17 H 15 Calculated value for ClO (M-): 270.76; Measured value: 270.

[0087] Synthesis of 1,3,5-tris(3-(anthracene-9-yloxy)propoxy)benzene RM-4 [ka]

[0088] A mixture of Int-8 (0.894 g, 3.3 mmol, 3.3 equivalents), phloroglucinol (0.126 g, 1.0 mmol, 1 equivalent), anhydrous potassium carbonate (0.552 g, 4.0 mmol, 4 equivalents), and anhydrous DMF (4 ml) was stirred at 85°C for 16 hours under an argon atmosphere. The cooled mixture was added to water (4 ml), acidified with 4N HCl, extracted to EA (2 × 35 mL), the organic layers were combined, washed with water (2 × 10 ml), and then concentrated to dryness. The crude yellow solid was purified by SiO2 column chromatography using hexane:EA (9:1) as the eluent to obtain 265 mg of colorless solid RM-4 (yield 32%). The product was stored in an amber vial. 1 H NMR (400MHz, chloroform-d) δ8.32~8.22(m, 6H), 8.20(s, 3H), 8.00~7.90(m, 6H), 7.44~7.33(m, 12H), 6.4 0(s, 3H), 4.47(t, J=5.9Hz, 6H), 4.42(t, J=6.1Hz, 6H), 2.52(p, J=6.0Hz, 6H). LCMS(APCI-), formula: C 57 H 48Calculated value for O6 (M-): 829.01; Measured value: 829.

[0089] Synthesis of RM-5:1,3,5-Tris(3-(anthracene-9-yloxy)propoxy)benzene)(1643-79) [ka]

[0090] 9-(6-bromohexyl)oxy)anthracene)Int-9 [ka]

[0091] To a stirred solution of anthrone (7.768 g, 40.0 mmol) in 50.0 mL of acetone, 1,6-dibromohexane (39.02 g, 24.24 mL, 160.0 mmol, 4 equivalents) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (8.292 g, 60.0 mmol). The mixture was then heated at 50°C for 8 hours. The reaction was monitored by TLC until all traces of the starting material (SM) anthrone were completely removed. The reaction mixture was concentrated under reduced pressure to remove the solvent. 150 mL of water was added to the residue, and the mixture was stirred at room temperature for 30 minutes. The precipitate was filtered and washed with 100 mL of hexane to obtain a pale brown crude product, which was purified by SiO2 column chromatography using eluent Hex:EA (9:1) to obtain 6.4 g of Int-9 (45% yield). 1 H NMR (400MHz, chloroform-d) δ8.32~8.25(m, 2H), 8.22(s, 1H), 8.05~7.95(m, 2H), 7.50~7.40(m, 4H), 4.21(t, J=6.6Hz, 2H), 3.48(t, J=6 .7Hz, 2H), 2.07(dt, J=14.6, 6.7Hz, 2H), 1.98(dt, J=14.3, 6.9Hz, 2H), 1.77~1.69(m, 2H), 1.66~1.58(m, 2H)

[0092] Synthesis of 9,9'-((((5-((7-(anthracene-9-yloxy)heptyl)oxy)-1,3-phenylene)bis(oxy))bis(hexane-6,1-diyl))bis(oxy))dianthrasene [ka]

[0093] Step 1: A mixture of Int-9 (2.358 g, 6.6 mmol, 3.3 equivalents), phloroglucinol (0.252 g, 2.0 mmol, 1 equivalent), anhydrous potassium carbonate (0.552 g, 4.0 mmol, 4 equivalents), and anhydrous DMF (4 ml) was stirred at 85°C for 16 hours under an argon atmosphere. The cooled mixture was added to water (4 ml), acidified with 4N HCl, and extracted to EA (2 × 35 mL). The organic layers were combined, washed with water (2 × 10 ml), and then concentrated to dryness. The crude brown, viscous solid was purified by SiO2 column chromatography using hexane:EA (9:1) as the eluent to obtain 286 mg of viscous solid RM-5 (yield 15%). 1 ¹H NMR (400MHz, chloroform-d): δ 8.36~8.24 (m, 6H), 8.20 (s, 3H), 8.05~7.88 (m, 6H), 7.57~7.39 (m, 12H), 6.11 (s, 3H), 4.20 (t, J=6.6Hz, 6H), 3.96 (t, J=6.4Hz, 6H), 2.11~2.03 (m, 6H), 1.86 (p, J=6.5Hz, 6H), 1.73 (q, J=7.7, 7.1Hz, 6H), 1.62 (q, J=8.0Hz, 6H). LCMS(APCI-), formula: C 67 H 68 Calculated value for O6 (M-): 969.28; Measured value: 969.

[0094] RM-6: 1,3,5-Tris(3-(Anthracene-9-yloxy)propoxy)benzene) [ka]

[0095] 2-Methyl-1,4-phenylenebis(4-acetoxybenzoate)Int-11 [ka]

[0096] 13.888 ml (0.194 mol) of thionyl chloride was added dropwise to 25.0 g (0.138 mol) of 4-acetoxybenzoic acid, which had been stirred in a 100 ml single-necked round-bottom flask. The resulting mixture was gently refluxed for 8 hours. The initial heterogeneous lumps were homogenized to obtain a yellowish liquid. Excess thionyl chloride was removed using a rotary evaporator at a water bath temperature of 26°C. Toluene (15 mL) was added to the residue, and the resulting mixture was concentrated using a rotary evaporator at a water bath temperature of 45°C.

[0097] The crude acid chloride was purified by double distillation under reduced pressure to yield 27 g of pale yellow liquid 4-acetoxybenzoyl chloride (Int-10), which later became a colorless solid (99% yield). 1 ¹H NMR (400 MHz, chloroform-d) δ 2.1 [3H, s], 7.1 [2H, d], and 8.0 [2H, d].

[0098] Step 2: A mixture of 2-methylhydroquinone (4.96 g, 0.04 mol) and 25 ml of pyridine (0.3 mol) was added to a mixture of 23.82 g of 4-acetoxybenzoyl chloride (0.12 mol) in 300 ml of dry 1,2-dichloroethane. The acid chloride solution was added to the 2-methylhydroquinone solution. The reaction mixture was stirred at room temperature for 48 hours under a nitrogen blanket. The reaction mixture was washed in the following order: 5% sodium carbonate solution, 5% hydrochloric acid, and distilled water. The 1,2-dichloroethane layer was evaporated to dryness using a rotary evaporator. The crude product was recrystallized with chloroform / petroleum ether (60:80). The product was filtered and dried in a vacuum oven at 80°C for 4 hours to obtain 15.24 g of light brown solid Int-11 (yield 85%). 1¹H NMR (400 MHz, chloroform-d): δ 2.2 (3H, s), 2.3 (6H, s), 7.4 (8H, d), and 8.4 (3H, d). LCMS(APCI-), formula: C 25 H 20 Calculated value for O8 (M-): 448.43; Measured value: 448.

[0099] 2-Methyl-1,4-phenylenebis(4-hydroxybenzoate).Int-12 [ka]

[0100] A solution of NH4OAc (9.68 g, 0.125 mol, 4 equivalents) in 100 mL of H2O was added to a mixture of 2-methyl-1,4-phenylenebis(4-acetoxybenzoate) (14.1 g, 0.0314 mol, 1 equivalent), 250 mL of MeOH, and 250 mL of THF, which had been stirred in a 1 L one-necked round-bottom flask. The resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was yellowish. The solvent was removed under reduced pressure. The residue was washed with H2O and dried in a vacuum oven to obtain 11.0 g of a light brown solid. The product Int-11 was used in the next step without further purification (yield 99%). 1 H NMR (400MHz, DMSO-d6) δ10.54(s, 2H), 8.02(d, J=8.8Hz, 2H), 7.99(d, J=8.8Hz, 2H), 7.24(d, J=5.9Hz, 1H), 7.2 3(s, 1H), 7.16~7.11(m, 1H), 6.95(d, J=4.0Hz, 2H), 6.93(d, J=3.9Hz, 2H), 2.16(s, 3H). LCMS(APCI-), formula: C 21 H 16 Calculated value for O6 (M-): 364.35; Measured value: 364.

[0101] 1,3,5-Tris(3-(anthracene-9-yloxy)propoxy)benzene)RM-6 [ka]

[0102] To a stirred solution of 2-methyl-1,4-phenylenebis(4-hydroxybenzoate) (1.45 g, 4.0 mmol) in 4.0 mL of anhydrous DMF, 9-((6-bromohexyl)oxy)anthracene (3.572 g, 10.0 mmol) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (1.658 g, 12.0 mmol). The mixture was then heated at 85 °C for 8 hours. LC-MS showed that, in addition to the dicoupling product, a monocoupling product and the starting material remained. The reaction mixture was then stirred at 78 °C for 6 hours. 500 mL of CHCl3 was added, followed by 100 mL of cold water (ice + water) to the RX mixture at room temperature. The resulting mixture was stirred at room temperature for 10 minutes. The organic layer was washed with 50 mL of water, separated, dried over MgSO4, filtered, and concentrated to dryness. The crude product was purified by SiO2 column chromatography, eluted with DCM alone, and then eluted with DCM:EtAcO(95:5). 3.0 g of a pale brown solid was obtained, which was recrystallized with methanol to yield the colorless solid product RM-6. 1 H NMR (400MHz, chloroform-d) δ8.29(ddd, J=6.6, 2.4, 1.4Hz, 4H), 8.22(s, 2H), 8.19~8.10(m, 4H), 8.06~7.94(m, 4H), 7.5 4~7.41(m, 8H), 7.18(d, J=8.7Hz, 1H), 7.13(d, J=2.7Hz, 1H), 7.08(dd, J=8.6, 2.7Hz, 1H), 7 .03~6.97(m, 4H), 4.23(t, J=6.6Hz, 4H), 4.12(td, J=6.5, 2.1Hz, 4H), 2.25(s, 3H), 2.12(q, J=7.7, 7.2Hz, 4H), 1.95(p, J=6.7Hz, 4H), 1.79(t, J=8.1Hz, 3H), 1.68(p, J=7.4, 6.9Hz, 4H). LCMS(APCI-), formula: C 61 H 56 Calculated value for O8 (M-): 917.11; Measured value: 917.

[0103] RM-7: 1,3,5-Tris((5-(anthracen-9-yloxy)pentyl)oxy)benzene

Chem.

[0104] 9-((5-Bromopentyl)oxy)anthracene. Int-13

Chem.

[0105] A stirred solution of anthrone (7.768 g, 40.0 mmol) in 50.0 mL of acetone was added with 1,3-dibromopentane (36.79 g, 21.9 mL, 160.0 mmol, 4 eq) at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (8.292 g, 60.0 mmol). Then, the mixture was heated at 50 °C for 8 h. The reaction was monitored by TLC until anthrone completely disappeared. The reaction mixture was cooled to room temperature, the solid was filtered off and washed with 100 mL of acetone. The filtrates were combined and concentrated under reduced pressure to give a red-orange residue, which was loaded onto a 220 g SiO2 column and eluted with hexane and then Hex:DCM (95:5) to give 4.5 g of an off-white solid Int-13, which was dried in a vacuum oven and used in the next step without further purification (yield 32%). 1 1H NMR (400 MHz, chloroform-d) δ 8.33~8.24 (m, 2H), 8.22 (s, 1H), 8.06~7.93 (m, 2H), 7.54~7.41 (m, 4H), 4.22 (t, J = 6.5 Hz, 2H), 3.52 (t, J = 6.7 Hz, 2H), 2.07 (ddt, J = 14.9, 12.4, 6.8 Hz, 4H), 1.91~1.82 (m, 2H). LCMS (APCI-), formula: C 19 1H 19 Calculated value (M-) for C19H19BrO: 343.26; Measured value: 343.

[0106] 1,3,5-Tris((5-(anthracen-9-yloxy)pentyl)oxy)benzene RM-7

Chem.

[0107] A mixture of Int-13 (1.132 g, 3.3 mmol, 3.3 eq), phloroglucinol (0.126 g, 1.0 mmol, 1 eq), potassium carbonate anhydrous (0.552 g, 4.0 mmol, 4 eq), and anhydrous DMF (25 mL) was stirred at 85 °C for 6 h under an argon atmosphere. The cooled mixture was filtered, the filtrate was concentrated, and the solid crude product was purified by SiO2 column chromatography using hexane:EA (9:1) as the eluent to obtain 98 mg of colorless solid RM-7 (yield 10%). 1 H NMR (400 MHz, chloroform-d) δ 8.34~8.24 (m, 6H), 8.20 (s, 3H), 8.03~7.92 (m, 6H), 7.55~7.37 (m, 12H), 6.16 (s, 3H), 4.22 (t, J = 6.5 Hz, 6H), 4.03 (t, J = 6.2 Hz, 6H), 2.12 (p, J = 6.7 Hz, 6H), 1.94 (q, J = 6.7, 6.0 Hz, 6H), 1.87 (q, J = 8.7, 8.2 Hz, 6H). LCMS (APCI-), formula: C 63 H 60 Calculated value (M-) for C48H54O6: 913.17; Measured value: 913.

[0108] RM-8: Synthesis of 1,3,5-Tris((5-(anthracen-9-yloxy)pentyl)oxy)benzene

Chem.

[0109] To a stirred solution of 9-((5-bromopentyl)oxy)anthracene (0.765 g, 2.1 mmol) in 4.0 mL of anhydrous DMF, 1643-81 (1.586 g, 4.62 mmol, 2.2 equivalents) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (0.58 g, 4.2 mmol). The mixture was then heated at 85°C for 12 hours. LC-MS revealed the presence of a dicoupling product, as well as a monocoupling product and residual starting material. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrates were combined and concentrated at 50°C using a rotary evaporator. The residue was triturated with water to obtain 1.5 g of a light brown solid product, which was purified by SiO2 column chromatography (eluent Hex:EtAcO (9:1 → 4:1)) to obtain 0.42 g of colorless solid RM-8 (22% yield). 1 H NMR (400MHz, chloroform-d) δ8.35~8.26(m, 4H), 8.23(s, 2H), 8.21~8.10(m, 4H), 8.05~7.96(m, 4H), 7.56~ 7.42(m, 8H), 7.18(d, J=8.7Hz, 1H), 7.14(d, J=2.7Hz, 1H), 7.11~7.07(m, 1H), 7 .05~6.98(m, 4H), 4.26(t, J=6.5Hz, 4H), 4.17(td, J=6.2, 2.3Hz, 4H), 2.25(s, 3 H), 2.16(p, J=6.8Hz, 4H), 2.02(dd, J=13.9, 6.7Hz, 4H), 1.92(q, J=8.3Hz, 4H). LCMS(APCI-), formula: C 59 H 52 Calculated value for O8 (M-): 889.06; Measured value: 889.

[0110] Synthesis of RM-9:7,7',7''-(((benzene-1,3,5-triyltris(oxy))tris(pentan-5,1-diyl))tris(oxy))tris(2H-chromen-2-one) [ka]

[0111] 1,3,5-Tris((5-bromopentyl)oxy)benzene.Int-14 [ka]

[0112] To a stirred solution of phloroglucinol (2.522 g, 20.0 mmol) in 120.0 mL of acetonitrile, 1,5-dibromopentane (55.184 g, 240 mmol, 12 equivalents) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (33.168 g, 240.0 mmol). The mixture was then heated at 85°C for 16 hours. The reaction was monitored by TLC until all traces of the starting material, phloroglucinol, were removed. The reaction mixture was cooled to room temperature, the solid was filtered, and washed with 100 mL of acetone. The filtrates were combined and concentrated under reduced pressure to obtain a reddish-orange residue, which was packed onto a 220 g SiO2 column and eluted with hexane, then Hex:EA (9:1), to obtain 4.58 g of a colorless liquid Int-14. This compound was used in the next step without further purification (yield 40%). 1 ¹H NMR (400MHz, chloroform-d): δ 6.05 (s, 3H), 3.92 (t, J=6.3Hz, 6H), 3.44 (t, J=6.8Hz, 6H), 1.98~1.89 (m, 6H), 1.84~1.75 (m, 6H), 1.66~1.57 (m, 6H). LCMS(APCI-), formula: C 21 H 33 Calculated value (M-) for Br3O3: 573.2; Measured value: 573.

[0113] RM-9.7,7',7''-(((Benzene-1,3,5-triyltris(oxy))tris(pentan-5,1-diyl))tris(oxy))tris(2H-chromen-2-one) [ka]

[0114] A stirred solution of coumarin (973 mg, 6.0 mmol) in 12.0 mL of anhydrous DMF was added with 1643-85 (573.2 mg, 2 mmol, 1 equivalent) at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (1.658 g, 12 mmol). Subsequently, the mixture was heated at 85 °C for 6 hours. The reaction was monitored by TLC until the starting material coumarin was completely gone. The reaction mixture was cooled to room temperature, diluted with 50 mL of DMF, the solid was filtered off and washed with 100 mL of acetone. The filtrates were combined and concentrated under reduced pressure to give an orange-red residue, which was triturated with water (50 ml), and the light brown solid product was loaded onto an 80 g SiO2 column and eluted with DCM and then DCM:EA (4:1) to give 450 mg of a sticky colorless solid RM-9 (yield 27%). 1 1H NMR (400 MHz, chloroform-d) δ 7.63 (d, J = 9.5 Hz, 3H), 7.36 (d, J = 8.5 Hz, 3H), 6.87~6.81 (m, 3H), 6.82~6.77 (m, 3H), 6.25 (d, J = 9.5 Hz, 3H), 6.07 (s, 3H), 4.04 (t, J = 6.4 Hz, 6H), 3.95 (t, J = 6.3 Hz, 6H), 1.87 (tt, J = 14.5, 6.5 Hz, 13H), 1.72~1.60 (m, 7H). LCMS (APCI-), formula: C 48 H 48 O 12 Calculated value (M-) for: 816.9; Measured value: 816.

[0115] Synthesis of RM-10: 7,7’,7’’-(((benzene-1,3,5-triyltris(oxy))tris(hexane-6,1-diyl))tris(oxy))tris(2H-chromen-2-one)

Chemical Structure

[0116] 1,3,5-tris((6-bromohexyl)oxy)benzene. Int-15

Chemical Structure

[0117] To a stirred solution of phloroglucinol (1.261 g, 10.0 mmol) in 50.0 mL of acetone, 1,6-dibromohexane (29.276 g, 120 mmol, 12 equivalents) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (16.584 g, 120.0 mmol). The mixture was then heated at 50°C for 8 hours. The reaction was monitored by TLC until all traces of phloroglucinol remained. The reaction mixture was cooled to room temperature, the solid was filtered, washed with 100 mL of acetone, the filtrates were combined, and concentrated under reduced pressure to obtain a reddish-orange residue. This residue was packed onto a 220 g SiO2 column and eluted with hexane, then Hex:EA (9:1) to obtain 1.45 g of colorless liquid Int-15. This liquid was dried in a vacuum oven and used in the next step without further purification (yield 23%). 1 H NMR (400MHz, chloroform-d) δ6.05(s, 3H), 3.91(t, J=6.4Hz, 6H), 3.42(t, J=6.8Hz, 6H), 1.89(p, J=6.9Hz, 6H), 1.77(p, J=6.4Hz, 7H), 1.55~1.39(m, 12H). LCMS(APCI-), formula: C 24 H 39 Calculated value (M-) for Br3O3: 615.29; Measured value: 615.

[0118] RM-10.7,7',7''-(((Benzene-1,3,5-triyltris(oxy))tris(hexane-6,1-diyl))tris(oxy))tris(2H-chromen-2-one) [ka]

[0119] A stirred solution of coumarin (498.5 mg, 3.075 mmol, 4 eq) in 6.0 mL of anhydrous DMF was added Int-15 (473.4 mg, 0.768 mmol, 1 eq) at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (0.424 g, 3.072 mmol, 4 eq). The mixture was then heated at 75 °C for 16 h. The reaction was monitored by TLC until the starting material coumarin completely disappeared. The reaction mixture was cooled to room temperature and diluted with 10 mL of DMF. The solid was filtered, washed with 50 mL of acetone, the filtrates were combined and concentrated under reduced pressure to give an orange-red residue, which was triturated with water (50 ml). The light brown solid product was loaded onto an 80 g SiO2 column and eluted with DCM and then DCM:EA (4:1) to give 0.47 g of a colorless sticky solid RM-10 (yield 68%). 1 1H NMR (400 MHz, chloroform-d) δ 7.63 (d, J = 9.5 Hz, 3H), 7.36 (d, J = 8.5 Hz, 3H), 6.83 (dd, J = 8.5, 2.5 Hz, 3H), 6.80 (d, J = 2.4 Hz, 3H), 6.24 (d, J = 9.5 Hz, 3H), 6.06 (s, 3H), 4.02 (t, J = 6.4 Hz, 6H), 3.93 (t, J = 6.4 Hz, 6H), 1.82 (dt, J = 18.1, 6.6 Hz, 12H), 1.54 (t, J = 3.9 Hz, 12H). LCMS (APCI-), formula: C 51 1 54 1 12 Calculated for (M-): 858.98; Found: 858.

[0120] RM-11: 5-((3-((5-(Anthracen-9-yloxy)pentyl)oxy)benzoyl)oxy)-1,3-phenylene bis(4-((5-(anthracen-9-yloxy)pentyl)oxy)benzoate)

Chemical formula

[0121] Methyl 4-((5-bromopentyl)oxy)benzoate. Int-16 [ka]

[0122] To a stirred solution of methyl 4-hydroxybenzoate (4.108 g, 27.0 mmol) in 20.0 mL of dimethylformamide, 1,5-dibromopentane (24.833 g, 108 mmol) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (7.463 g, 54 mmol). The reaction mixture was stirred at 56 °C for 16 hours. After cooling to room temperature, the reaction mixture was filtered. The filtrate was concentrated, the residue was dissolved in DCM (250 mL), washed with 100 mL of cold water, dried over MgSO4, and concentrated. The crude product was purified by SiO2 column chromatography using hexane:EA (9:1) to obtain 7.3 g of colorless liquid Int-16 (yield 89%). 1 H NMR (400MHz, chloroform-d) δ7.98(d, J=8.9Hz, 2H), 6.89(d, J=8.9Hz, 2H), 4.02(t, J=6.3Hz, 2H), 3.88(s, 3H), 3.43(t, J=6.7Hz, 2H), 2.00~1.89(m, 2H), 1.87~1.78(m, 2H), 1.63(t, J=7.9Hz, 2H). LCMS(APCI-), formula: C 13 H 17 Calculated value (M-) for BrO3: 301.18; Measured value: 301.

[0123] 4-((5-(anthracene-9-yloxy)pentyl)oxy)methyl benzoate.Int-17 [ka]

[0124] Procedure 1: To a stirred solution of anthrone (1.9423 g, 10.0 mmol) in 10.0 mL of dimethylformamide, Int-16 (3.018 g, 10.0 mmol) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of potassium carbonate (2.764 g, 20 mmol). The reaction mixture was stirred at 85 °C for 16 hours. The reaction mixture was filtered. The insoluble material was washed with ethyl acetate. The filtrates were combined and concentrated. The residue was washed with 1.01 cold water and then with 1.01 heptane. The crude product was purified by silica gel column chromatography using hexane alone → hexane:DCM (1:1) to afford 3.02 g of a pale orange sticky liquid Int-17 (yield 72%). The product contained some starting material anthrone and was carried on to the next step without further purification. 1 1H NMR (400 MHz, chloroform-d) δ 8.32 - 8.24 (m, 2H), 8.22 (s, 1H), 8.10 - 8.03 (m, 2H), 8.03 - 7.95 (m, 2H), 7.52 - 7.41 (m, 4H), 6.97 (d, J = 9.0 Hz, 2H), 4.25 (t, J = 6.5 Hz, 2H), 4.14 (t, J = 6.3 Hz, 2H), 2.14 (dt, J = 14.1, 6.7 Hz, 2H), 2.05 - 1.85 (m, 5H). LCMS (APCI-), formula: C 27 H 26 O4 calculated value (M-): 414.5; found: 414.

[0125] Procedure 2: A solution of 4N NaOH in H2O (7.4 mL, 29.63 mmol, 3.2 eq) was added to a mixture of the product from the above step (3.0 g, 7.2 mmol) in THF (50 mL) and methanol (8 mL). The resulting mixture was stirred at 53 °C for 3 hours. The reaction was monitored by TLC. Upon completion, it was cooled to 0 °C, acidified with 6N HCl (ca. 4 mL), and then extracted with 100 mL of EA. The organic layer was separated, dried over MgSO4, and concentrated. The white solid was washed with water, filtered, and then dried in a vacuum oven to afford 2.68 g of a colorless solid Int-17 (yield 95%). 1H NMR (400MHz, chloroform-d) δ8.33~8.25(m, 2H), 8.22(s, 1H), 8.09~8.02(m, 2H), 8.02~7.95(m, 2H), 7.52~7.41(m, 4H), 7.01~6.93 (m, 2H), 4.25(t, J=6.5Hz, 2H), 4.14(t, J=6.2Hz, 2H), 2.20~2.09(m, 2H), 2.01(dt, J=13.4, 6.6Hz, 2H) LCMS(APCI-), formula: C 26 H 24 Calculated value for O4 (M-): 400.47; Measured value: 400.

[0126] Benzene-1,3,5-triyltris(4-((5-(anthracene-9-yloxy)pentyl)oxy)benzoate.RM-11 [ka]

[0127] A mixture of RM-17 (1 g, 2.49 mmol, 4 equivalents), DMAP-pTSA (1.467 g, 4.99 mmol, 8 equivalents), and EDC·HCl (1.431 mg, 7.47 mmol, 12 equivalents) was mixed with DCE:CHCl3 (1:1) (45 mL), followed by the addition of phloroglucinol (0.0785 g, 0.622 mmol, 1 equivalent). The resulting mixture was stirred under an argon atmosphere at room temperature for 16 hours. Further additions of 1643-92 (324 mg) and EDC·HCl (298 mg) were added. The resulting mixture was stirred for a further 3 hours. H2O (10 mL) was added, followed by stirring for another 15 minutes. The organic layer was separated, concentrated to 20 ml, packed into a 40 g SiO2 column, and eluted using Hex-DCM (7 / 3), and then gradually transitioned to DCM alone. The pure fraction was collected, concentrated, and dried in a vacuum oven to obtain 470 mg of colorless solid RM-11 (yield 37%). 1H NMR (400MHz, chloroform-d) δ8.34~8.24(m, 6H), 8.22(s, 3H), 8.14(d, J=8.9Hz, 6H), 8.04~7.94(m, 6H), 7.54~7.40(m, 12H), 7.13(s, 3H), 7.00(d, J=9 .0Hz, 6H), 4.25(t, J=6.5Hz, 6H), 4.16(t, J=6.3Hz, 6H), 2.15(p, J=6.7Hz, 6H), 2.02(p, J=6.4Hz, 6H), 1.95~1.85(m, 6H). LCMS(APCI-), formula: C 84 H 72 O 12 Calculated value (M-): 1273.49; Measured value: 1273.

[0128] RM-12: 1,3,5-Tris(4-(anthracene-9-yloxy)butoxy)benzene [ka]

[0129] 9-(4-bromobutoxy)anthracene.Int-18 [ka]

[0130] To a stirred solution of anthrone (4.0 g, 20.6 mmol) in 20.0 mL of anhydrous DMF, potassium carbonate (5.694 g, 41.2 mmol) was added at ambient temperature under a nitrogen atmosphere, followed by the addition of 1,4-dibromobutane (18 g, 83.36 mmol). The mixture was then heated at 65 °C for 8 hours. The reaction was monitored by TLC until all anthrone remained and the reaction mixture turned pale beige. The reaction mixture was cooled to room temperature, the solid was filtered, and washed with 100 mL of acetone. The filtrates were combined and concentrated under reduced pressure to obtain an orange product, which was packed into a 220 g SiO2 column and eluted with hexane, then Hex:DCM (95:5) to obtain 3.5 g of white solid Int-18, which was dried in a vacuum oven and used in the next step without further purification (yield 51%). 1 ¹H NMR (400MHz, chloroform-d): δ 8.29~8.25 (m, 1H), 8.24 (dt, J=2.8, 1.0Hz, 1H), 8.22 (s, 1H), 8.00 (tt, J=2.2, 1.4Hz, 1H), 7.98 (dd, J=1.9, 1.2Hz, 1H), 7.51~7.41 (m, 4H), 4.23 (t, J=6.2Hz, 2H), 3.61 (t, J=6.6Hz, 2H), 2.39~2.26 (m, 2H), 2.26~2.15 (m, 2H). LCMS(APCI-), formula: C 18 H 17 Calculated value (M-) for BrO: 329.24; Measured value: 329.

[0131] 1,3,5-Tris(4-(anthracene-9-yloxy)butoxy)benzene.RM-12 [ka]

[0132] A mixture of Int-18 (2.43 g, 7.38 mmol, 3.69 equivalents), phloroglucinol (0.250 g, 2.0 mmol, 1 equivalent), anhydrous potassium carbonate (1.104 g, 8.0 mmol, 4 equivalents), and anhydrous DMF (25 ml) was stirred at 85°C for 16 hours under an argon atmosphere. The cooled mixture was filtered, the filtrate was concentrated, the crude solid product was washed with water, and then packed onto an 80 g SiO2 column. Elution was performed using hexane:DCM → DCM alone as the eluent. Fractions 8-10 were recovered and concentrated to obtain 1.2 g of a rubbery solid (yield 68%). Some impurities were indicated by NMR. The above impurity product was packed into a second column of 80 g SiO2 and eluted with Hex:EA (100% → 20%) to obtain a solid containing off-white, which was then triturated with ethyl acetate to obtain 0.85 g of colorless solid RM-12 (yield 48%). 1 ¹H NMR (400MHz, chloroform-d): δ 8.33~8.25 (m, 6H), 8.21 (s, 3H), 8.03~7.94 (m, 6H), 7.51~7.40 (m, 13H), 6.19 (s, 3H), 4.31~4.24 (m, 6H), 4.15~4.08 (m, 6H), 2.32~2.16 (m, 12H). LCMS(APCI-), formula: C 60 H 54 Calculated value for O6 (M-): 871.09; Measured value: 871.

[0133] RM-13: Benzene-1,3,5-triyltris(4-(3-(anthracene-9-yloxy)propoxy)benzoate) [ka]

[0134] 4-((4-(anthracene-9-yloxy)butoxy)methyl)benzoic acid.Int-19 [ka]

[0135] Step 1: To a stirred solution of Int-18 (3.29 g, 10.0 mmol) in 10.0 mL of dimethylformamide, methyl 4-hydroxybenzoate (1.67 g, 11 mmol) was added at ambient temperature under a nitrogen atmosphere, followed by potassium carbonate (2.764 g, 20 mmol). The reaction mixture was stirred at 85°C for 16 hours. The reaction mixture was filtered. Insoluble substances were washed with ethyl acetate. The filtrates were combined and concentrated to dryness. The residue was washed with cold water and then with hexane to obtain 4.14 g of an off-white solid product, which was then removed without further purification and proceeded to the next step.

[0136] Step 2: A solution of 4N NaOH in H2O (10 mL, 40 mmol) was added to the above mixture (4.0 g) in THF (50 mL) and methanol (5 mL). The resulting mixture was stirred at 45°C for 12 hours. The reaction was monitored by TLC and LC-MS. Once the conversion was complete, the reaction mixture was poured into water (100 mL). The off-white solid product was washed with water. Acetone, then DCM, was added, and the mixture was then dried in a vacuum oven to obtain 3.9 g of off-white solid Int-19 (total yield of 90% in the two steps). 1 H NMR (400MHz, DMSO-d6) δ8.38(s, 1H), 8.30~8.22(m, 2H), 8.13~8.05(m, 2H), 7.87~7.79(m, 2H), 7.58~7.49(m, 4H), 6.88~ 6.80(m, 2H), 4.23(t, J=6.2Hz, 2H), 4.13(t, J=6.1Hz, 2H), 2.26~2.13(m, 2H), 2.13~2.00(m, 2H). LCMS(APCI-), formula: C 26 H 24 Calculated value for O4 (M-): 400.47; Measured value: 400.

[0137] Benzene-1,3,5-triyltris(4-(4-(anthracene-9-yloxy)butoxy)benzoate)RM-13 [ka]

[0138] A mixture of Int-19 (1.082 g, 2.8 mmol, 4.5 equivalents), DMAP-pTSA (1.467 g, 4.99 mmol, 8 equivalents), and EDC·HCl (1.431 g, 7.47 mmol, 12 equivalents) was mixed with DCE:CHCl3 (1:1) (45 mL), followed by the addition of phloroglucinol (0.0785 g, 0.622 mmol, 1 equivalent). The resulting mixture was stirred under an argon atmosphere at room temperature for 16 hours. The resulting mixture was stirred for a further 3 hours. H2O (10 mL) was added, followed by stirring for a further 15 minutes. The organic layer was separated, concentrated to 20 ml, and packed onto an 80 g SiO2 column. Elution was performed by transitioning to Hex-DCM (7 / 3) and then gradually to DCM alone. The pure fraction was collected, concentrated, and dried in a vacuum oven to obtain 570 mg of colorless solid RM-13 (yield 77%). 1 H NMR (400MHz, chloroform-d) δ8.34~8.25(m, 2H), 8.23(s, 1H), 8.19~8.11(m, 2H), 8.04~7.96(m, 2H), 7.53~7.42(m, 4H), 7. 14(s, 1H), 7.07~6.98(m, 2H), 4.30(t, J=5.1Hz, 2H), 4.28~4.19(m, 2H), 2.27(p, J=3.0Hz, 4H). LCMS(APCI-), formula: C 81 H 66 O 12 Calculated value (M-): 1231.4; Measured value: 1231.

[0139] RM-14: 2-methyl-1,4-phenylenebis(4-(4-(anthracene-9-yloxy)butoxy)benzoate) [ka]

[0140] A mixture of Int-19 (0.932 g, 2.4 mmol, 2.4 equivalents), DMAP-pTSA (1.47 g, 5.0 mmol, 5 equivalents), and EDC·HCl (1.437 g, 7.5 mmol, 7.5 equivalents) was mixed with DCE:CHCl3 (1:1) (45 mL), followed by the addition of methylhydroquinone (0.124 g, 1 mmol, 1 equivalent). The resulting mixture was stirred under an argon atmosphere at room temperature for 16 hours. The mixture was stirred for a further 3 hours. H2O (10 mL) was added, followed by stirring for a further 15 minutes. The organic layer was separated, concentrated to 20 mL, and packed onto an 80 g SiO2 column. Elution was performed by transitioning to Hex-DCM (7 / 3), and then gradually to DCM alone. The pure fraction was collected, concentrated, and dried in a vacuum oven to obtain 730 mg of colorless solid RM-14 (yield 85%). 1 H NMR (400MHz, chloroform-d) δ8.37~8.27(m, 4H), 8.23(s, 2H), 8.21~8.10(m, 4H), 8.06~7.95(m, 4H), 7.48(qd, J=6.7, 3.3Hz, 8H), 7.19(d, J=8.7Hz, 1H), 7.14(d, J=2.8Hz, 1H), 7.09(dd, J=8.6, 2.8Hz, 1H), 7.06~6.97(m, 4H), 4.30(q, J=4.3, 3.1Hz, 4H), 4.25(h, J=2.5Hz, 4H), 2.36~2.19(m, 11H). LCMS(APCI-), formula: C 57 H 48 Calculated value for O8 (M-): 861.00; Measured value: 861.

[0141] RM-15: 5-(anthracene-9-yloxy)pentyl 2,4,6-tris((5-(anthracene-9-yloxy)pentyl)oxy)benzoate [ka]

[0142] A mixture of Int-18 (0.799 g, 2.345 mmol, 4.69 equivalents), 2,4,6-trihydroxybenzoic acid (85 mg, 0.5 mmol, 1 equivalent), anhydrous potassium carbonate (0.276 g, 2.0 mmol, 4 equivalents), and anhydrous DMF (15 ml) was stirred at 75°C for 16 hours under an argon atmosphere. The cooled mixture was filtered, and the filtrate was concentrated. The crude solid product was washed with water and then packed onto an 80 g SiO2 column. Elution was performed using hexane:DCM → DCM alone as the eluent. Fractions 8-10 were collected and concentrated until a rubbery solid was obtained, and this was triturated with ethyl acetate to obtain 0.250 g of off-white RM-15 (yield 40%). 1 H NMR (400MHz, chloroform-d) δ8.31~8.24(m, 2H), 8.24~8.14(m, 6H), 8.13(d, J=2.1Hz, 4H), 8.01~7.94(m, 2H), 7.94~7.86(m, 6H), 7.50~7.42(m, 5H), 7.42~7.31(m, 12H), 6.17(s, 2H), 4.34(t, J=6.7Hz, 2H), 4.22(t, J=6.4Hz , 2H), 4.12(t, J=6.5Hz, 4H), 4.05(t, J=6.2Hz, 6H), 3.95(t, J=6.5Hz, 2H), 2.11(q, J=7.0Hz, 2H) , 2.01(q, J=6.9Hz, 4H), 1.89(tt, J=14.9, 7.5Hz, 10H), 1.79(q, J=7.7Hz, 6H), 1.66~1.58(m, 2H). LCMS(APCI-), formula: C 83 H 78 Calculated value for O9 (M-): 1219.53; Measured value: 1219.

[0143] RM-16: 5-(anthracene-9-yloxy)pentyl 2,4,6-tris((5-(anthracene-9-yloxy)pentyl)oxy)benzoate [ka]

[0144] A mixture of Int-18 (0.823 g, 2.5 mmol, 5 equivalents), 2,4,6-trihydroxybenzoic acid (85 mg, 0.5 mmol, 1 equivalent), anhydrous potassium carbonate (0.345 g, 2.5 mmol, 5 equivalents), and anhydrous DMF (15 ml) was stirred at 75°C for 16 hours under an argon atmosphere. The cooled mixture was filtered, and the filtrate was concentrated. The crude solid product was washed with water and then packed onto an 80 g SiO2 column. Elution was performed using hexane:DCM → DCM alone as the eluent to obtain a rubbery solid, which was then triturated with ethyl acetate to obtain 0.275 g of off-white solid RM-16 (yield 47%). 1 H NMR (400MHz, chloroform-d) δ8.32~8.25(m, 2H), 8.24~8.16(m, 5H), 8.15(s, 2H), 8.12~8.07(m, 2H), 8.05(s, 1H), 8.0 2~7.90(m, 6H), 7.84(d, J=8.4Hz, 2H), 7.51~7.42(m, 4H), 7.43~7.34(m, 8H), 7.34~7.28(m , 2H), 7.25~7.20(m, 2H), 6.23(s, 2H), 4.41(d, J=5.9Hz, 2H), 4.26(s, 2H), 4.16(d, J=4.6H z, 10H), 4.09 (d, J=5.8Hz, 2H), 2.20 (s, 4H), 2.16 (d, J=1.2Hz, 8H), 2.10 (d, J=3.2Hz, 4H). LCMS(APCI-), formula: C 83 H 78 Calculated value for O9 (M-): 1163; Measured value: 1163.

[0145] RM-17: 2-Methyl-1,4-phenylenebis(3,5-bis(4-(anthracene-9-yloxy)butoxy)benzoate) [ka]

[0146] 3,5-Bis(4-(anthracene-9-yloxy)butoxy)benzoic acid.Int-20 [ka]

[0147] Step 1: A mixture of Int-18 (1.9754 g, 6.0 mmol, 3 equivalents), methyl 3,5-dihydroxybenzoate (336.3 mg, 2.0 mmol, 1 equivalent), anhydrous potassium carbonate (1.104 g, 8.0 mmol, 4 equivalents), and anhydrous MeCN (25 ml) was stirred at 65°C for 8 hours, and then stirred at 75°C for 8 hours under argon. The cooled mixture was filtered, and the filtrate was concentrated. The crude solid product was washed with water and then packed onto an 80 g SiO2 column. Elution was performed using hexane:DCM → DCM alone as the eluent to obtain 1.1 g of a colorless, viscous solid (yield 82%). 1 H NMR (400MHz, chloroform-d) δ8.33~8.24(m, 2H), 8.22(s, 1H), 8.04~7.94(m, 2H), 7.52~7.41(m, 4H), 7.21(dd, J=2.3, 1.3Hz, 1H), 7.13(dd, J=2.4, 1.3Hz, 1 H), 6.64(t, J=2.3Hz, 1H), 5.20(s, 1H), 4.32~4.24(m, 2H), 4.20~4.13(m, 2H), 3.90(s, 3H), 2.22(dqt, J=5.9, 3.7, 2.2Hz, 4H). LCMS(APCI-), formula: C 44 H 40 Calculated value for O5 (M-): 664; Measured value: 664.

[0148] Step 2: The mixture of the above compounds was dissolved in 16 mL of THF / MeOH (15 / 1), and 10 mL of 4N NaOH aqueous solution (40 mmol) was added. The resulting mixture was stirred at 45°C for 5 hours. After cooling to 0°C, it was acidified with 4N HCl. The product was extracted with CHCl3. The organic layer was separated, washed with water, and concentrated to dryness. The crude product was purified by SiO2 column chromatography using DCM alone to obtain 1.0 g of colorless solid Int-20. 1H NMR (400MHz, chloroform-d) δ8.34~8.26(m, 4H), 8.22(s, 2H), 8.03~7.95(m, 4H), 7.54~7.40(m, 8H), 7.29(d, J=2.3Hz, 2 H), 6.79(t, J=2.3Hz, 1H), 4.33~4.25(m, 4H), 4.18(d, J=5.1Hz, 4H), 2.24(t, J=3.0Hz, 7H). LCMS(APCI-), formula: C 43 H 38 Calculated value for O5 (M-): 650; Measured value: 650.

[0149] 2-Methyl-1,4-phenylenebis(3,5-bis(4-(anthracene-9-yloxy)butoxy)benzoate)RM-17 [ka]

[0150] A mixture of Int-20 (0.88 g, 1.352 mmol, 2.5 equivalents), DMAP-pTSA (0.635 g, 4.99 mmol, 2.16 mmol, 4 equivalents), and EDC·HCl (0.62 g, 3.24 mmol, 6 equivalents) was mixed with DCE:CHCl3 (1:1) (45 mL), followed by the addition of methylhydroquinone (0.067 g, 0.54 mmol, 1 equivalent). The resulting mixture was stirred at room temperature under an argon atmosphere for 6 hours. An additional 250 mg of EDC·HCl was added, and the resulting mixture was stirred at room temperature for a further 3 hours. H2O (10 mL) was added, followed by stirring for a further 15 minutes. The organic layer was separated and washed with 1N HCl. The organic layer was separated and concentrated, and the crude product was packed into an 80 g SiO2 column and eluted by transitioning to Hex-DCM, and then gradually to DCM alone. The pure fraction was collected, concentrated, and dried in a vacuum oven to obtain 570 mg of colorless solid RM-17 (yield 72%). 1H NMR (400MHz, chloroform-d) δ8.34~8.26(m, 9H), 8.22(s, 4H), 8.03~7.95(m, 9H), 7.50~7.43(m, 16H), 7.43(d, J=2.4Hz, 2H), 7.40(d, J=2.3Hz, 2H) , 7.22~7.07(m, 4H), 6.83(dt, J=4.7, 2.3Hz, 2H), 5.29(s, 3H), 4.29(d, J=5.6Hz, 8H), 4.25~4.18(m, 8H), 2.26(s, 19H). LCMS(APCI-), formula: C 93 H 50 O 12 Calculated value (M-): 1389; Measured value: 861.

[0151] RM-18: 1,3,5-Triyltris(4-(3-(Anthracene-9-yloxy)propoxy)benzoate) [ka]

[0152] A mixture of Int-4 (1.042 g, 2.8 mmol, 4.5 equivalents), DMAP-pTSA (1.467 g, 4.99 mmol, 8 equivalents), and EDC·HCl (1.431 mg, 7.47 mmol, 12 equivalents) was mixed with DCE:CHCl3 (1:1) (45 mL), followed by the addition of phloroglucinol (0.0785 g, 0.622 mmol, 1 equivalent). The resulting mixture was stirred under an argon atmosphere at room temperature for 16 hours. H2O (10 mL) was added, and the mixture was stirred for a further 15 minutes. The organic layer was separated, concentrated to 20 mL, and packed onto an 80 g SiO2 column. Elution was performed by transitioning to Hex-DCM (7 / 3), and then gradually to DCM alone. The pure fraction was collected, concentrated, and dried in a vacuum oven to obtain 570 mg of colorless solid RM-18 (yield 77%). 1H NMR (400MHz, chloroform-d) δ8.22(ddd, J=8.9, 7.6, 1.6Hz, 15H), 8.03~7.94(m, 6H), 7.49~7.34(m, 12H), 7.18(s, 3H) , 7.15~7.08(m, 6H), 4.57(t, J=6.0Hz, 6H), 4.43(t, J=6.0Hz, 6H), 2.55(p, J=6.0Hz, 6H). LCMS(APCI-), formula: C 78 H 60 O 12 Calculated value (M-): 1189.33; Measured value: 1189.

[0153] Fabrication of liquid crystal-based dimmable devices using the capillary method A selectively dimmable device based on a heterocyclic basic liquid crystal compound with positive dielectric anisotropy was fabricated using the capillary method. The device was manufactured using a uniform liquid crystal test cell (KSRO-10 / B107M1NSS05, EHC Corporation, Tokyo, Japan). The test cell consisted of two substrates and a support member defining the active orientation region between them. The glass / ITO substrates were 20mm x 25mm in size, with a sheet resistance of approximately 100Ω / sq, an active orientation region of approximately 10mm x 10mm, and a cell gap of 10μm. Since the cell was procured with a pre-coated polyamide orientation layer (LX-1400, Hitachi Chemical Trading Co., Ltd., Tokyo, Japan), the application of the orientation layer was unnecessary. Because the cell shape included a support member to maintain the cell gap, it was not necessary to insert a separate spacer into the cell before applying the liquid crystal mixture.

[0154] First, a liquid crystal mixture was prepared by mixing a fluorinated liquid crystal with a reactive mesogen, such as RM-1 to RM-18, in a weight ratio of 95% to 5%. The mixtures were then mixed at 75°C using a vortex mixer. Next, the substrate was heated on a hot plate at 75°C for 5 minutes to preheat the test cell for liquid crystal injection. The hot coating mixture was then injected near the opening of the test cell. The solution then flowed into the test cell by capillary action, covering the entire active orientation region. In some embodiments, the test cell was placed on a hot plate after the injection of the coating mixture to help ensure uniform and complete coating of the liquid crystal. The resulting coated substrate was then soft-baked on the hot plate at 75°C for approximately 3 minutes to remove all residue. After the soft-baking process, a layered cell assembly ready for ultraviolet curing (UV curing) was obtained.

[0155] The layered cell assembly was soldered to conductive wire using indium for subsequent haze measurements. The layered cell assembly was then placed in a UV chamber (365 nm, UWAVE, Villebon-sur-Yvette, France). The layered cell assembly was subjected to a UV emission of 187 mW / cm². 2 The material cured with an incident power of 1 to 20 minutes (corresponding to 11 to 220 joules).

[0156] Next, a dimmable assembly was placed in the telecommunications port, and conductive clips and wiring were connected. An electric field was generated throughout the liquid crystal by applying an AC voltage. Subsequently, it was shown that the orientation of the reactive mesogens within the liquid crystal composite changed, and the cells changed from transparent to opaque.

[0157] Haze measurement Haze was measured using an HM-150 spectrophotometer manufactured by Murakami Color Technology Laboratory Co., Ltd. (Tokyo, Japan), in accordance with JIS K 7136.

[0158] [Table 1]

[0159] [Table 2]

[0160] [Table 3]

[0161] Reversibility test of photodimerization ⇔ photodissociation Test I: Dimmable assembly using UV365nm⇔UV254nm (dimerization⇔dissociation) (LC / anthracene (95 / 5) mixture in an ITO test cell) Furthermore, a UV LED (254nm, Analytik Jena, California, USA) was used on the prepared dimmable assembly sample with an incident power of 9mW / cm². 2 The samples were irradiated with a UV LED (365nm, UWAVE, France, Villebon-sur-Yvette) and the reversibility of the drive voltage change at a specific haze value was investigated. First, each sample was irradiated with a UV LED (365nm, UWAVE, France, Villebon-sur-Yvette) at an incident power of 187mW / cm². 2 It was left for 0 to 60 minutes (approximately 673.2 J / cm²). 2 (The dimerization process increases the crosslinking density, which in turn increases the driving voltage.) Next, the sample is irradiated with a UV LED (254 nm) for 0 to 20 minutes (approximately 32.4 J / cm²). 2 (A crack occurred, and the drive voltage decreased), and then the haze value was examined. The reversibility results are shown in Figures 5 and 6.

[0162] Test II: UV365nm (dimerization) / UV254nm (dissociation) of liquid crystal solution in THF by GPC measurement. dimerization 10 mg to 100 mg of RM-13 and 10 ml of THF were introduced into a stirring quartz vial attached to a condenser equipped with an argon gas inlet. While stirring the mixture at room temperature, argon gas was introduced for at least 30 minutes to remove oxygen from the reaction system. Then, the vial, fitted with a sealed cap, was transferred to a UV 365 nm photoreactor (Photoreactor M2, Penn PHD, Sigma-Aldrich, Germany) and the dimerization reaction was carried out for approximately 0 to 60 minutes. After the reaction was stopped, a phototuner-containing solution was obtained. Next, the apparent molecular weight of the phototuner solution was determined by GPC measurement (Hitachi Chromaster GPC system).

[0163] [Table 4]

[0164] [Table 5]

[0165] dissociation A dimerization solution of a predetermined concentration was packed into a quartz cuvette with a path length of 1 mm, and then exposed to a UV LED (254 nm, Analytik Jena) for approximately 0 to 60 minutes. After exposure, a dissociated solution was obtained. Next, the apparent molecular weight of the dissociated solution was determined by GPC measurement (Hitachi Chromaster GPC system).

[0166] [Table 6]

[0167] Unless otherwise specified, all numerical values ​​used in the specification and claims to represent the quantities of components, molecular weights and other properties, reaction conditions, etc., shall always be understood as being modified by the term "approximately." Therefore, the numerical parameters described in the specification and the attached claims are approximations that may vary depending on the desired properties intended to be obtained, unless otherwise specified. At the very least, this is not intended to limit the application of the doctrine of equivalents to the scope of the claims, and each numerical parameter should be interpreted using normal rounding in light of the number of significant figures reported.

[0168] In the context of the description of the invention (particularly in the context of the appended claims), the terms “a,” “an,” “the,” and similar demonstrative pronouns should be interpreted as including both singular and plural forms unless otherwise stated herein or unless clearly contradicted by the context. All methods described herein can be implemented in any appropriate order unless otherwise stated herein or unless clearly contradicted by the context. The use of any examples or representative expressions (e.g., “etc.”) described herein is intended merely to more clearly describe the invention and does not constitute a limitation on the scope of any claim. No expression herein should be interpreted as indicating an element that is essential for the implementation of the invention but is not described in the claims.

[0169] The grouping of alternative elements or embodiments disclosed herein should not be construed as limitation. Each group component may be referred to and claimed individually or in any combination with other components within the group or other elements described herein. For convenience and / or patentability, it is anticipated that one or more components within a group may be included in or removed from the group. If such inclusion or removal occurs, the specification shall be deemed to include the modified group, thereby satisfying the written description of all Markash groups used in the appended claims.

[0170] This specification describes certain embodiments, including the best known embodiment for carrying out the invention. Naturally, variations of these described embodiments will be apparent to those skilled in the art upon reading the preceding description. The inventors expect that those skilled in the art will adopt such variations where appropriate, and they intend that the invention will be carried out in ways other than those specifically described herein. Accordingly, the claims include, to the extent permitted by applicable law, all variations and equivalents of the subject matter described in the claims. Furthermore, unless otherwise stated herein or unless it is clearly inconsistent with the context, all combinations of the above elements are assumed in all possible variations.

[0171] Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the claims. Other modifications that may be adopted are within the scope of the claims. Therefore, alternative embodiments can be utilized, not limitingly but exemplary, in accordance with the teachings herein. Accordingly, the claims are not strictly limited to the embodiments shown and described.

Claims

1. The following formula: 【Chemistry 1】 (In the formula, R ７ is a bond, hydrogen, or C １ ~C ３ Selected from alkyl groups, L １ 、 L ３ 、 L ４ 、 and L ５ are, independently, selected from C ２ to C ８ diether linkers or C ２ to C ８ ether acetate linkers, R １ , R ３ , R ４ , and R ５ A photoreactive liquid crystal compound (independently selected from anthracenyl, coumarinyl, cinnamylate group, stilbenyl, or thymyl).

2. L １ , L ３ , L ４ , and L ５ However, they became independent, 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 A photoreactive liquid crystal compound according to claim 1, selected from (wherein n or m is an integer from 1 to 10).

3. R １ , R ３ , R ４ , and R ５ However, they became independent, 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 And, 【Chemistry 9】 A photoreactive liquid crystal compound according to claim 1, selected from the following.

4. The following structure: 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 And, 【Chemistry 27】 A photoreactive liquid crystal compound according to claim 1, having one of the following.

5. A polymer-dispersed liquid crystal composition comprising one or more compounds described in any one of claims 1 to 4.

6. A liquid crystal element comprising the polymer-dispersed liquid crystal composition described in claim 5.

7. To prepare an oligomer or polymer containing one or more compounds according to any one of claims 1 to 4, To provide a crosslinked oligomer or polymer by irradiating the aforementioned oligomer or polymer with crosslinking ultraviolet light, Methods that include...

8. The method according to claim 7, wherein the crosslinking ultraviolet light includes wavelengths in the range of about 305 nm to about 395 nm.

9. The irradiation is 0.1 J / cm² of the crosslinking ultraviolet light. ２ ~2500 J / cm ２ The method according to claim 7 or 8, including the method described in claim 7 or 8.

10. The method according to claim 7, further comprising irradiating the crosslinked oligomer or polymer with cleavage-inducing ultraviolet light.

11. The method according to claim 10, wherein the ultraviolet light for dehiscing includes wavelengths in the range of about 254 nm to about 280 nm.

12. The irradiation of the aforementioned cleavage-causing ultraviolet light was 0.1 J / cm². ２ From 2500 J / cm ２ The method according to claim 10, comprising the aforementioned ultraviolet light for dehiscence.

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