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

Abstract

Photoreactive liquid crystal compounds having reversible photodimerization functional groups and devices including the same are described. The liquid crystal composition containing the reversibly photodimerizable liquid crystal compound may allow a depicted display to be changed upon application of an electric field.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 493,132, filed March 30, 2023, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0003] This disclosure relates to reversibly polymerizable compounds or compositions, and to elements or devices comprising reversibly polymerizable compounds or compositions.

[0004] For window shading, smart windows offer an attractive alternative to conventional mechanical shutters, blinds, or hydraulic shading methods. Technologies used in smart window applications include suspended particle displays (SPDs), polymer-dispersed liquid crystals (PDLCs), and electrochromic (ECs). (References: S. Rudolph, J. Dieckmann, & J. Brodrick, Technologies for Smart Windows, ASHRAE Journal 104 (Jul. 2009); D. Cupelli et al., Reverse Mode Operation Polymer Disperse Liquid Crystal with a Positive Dielectric Anisotropy Liquid Crystal, 49 J. Polymer Sci. Part B: PolymerPhysics 257-62 (2011).) Regarding PDLCs, after a PDLC image is created, the image is fixed, and changes or alterations to the image may require reloading a new image on or within the device.

[0005] Therefore, additional contributions are needed in this technological field. Summary of the Invention

[0006] In one embodiment, this document describes a material that can be used in a rewritable PDLC dimmable device. The material can be integrated with a window or applied as a coating to provide a modifiable image by incorporating the photoreactive compounds described herein, but other applications are also possible and anticipated.

[0007] In one embodiment, the photoreactive liquid crystal composition can be made photoreversible by applying radiation to the composition to provide selective polymerization and / or depolymerization of crosslinked entities (e.g., reversible photodimerizing functional groups). In some embodiments, the photoreactive liquid crystal composition includes at least one photoreactive compound, which may include at least two (two types) photodimerizing functional groups.

[0008] In some embodiments, the photoreactive liquid crystal compound comprises a structure or substructure according to the following general formula:

[0009]

[0010] In this formula, R1, R3, R4, R5 and / or R7 can be independently selected from anthracene, coumarin, cinnamic acid, stilbene, or thymine groups, and R7 can be selected from a bond, hydrogen, or C1-C3 alkyl group.

[0011] L1, L3, L4, and L5 can be independently selected from C1-C 10 Diether linker unit or C1-C 10 Ether acetate linker unit.

[0012] In some implementations, the connecting units L1, L3, L4, and L5 can be independently selected from:

[0013]

[0014] Where n or m is an integer from 1 to 10.

[0015] In some embodiments, the photoreactive liquid crystal compound or mesogen may include a reversible photodimerizing R functional group. In some embodiments, the reversible photodimerizing R functional group may include R groups R1, R3, R4, and / or R5. In some embodiments, the R1, R3, R4, or R5 groups may be independently selected from: In some embodiments, the photoreactive liquid crystal compound may have one of the following structures:

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022] In some embodiments, the polymer-dispersed liquid crystal (PDLC) composition may include the photoreactive liquid crystal compound described herein. In some embodiments, the photoreactive compound may include at least two reversible photodimerizing functional groups described herein. In some embodiments, the polymer-dispersed liquid crystal element may include the polymer-dispersed liquid crystal composition described herein.

[0023] In some embodiments, the method for reversibly crosslinking a polymer network includes providing a monomer, oligomer, or polymer comprising a liquid crystal composition. In one form, 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 form, the liquid crystal composition may comprise two photoreactive liquid crystal compounds as described herein. The method also includes irradiating the oligomer or polymer with ultraviolet radiation. In one aspect, the UV radiation may include a first crosslinking wavelength between about 305 nm and about 395 nm (e.g., about 365 nm) to reversibly crosslink and photodimerize terminal R groups, said terminal R groups being, for example, anthracene, coumarin, cinnamic acid, stilbene, or thymine (one or more) disposed at the ends of connecting units L. In some embodiments, the method may further include irradiating the crosslinked oligomer or polymer with ultraviolet radiation including a second cleavage wavelength between about 254 nm and about 280 nm. In some embodiments, a liquid crystal element may include a transparency-changing layer defining two opposite surfaces, the composition described herein, and at least two alignment layers, wherein the transparency-changing layer may be defined on the two opposite surfaces by respective alignment layers of the at least two alignment layers.

[0024] In some embodiments, the selectively dimmable device includes a first conductive substrate and a second conductive substrate, a liquid crystal element as described herein disposed between the first and second conductive substrates, and a voltage source. The first conductive substrate, the second conductive substrate, the liquid crystal element, and the voltage source are all electrically connected such that when a voltage is applied from the voltage source, an electric field is applied across the element.

[0025] In some forms, a selectively dimmable device can be characterized as having a haze of up to 10% when no voltage is applied, but at least 35% haze when a voltage of less than 40 volts is applied across the device. In some embodiments, the substrate may be flexible, and the device may be in the form of a flexible sheet.

[0026] These and other implementation schemes are described in more detail below. Attached Figure Description

[0027] Figure 1A A liquid crystal element with a liquid crystal having positive dielectric anisotropy is shown.

[0028] Figure 1B A liquid crystal element with liquid crystal having negative dielectric anisotropy is shown.

[0029] Figure 2 This invention illustrates a non-limiting form of a selectively dimmable device having a polymer-dispersed liquid crystal with positive dielectric anisotropy.

[0030] Figure 3 This invention illustrates a non-limiting form of a selectively dimmable device for polymer-dispersed liquid crystals with negative dielectric anisotropy.

[0031] Figure 4 Another non-limiting form of a selectively dimmable device is shown.

[0032] Figure 5 It is a graphic illustration showing the haze results between various selective dimming devices.

[0033] Figure 6 This is another illustration showing the haze results among various selective dimming devices.

[0034] Figure 7 This is a graphical illustration showing dimerization (molecular weight) as a function of UV 365 exposure time.

[0035] Figure 8 This is a graphical illustration showing dimerization (molecular weight) as a function of RM-13 concentration.

[0036] Figure 9 This is a graphical illustration showing the breakdown (molecular weight) as a function of UV 254 exposure time.

[0037] Figure 10 This is a graphical illustration showing the effect of measurements of the cleavage molecular weight (Molecular Weight) as a function of UV 365 20-minute exposure time and UV 254 60-minute exposure time. Detailed Implementation

[0038] As used in this article, the term "C" X-Y "" refers to a carbon chain with X to Y carbon atoms. For example, C 3-8 Alkyl groups include alkyl or cycloalkyl groups containing 3, 4, 5, 6, 7 or 8 carbon atoms.

[0039] As used herein, the term "alkyl" refers to a carbon and hydrogen moiety that does not contain double or triple bonds. Alkyl groups can be straight-chain, branched, cyclic, or combinations thereof, and contain 1 to 35 carbon atoms. Examples of alkyl groups include, but are not limited to, C3 alkyl groups; C4 alkyl groups, such as (CH2)3CH3; C5 alkyl groups, such as -(CH2)3CH3; C6 alkyl groups; C7 alkyl groups; C8 alkyl groups; and so on.

[0040] As used herein, the terms “positive dielectric anisotropy,” “negative dielectric anisotropy,” and “neutral dielectric anisotropy” have meanings known to those skilled in the art. Dielectric anisotropy relates to dielectric and optical properties, which depend on orientation, either along the length of the molecule (or molecular axis) or perpendicular to the length of the molecule (or molecular axis). Dielectric properties depend on the molecular shape and the substituent moieties and their positions on a given molecule.

[0041] If the dielectric constant parallel to the molecular length is greater than the dielectric constant perpendicular to the molecular length, then the molecule is said to have positive dielectric anisotropy, where the molecular length is defined as the vector between the two farthest parts.

[0042] If the dielectric constant perpendicular to the molecular length is greater than the dielectric constant parallel to the molecular length, then the molecule is said to have negative dielectric anisotropy, where the molecular length is defined as the vector between the two farthest parts.

[0043] If the dielectric constant perpendicular to the length of the molecule is approximately the same as the dielectric constant parallel to the length of the molecule (i.e., the difference between the dielectric constants is less than 1%), then the molecule is said to have neutral dielectric anisotropy, where the length of the molecule is defined as the vector between the two farthest parts.

[0044] As used herein, the term “opposite surface” refers to a group of two surfaces or sides of a shape or polygon that are located opposite each other (e.g., the top and bottom of a layer, the front and back of a shape). When used in the singular, the term “opposite surface” refers to one of the two surfaces.

[0045] The terms nematic, smectic, and isotropic all have the meanings used by those skilled in the art when referring to liquid crystal phases.

[0046] This disclosure relates to reversible crosslinkable monomers, oligomers and / or polymers, liquid crystal compositions, polymer-dispersed liquid crystal (PDLC) elements and / or selectively dimmable devices including polymer-dispersed liquid crystal (PDLC) elements.

[0047] This disclosure also relates to display devices that can repeatedly record (write) and erase visible information. For example, in one form, the writing pattern can be written by irradiating (photopolymerizing) dimer with light, including a crosslinking wavelength between about 305 nm and about 395 nm, and the erasing pattern can be achieved by irradiating with light of a shorter wavelength (e.g., between about 250 nm and about 280 nm) or by heating.

[0048] This disclosure also relates to electrically switchable and optically rewritable displays based on the photopolymerization / photodepolymerization of photoreactive liquid crystal (LC) compounds. In some embodiments, the photoreactive liquid crystal compound includes one or more reversible photodimerizable functional groups. Optically rewritable patterns can be generated by employing nematic LCs as a reaction solvent and a spatially non-uniform electric field without using lithography or holographic tools. A nematic mixture containing 5.0 wt.% RMs (95% LC) sandwiched between electrodes is exposed to spatially uniform reaction-initiated radiation. The spatially non-uniform electric field induces optical patterns in a reaction template with spatially varying elastic deformation. The resulting polymerized liquid crystal network is spatially and optically patterned with good fidelity relative to the electrode pattern and subsequent periodic director distribution. The pattern can be erased by irradiating the polymerized liquid crystal network with ultraviolet light with a wavelength between about 250 nm and about 280 nm to dissociate it.

[0049] The display device can repeatedly record (write) and erase visual information. For example, it can be written by irradiating a pattern, such as by dimerization with light of wavelengths between about 305 nm and about 395 nm (photopolymerization), and erased by irradiation with light of shorter wavelengths (between about 250 nm and about 280 nm) or by heat (dimer dissociation leads to erasure). The techniques used herein can also be used to incorporate LED light sources into laminated glass plates or for holographic storage systems to repeatedly generate unique patterns, images, and logos, but other applications are possible and anticipated.

[0050] Liquid crystal composition

[0051] In some embodiments, the composition comprises both liquid and crystalline characteristics and may be referred to as a liquid crystal composition. In some embodiments, the liquid crystal composition may include one or more compounds described herein. In some embodiments, the liquid crystal composition may exhibit a mesocrystalline liquid crystal phase. In some embodiments, the liquid crystal composition may include compounds having positive dielectric anisotropy, and in some embodiments, the liquid crystal composition may include compounds having negative dielectric anisotropy. In some embodiments, the liquid crystal composition may include compounds having positive dielectric anisotropy and compounds having negative dielectric anisotropy.

[0052] 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, PA).

[0053] Photoreactive liquid crystal compounds

[0054] 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 reversibly crosslinked oligomers or polymers, and the monomer may include a substituted benzyl derivative. In some embodiments, the substituted benzyl derivative may include at least two linked functionalized substituents. In some embodiments, the substituted benzyl derivative may include two linked functionalized substituent arms, three linked functionalized substituent arms, four linked functionalized substituent arms, five linked functionalized substituent arms, and / or six linked functionalized substituent arms.

[0055] In some embodiments, the substituted benzyl derivative may have the following general structure:

[0056]

[0057] T1, T2, T3, T4, T5, or T6 can be bonds, hydrogen, C1-C3 alkyl groups, and / or LR functional groups, where L can be C1-C6. 10 Diether linker unit or C1-C 10 The ether acetate linker unit, wherein R may be a reversible photodimeric functional group, such as anthracene, coumarin, cinnamic acid, stilbene, and / or thymine group.

[0058] In some embodiments, the substituted benzyl derivative may have the following general structure:

[0059]

[0060] In some embodiments, the substituted benzyl derivative may have the following general structure:

[0061]

[0062] In some embodiments, the substituted benzyl derivative may have the following general structure:

[0063]

[0064] In some embodiments, R7 may be a bond, hydrogen, or a C1-C3 alkyl group. In some embodiments, the liquid crystal compound and / or monomer capable of forming reversibly crosslinked oligomers or polymers may include an R group disposed at the end of a linking unit opposite to the benzyl core group. In some embodiments, the R group may include R1, R2, R3, R4, R5, and / or R6 groups. In some embodiments, the R1, R2, R3, R4, R5, and / or R6 groups may be independently selected from anthracene, such as anthracenel; coumarin, such as coumarin; cinnamic acid, such as cinnamic acid / ester; stilbene, such as stilbene; or thymine, such as thymine. In some embodiments, the anthracene, coumarin, cinnamic acid, stilbene, or thymine group may have the following general formula:

[0065] (anthrayl), ( Coumarin base) (Cinnamyl esters) (stilbene) and ( (thymidine group).

[0066] In some embodiments, each R group may include the same substituent; for example, all R groups may be anthracene groups. In some embodiments, the corresponding R groups may include any arrangement of the aforementioned substituents; for example, one arm may be functionalized with one of the aforementioned substituents, and another arm may be functionalized with another of the aforementioned substituents. Thus, the plurality of arms may be a mixture of anthracene, coumarin, cinnamic acid, stilbene, and / or thymine functionalized arms. In some embodiments, at least one of the corresponding R groups may dimerize, covalently bond, or link with a similar R group; for example, an anthracene terminal group may dimerize, covalently bond, or link with another anthracene terminal group. In some embodiments, the composition may include 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 the following:

[0067]

[0068]

[0069] It is believed that the aforementioned photoreversible dimerization or covalent bonding is an example of how the bonding of the terminal R groups enables the formation of linkages. In some embodiments, the corresponding structural changes can be determined by proton NMR. It is believed that photoreversible dimerization allows for the rewriting and erasure properties of current materials.

[0070] In some embodiments, the liquid crystal compound and / or monomer capable of forming photoreactive reversible dimerization or crosslinking oligomers or polymers may include a linking unit L between a benzyl core group and an R group. In some embodiments, the linking unit L may include L1, L2, L3, L4, L5 and / or L6 and / or any further similar arms. In some embodiments, the linking unit L may be selected from a C2-C8 diether linking unit or a C2-C8 ether acetate linking unit. In some embodiments, L may be C1-C 10 Diether linking units (e.g., C2 diether linking units, C3 diether linking units, C4 diether linking units, C5 diether linking units, C6 diether linking units, C7 diether linking units, C8 diether linking units, C9 diether linking units and / or C...) 10 (diether linker unit) or C1-C 10 Ether acetate linking units (e.g., C1 ether acetate linking units, C2 ether acetate linking units, C3 ether acetate linking units, C4 ether acetate linking units, C5 ether acetate linking units, C6 ether acetate linking units, C7 ether acetate linking units, C8 ether acetate linking units, C9 ether acetate linking units and / or C... 10 (Ether acetate linker unit). In some embodiments, the linker unit L may be independently selected from:

[0071]

[0072] Where n or m can be 1-10, for example 3, 4, 5 and / or 6.

[0073] In some embodiments, the monomers capable of forming photoreactively dimerizable oligomers or polymers may include compounds selected from the following, or may include at least two compounds selected from the following:

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083] In some embodiments, the monomer, oligomer, or polymer may include a substructure, which may include the aforementioned monomer and / or photoreactive liquid crystal compound.

[0084] 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 polymeric liquid crystal compositions described herein.

[0085] In some embodiments, methods for reversibly crosslinking polymer networks may include providing oligomers or polymers comprising the photoreactive monomers, oligomers, and / or polymers described herein. In one form of the method, the oligomers or polymers are irradiated with crosslinking ultraviolet radiation at a crosslinking wavelength between about 305 nm and about 395 nm to provide crosslinked oligomers or polymers. In some embodiments, irradiation of at least one of the aforementioned R groups may covalently bond a similar R group to another. In some embodiments, the bonding may be selected from those described herein. The method may also include irradiating the oligomers or polymers with ultraviolet radiation having a cleavage wavelength between about 220 nm and about 280 nm (e.g., 254 nm). In some embodiments, irradiation of the aforementioned R groups, such as anthracene or coumarin, results in cleavage from the similar R groups. In some embodiments, the bonding may be selected from those described herein.

[0086] The method may include repeated irradiation steps of applying crosslinking and cleaving ultraviolet radiation.

[0087] Liquid crystal element

[0088] For example, such as Figure 1A or Figure 1B As shown, 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 includes two opposing surfaces, and the two opposing surfaces are defined by corresponding first and second alignment layers in the alignment layers 120. In some embodiments, any of the above layers may further include a dispersant, plasticizer, binder, and / or solvent.

[0089] In the illustrated form, 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 liquid crystal mixture compound described herein. Those skilled in the art will recognize that additional PDLC materials may be present in the PDLC matrix, including, for example, positive dielectric anisotropic compounds, negative dielectric anisotropic compounds, and / or polymers. Non-limiting examples of positive dielectric anisotropic compounds may be described in detail elsewhere herein, or found in WO 2017 / 180923 and / or WO 2018 / 152257, the contents of which are incorporated herein by reference in their entirety. In some embodiments, such as Figure 1B As shown, the composition may include negative dielectric anisotropic compound 114, while Figure 1A The embodiments include a positive dielectric anisotropic compound 113. In some embodiments, composition 111 may include a positive dielectric anisotropic compound and a negative dielectric anisotropic compound. In some embodiments, the transparency-changing layer 110 may further include a polymer 112, and composition 111 may be dispersed in the polymer. In the form shown in FIG. 1, composition 111 is dispersed within the transparency-changing layer such that the composition forms droplets suspended within polymer 112. Transparency-changing layer 110 may be considered as polymer-dispersed liquid crystal (PDLC). Figure 1A and 1B In the illustrated form, the transparency-changing layer 110 includes spacers 115, although a form without spacers 115 is also conceivable. In some embodiments, the transparency-changing layer 110 may include one or more photoreactive liquid crystal compounds described herein. In some embodiments, the liquid crystal element 100 may be opaque to visible light but becomes transparent when an electric field is applied, or a normal-mode PDLC. In some embodiments, the liquid crystal element 100 may be transparent to visible light but opaque when an electric field is applied, or a reverse-mode element.

[0090] In some embodiments, the transparency-changing layer 110 may be a polymer-dispersed liquid crystal layer, wherein the liquid crystal composition forms droplets within a polymer matrix. In some embodiments, the liquid crystal droplets form 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 comprise a substrate material having transparent electrode layers disposed on both sides of the polymer-dispersed liquid crystal layer.

[0091] Selective dimming device

[0092] Now for reference Figure 2 and Figure 3A selectively tunable light device 200 is illustrated. Device 200 includes two conductive substrates (or electrode layers) 210, a liquid crystal element 100, and a voltage source. In the illustrated configuration, the first and second conductive substrates 210 define a gap therebetween, wherein the liquid crystal element 100 is disposed within the gap between the first and second conductive substrates 210. In some embodiments, a polymer matrix comprising one or more photoreactive compounds as described herein may be disposed within a flexible film comprising the materials described herein. In some embodiments, a polymer matrix comprising the photoreactive compounds described herein may be disposed within a polymer liquid crystal composition comprising the materials described herein. In some embodiments, the liquid crystal element 100, the conductive substrates 210, and the voltage source are all electrically connected such that an electric field is applied across the liquid crystal element 100 when a voltage is applied from the voltage source. In some embodiments, the application of voltage from the voltage source provides a discernible image when the liquid crystal composition and / or device 200 are observed.

[0093] like Figure 2 and Figure 3 As shown, the liquid crystal element 100 integrated into device 200 includes a polymer matrix 112, in which polymer-dispersed liquid crystal droplets are suspended and defined 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. In some embodiments of device 200, for example, Figure 2 As shown, the liquid crystal droplets may include a positively dielectric anisotropic compound 113. In other embodiments of device 200, such as... Figure 3 As shown, the liquid crystal droplets may include a negative dielectric anisotropic compound 114. In other embodiments, the liquid crystal droplets may include a combination of a positive dielectric anisotropic compound and a negative dielectric anisotropic compound.

[0094] In some embodiments of device 200, liquid crystal element 100 may be selected such that, in the absence of an induced electric field within transparency-changing layer 110, the refractive index of liquid crystal composition 111 and the refractive index of polymer 112 are similar to each other, such that the total transmittance of visible light allowed through device 200 may 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 a circuit, the refractive index of liquid crystal composition 111 and the refractive index of polymer 112 may vary relative to each other, such that incident light is scattered, and at most only about 70%, only about 65%, only about 60%, only about 50%, only about 30%, only about 25%, only about 15%, only about 10%, or only about 5% of visible light may pass through device 200. In some embodiments, the magnitude of the electric field required to achieve scattering corresponds to a voltage applied to device 200 that is 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. In some embodiments, the electric field across device 200 is less than about 500kV / m, less than about 1,000kV / m, less than about 5,000kV / m, less than about 10,000kV / m, less than about 20,000kV / m, less than about 40,000kV / m, or less than about 80,000kV / m. It is believed that the dimming effectiveness of device 200 can also be described as a haze percentage, which is typically defined as:

[0095]

[0096] The total transmitted light is light from a known source, and the diffuse transmitted light is light transmitted through element 100. In some embodiments, when no voltage is applied to the device, the haze of device 200 can be a maximum of about 5%, about 10%, about 15%, about 20%, about 25%, or about 30%. In some embodiments, when a voltage of about 40 volts or less is applied to achieve scattering, the haze of the device can be at least about 30%, about 35%, about 40%, about 50%, about 70%, about 75%, about 85%, about 90%, or about 95%. In some embodiments, the amount of haze change between a voltage-applied state and a voltage-unapplied state can be altered by a reversible photodimerization reaction of the photoreactive liquid crystal composition.

[0097] In some embodiments, the device 200 may be semi-rigid or rigid. In some embodiments, the device 200 may be flexible. In some embodiments, the selectively dimmable device 200 may be formed into a flexible sheet, such as... Figure 4As shown, it can be applied between or on a pre-existing window pane or surface. In some embodiments, the conductive substrate 210 can be formed of a flexible material, such that the aforementioned device can be a flexible film. In some embodiments, the flexible device can be placed between or on one side of a pre-existing window pane to provide dimming capability. In other embodiments, the device can be rigid, including non-flexible materials.

[0098] In some embodiments, the conductive substrate 210 may include a substrate 211, which in some forms may be formed of a conductive material.

[0099] In some embodiments, each conductive substrate 210 may further include an electronically conductive layer 212, wherein the layer is physically in communication with the substrate 211. In some embodiments, the electronically conductive layer is positioned in direct physical communication with the substrate 211, for example, as a layer on top of the substrate 211. In other embodiments, the electronically conductive layer may be directly impregnated into the substrate (e.g., ITO glass, ITOPET, or ITO PEN) or sandwiched between two substrates 211 to form a single conductive substrate. In some embodiments, where an electronically conductive layer is present, the substrate 211 may be formed of a non-conductive material. In some embodiments, for example, Figure 2 and Figure 3 As shown, the selectively dimmable device 200 may also include a sealant 250. In some embodiments, the sealant 250 encapsulates the liquid crystal element 110 between conductive substrates 210 to protect the element 110 from environmental influences. In some embodiments, the sealant 250 may include a two-part real-time curable epoxy resin, 3-Bond 2087, etc. In some embodiments, the sealant 250 may include a UV-curable photopolymer, such as NOA-61, etc. In some embodiments, such as... Figure 4 As shown, the selectively dimmable device 200 may further include an adhesive layer 260. In some embodiments, the adhesive layer 260 will allow the flexible sheet embodiment of the aforementioned device 200 to be mounted on a pre-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 further include a removable carrier substrate 261 to protect the adhesive layer 260 from contamination that will be peeled off before the device is applied.

[0100] In one or more embodiments, the method of using the polymer-dispersed liquid crystal composition or a film comprising thereof includes a fixation process to generate a liquid crystal polymer by photodimerization of the photoreactive liquid crystal compound and a reset process to generate a photoreactive liquid crystal compound by depolymerization of the liquid crystal polymer. In some embodiments, the fixation process is performed again after the reset process. In some embodiments, the fixation process and / or the reset process are repeated. In some embodiments, the area where the liquid crystal polymer is generated in the second or subsequent fixation process is different from the area where the liquid crystal polymer was generated in the previous fixation process.

[0101] In one or more embodiments, a method for reversibly crosslinking a polymer network may include providing an oligomer or polymer comprising one or more photoreactive liquid crystal compounds described herein; and using 0.1-2500.0 J / cm². 2 For example, 32.4 J / cm 2 Or 673.2 J / cm 2 The oligomer or polymer is irradiated with ultraviolet radiation, wherein the UV radiation has 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 forms, the first crosslinking wavelength is between about 305 nm and about 395 nm. In some embodiments, the method for reversibly crosslinking the polymer network may further include using 0.1 J / cm 2 Up to 2500.0 J / cm 2 For example, 32.4 J / cm 2 Or 673.2 J / cm 2 The crosslinked oligomers or polymers are irradiated with ultraviolet radiation, wherein the UV radiation has a second cleavage wavelength less than 300 nm, 260 nm, 280 nm, 249 nm, and / or 280 nm. In one form, the second cleavage wavelength is 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 previously described, the crosslinking wavelength of 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); and the depolymerization wavelength may be less than 300 nm (anthracene), 260 nm (cinnamic acid), 280 nm (coumarin), 249 nm (thymine), and / or 280 nm (stilbene).

[0102] Example

[0103] It should be understood that the following embodiments are for illustrative purposes and are not intended to be construed as limiting the subject matter disclosed in this document to the implementations disclosed in these embodiments.

[0104] The compounds in the following examples are photoreactive liquid crystal compounds comprising at least two reversible photodimerizing functional groups, which were synthesized and their PDLC properties were evaluated.

[0105] Example 1: Synthesis of liquid crystal compounds and / or monomers

[0106] Generally, the preparation of the compound is carried out in an argon atmosphere (Airgas, San Marcos, CA USA) within a fume hood. Furthermore, degassing can be performed by bubbling argon gas through the compound or by other similar methods.

[0107] RM-1: 2-Methyl-1,4-phenylenebis(4-(3-((2-oxo-2H-benzopyran-7-yl)oxy)propoxy) Synthesis of benzoic acid esters

[0108]

[0109] Methyl 4-(3-chloropropoxy)benzoate. Int-1

[0110]

[0111] K₂CO₃ (MW: 138.21) (20.73 g, 0.15 mol, 1.5 equivalents) was added to a solution of methyl 4-hydroxybenzoate (15.215 g, 0.1 mol) in acetone (230 mL). Then, 1-bromo-3-chloropropane (MW: 157.44, d = 1.592 g / mL) (34.62 g, 21.74 mL, 0.11 mol, 1.1 equivalents) was added, and the mixture was stirred at 76 °C for 8 hours, followed by stirring at room temperature for 16 hours. The precipitate was filtered off. The filtrate was concentrated to give a pale yellow-green transparent oil (22.5 g, 0.098 mmol), in 98% yield. Product Int-1 was used in the next step without further purification.

[0112] 1 ¹H NMR (400MHz, chloroform-d) δ 8.09–7.87 (m, 2H), 7.00–6.84 (m, 2H), 4.18 (t, J = 5.9 Hz, 2H), 3.89 (s, 3H), 3.75 (t, J = 6.2 Hz, 2H), 2.26 (p, J = 6.1 Hz, 2H). LCMS (APCI-), calculated values ​​(M-) for equation: C 11 H 13 ClO3: 228.6; Measured value: 228.

[0113] 4-(3-((2-oxo-2H-benzopyran-7-yl)oxy)propoxy)methyl benzoate.Int-2

[0114]

[0115] 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 under argon atm for 16 hours. The cooled mixture was added to water (100 mL), the precipitate was filtered, washed with water (2 × 50 mL) and MeOH (50 mL x 2), and then dried in a vacuum oven to give 3.31 g of a grayish-white solid, methyl 4-(3-((2-oxo-2H-benzopyran-7-yl)oxy)propoxy)benzoate, in 93.4% yield. Product Int-2 was retained in an amber vial.

[0116] 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 = 9.5 Hz, 1H), 4.23 (td, J = 6.0, 1.5 Hz, 4H), 3.88 (s, 3H), 2.33 (p, J = 6.0 Hz, 2H).

[0117] LCMS(APCI-), calculated value (M-) for formula: C 20 H 18 O6: 354.36; Measured value: 354.

[0118] 4-(3-((2-oxo-2H-benzopyran-7-yl)oxy)propoxy)benzoic acid.Int-3

[0119]

[0120] A solution of 4N NaOH in H₂O (4 mL, 16 mmol, 3.2 equivalences) was added to a mixture of methyl 4-(3-((2-oxo-2H-benzopyran-7-yl)oxy)propoxy)benzoate Int-2 (1.7718 g, 5.0 mmol) in THF (25 mL) and MeOH (4 mL), and the resulting mixture was stirred at 53 °C for 3 h. The reaction was monitored by TLC and LCMS. When 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 and acidified with 6N HCl (4 mL), diluted with water (100 mL), and the white solid was filtered off, washed with water, and then dried in a vacuum oven to give 1.701 g of Int-3 as a grayish-white solid, in quantitative yield.

[0121] 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).

[0122] LCMS(APCI-), calculated value (M-) for formula: C 19 H 16 O6: 340.33; Measured value: 340.

[0123] 2-Methyl-1,4-phenylenebis(4-(3-((2-oxo-2H-benzopyran-7-yl)oxy)propoxy)benzoic acid RM-1 (ester)

[0124]

[0125] 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 anhydrous THF + 5 mL anhydrous DCM + 5 mL Me₂CO was stirred at room temperature under an argon atmosphere for 48 hours. LCMS showed >60% of the desired diester product and 10% of the monoester product; an additional 25 mg of 1643-49 and 11 mg of EDC were added, and stirring continued overnight.

[0126] The next day, the mixture was poured into an NH4Cl solution (0.3 g in 20 mL of water) and extracted twice with CH2Cl2. The combined organic layers were washed with water and dried over MgSO4, then filtered and evaporated under reduced pressure to give 660 mg of crude product as a grayish-white solid after washing with MeOH. The crude product was purified by elution with 80 g SiO2 using a 2.5% EA DCM solution as the eluent to give 319 mg of RM-1 of colorless solid, in a yield of 45%.

[0127] 1 H 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 =8.6,2.8Hz,1H),6.98-6.91(m,4H),6.81(dd,J=8.6,2.4Hz,2H),6.77(d,J=2.4H z, 2H), 6.16 (d, J = 9.5Hz, 2H), 4.25-4.11 (m, 8H), 2.35-2.22 (m, 4H), 2.15 (s, 3H).

[0128] LCMS(APCI-), calculated value (M-) for formula: C 45 H 36 O 12 : 768.77; Measured value: 768.

[0129] RM-2: 2-Methyl-1,4-phenylenebis(4-(3-(anthracene-9-yloxy)propoxy)benzoate)

[0130]

[0131] 4-[3-(anthracite-9-yloxy)propoxy]benzoic acid.Int-4

[0132]

[0133] Step 1: A mixture of methylInt-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 under argon atm for 16 hours. The cooled mixture was added to water (350 mL), acidified with 4N HCl, extracted into EA (2 x 350 mL), and the organic layers were combined. The mixture was washed with water (2 x 100 mL) and then concentrated to dryness. The crude yellow solid was used directly in the next step without further purification, yielding 7.5 g (97% yield). The product was stored in an amber vial.

[0134] Step 2: A solution of 4N NaOH in H₂O (10 mL, 40 mmol) (2 mL, 8 mmol) was added to the mixture of (5.28 g, 20.0 mmol) in THF (75 mL) and MeOH (25 mL) from the previous step; the resulting mixture was stirred at 53 °C for 3 hours. The reaction was monitored by TLC and LCMS. When 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 and acidified with 6N HCl (10 mL) and diluted with water (100 mL). The white solid was filtered off, washed with water and MeOH, and then dried in a vacuum oven to give 2.887 g of Int⁻⁴ as a grayish-white solid, with an overall yield of 38% for both steps.

[0135] 1 H 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), 7.35-7.29 (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).

[0136] LCMS(APCI-), calculated value (M-) for formula: C 24 H 20 O4: 372.4; Measured value: 372.

[0137] 2-Methyl-1,4-phenylenebis(4-(3-(anthracene-9-yloxy)propoxy)benzoate)RM-2:

[0138]

[0139] At room temperature, under an argon atmosphere, a solution of Int-4 (2.188 g, 5.876 mmol, 2.06 equivalences), methylhydroquinone (0.354 g, 2.851 mmol, 1 equivalence), EDC (1.238 g, 6.463 mmol, 2.26 equivalences), and DMAP (107.6 mg, 0.881 mmol, 0.309 equivalences) in 50.0 mL of anhydrous THF and 30 mL of anhydrous DCM was stirred for 48 hours. LCMS showed >60% of the desired diester product and 10% of the monoester product; additional 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 an NH4Cl solution (0.9 g in 60 mL of water) and extracted twice with CH2Cl2 (2 x 250 mL). The combined organic layers were washed with water, dried over MgSO4, filtered, and evaporated under reduced pressure. After washing with MeOH, 2.02 g of a grayish-white solid crude product was obtained. The crude product was purified by eluting with 80 g of SiO2 using a solution of 2.5% EA in DCM as the eluent, yielding 0.83 g of RM-2 as a colorless solid, in a yield of 35%.

[0140] 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),7.1 5(d,J=8.7Hz,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).

[0141] LCMS(APCI-), calculated value (M-) for formula: C 55 H 44 O8: 832.95; Measured value: 832.

[0142] RM-3: 2-Methyl-1,4-phenylenebis(4-(3-(4-((E)-3-butoxy-3-oxopropyl-1-en-1-yl)benzene) Synthesis of (oxy)propoxy)benzoate (1643-59)

[0143]

[0144]

[0145] 4-(3-(4-iodophenoxy)propoxy)benzoic acid.Int-6

[0146]

[0147] 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 equivalent), anhydrous potassium carbonate (2.75 g, 19.895 mmol, 1.99 equivalent), and anhydrous DMF (20 mL) was stirred at 90 °C under argon atm for 4 hours. The solid was filtered, and the crude solid product methyl 4-(3-(4-iodophenoxy)propoxy)benzoate was washed with hexane and dried in a vacuum oven at 65 °C for 3 hours to give 3.8173 g of off-white solid methyl 4-(3-(4-iodophenoxy)propoxy)benzoate, 92.6% yield.

[0148] 1 ¹H NMR (400 MHz, chloroform-d) δ 8.01–7.96 (m, 2H), 7.57–7.53 (m, 2H), 6.94–6.90 (m, 2H), 6.71–6.66 (m, 2H), 4.20 (t, J = 6.1 Hz, 2H), 4.12 (t, J = 6.0 Hz, 2H), 3.88 (s, 3H), 2.27 (p, J = 6.1 Hz, 2H).

[0149] Step 2: A solution of 4N NaOH in H₂O (7.4 mL, 29.63 mmol, 3.2 equivalences) was added to a mixture of the product from the previous step (3.8173 g, 9.26 mmol) in THF (50 mL) and MeOH (8 mL), and the resulting mixture was stirred at 53 °C for 3 hours. The reaction was monitored by TLC, and when complete, it was cooled to 0 °C and acidified with 6N HCl (~4 mL), followed by extraction with 100 mL EA. The organic layer was separated, dried with MgSO₄, concentrated, and the white solid was washed with water, filtered, and then dried in a vacuum oven to give 3.68 g of colorless solid Int₆, in quantitative yield.

[0150] LCMS(APCI-), calculated value (M-) for formula: C 16 H 15 IO4: 398.2; Measured value: 398.

[0151] 4-((4-(3-((4-iodocyclohexyl-1,3-dien-1-yl)oxy)propoxy)benzoyl)oxy)-2-methylphenyl 4-(3-(4-iodophenoxy)propoxy)benzoate.Int-7

[0152]

[0153] At room temperature and under an argon atmosphere, a mixture of Int-6 (2.339 g, 5.876 mmol, 2.06 equivalents), EDC (1.238 g, 6.463 mmol, 2.26 equivalents) in 50.0 mL of anhydrous DCM was stirred for 10 minutes. The mixture became a pale yellow solution. At room temperature, a mixture of methylhydroquinone (0.354 g, 2.851 mmol, 1 equivalent), EDC, and DMAP (107.6 mg, 0.881 mmol, 0.309 equivalents) in 10.0 mL of anhydrous THF was added via syringe and needle. The resulting mixture was stirred for 24 h under an argon atmosphere. LCMS showed >60% of the desired diester product and 10% of the monoester product. Add 1643-49 (148.5 mg, 0.436 mmol), EDC (91.9 mg, 0.479 mmol), and DMAP (2.71 mg, 0.022 mmol), and stir the resulting mixture overnight. The next day, pour the mixture into NH4Cl solution (0.9 g in 60 mL of water), stir for 10 minutes, and collect the white solid by filtration. Extract the filtrate twice with CHCl3 (150 mL). Combine the crude solids from the filtration and filtrate, and purify by column chromatography using an 80 g SiO2 column with 2.5% EA in DCM solution as the eluent to give 3.5 g of colorless Int-7 solid in 85% yield.

[0154] 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).

[0155] LCMS(APCI-), calculated value (M-) for formula: C 39 H 36 I2O8: 884.5; Measured value: 884.

[0156] 2-Methyl-1,4-phenylenebis(4-(3-(4-((E)-3-butoxy-3-oxopropyl-1-en-1-yl)phenoxy)propoxy)benzoate)(1643-59)

[0157]

[0158] 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 eq), and PPh3 (15.73 mg, 0.06 mmol, 0.06 eq) 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 under an argon atmosphere for 16 hours. After cooling to room temperature, the mixture was quenched with 1 M HCl aqueous solution (1 mL) and extracted into CHCl3 (3 x 10 mL). The organic phase was washed with water, dried over Na2SO4, filtered, and concentrated under vacuum to obtain the crude product. It was purified by SiO2 column chromatography, eluting with Hex:DCM (1:1), to give 0.454 g of a colorless solid of RM-3, in 55% yield.

[0159] 1 H NMR (400MHz, chloroform-d) δ8.21-8.10(m,4H),7.63(d,J=15.9Hz,2H),7.51-7.42(m,4H),7.1 7(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, 4H), 1.68 (dq, J = 8.6, 6.8Hz, 4H), 1.49-1.38 (m, 4H), 0.96 (t, J = 7.4Hz, 6H).

[0160] LCMS(APCI-), calculated value (M-) for formula: C 53 H 56 O 12 : 885.02; Measured value: 885.

[0161] RM-4: 1,3,5-Tris(3-(anthracite-9-yloxy)propoxy)benzene)

[0162]

[0163] 9-(3-Chloropropoxy)anthracene.Int-8

[0164]

[0165] Under a nitrogen atmosphere and at ambient temperature, 1-bromo-3-chloropropane (12.58 g, 80 mmol) was added to a solution of anthrone (7.768 g, 40 mmol) in 50.0 mL of acetone, followed by the addition of K₂CO₃ (MW: 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 give 14.69 g of a deep yellow semi-solid, which was washed with hexane to give 11.7 g of a pale yellow solid, with a yield of 48%. The product Int-8 was used in the next step without further purification.

[0166] 1 ¹H NMR (400MHz, chloroform-d) δ 8.30–8.23 (m, 2H), 8.21 (s, 1H), 8.01–7.95 (m, 2H), 7.46 (tt, J = 6.6, 5.0 Hz, 4H), 4.33 (t, J = 5.9 Hz, 2H), 4.03 (t, J = 6.3 Hz, 2H), 2.47 (p, J = 6.1 Hz, 2H).

[0167] LCMS(APCI-), calculated value (M-) for formula: C 17 H 15 ClO: 270.76 Measured value: 270.

[0168] Synthesis of 1,3,5-tris(3-(anthracene-9-yloxy)propoxy)benzene)RM-4

[0169]

[0170] 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 under an argon atmosphere for 16 hours. The cooled mixture was added to water (4 mL), acidified with 4N HCl, and extracted into EA (2 x 35 mL). The organic layers were combined, washed with water (2 x 10 mL), and 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 RM-4 as a colorless solid, in 32% yield. The product was stored in amber vials.

[0171] 1H 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), 6.40 (s, 3H), 4.47 (t, J = 5.9Hz, 6H), 4.42 (t, J = 6.1Hz, 6H), 2.52 (p, J = 6.0Hz, 6H).

[0172] LCMS(APCI-), calculated value (M-) for formula: C 57 H 48 O6: 829.01; Measured value: 829.

[0173] Synthesis of RM-5: 1,3,5-tris(3-(anthracene-9-yloxy)propoxy)benzene)(1643-79)

[0174]

[0175] 9-(6-bromohexyl)oxy)anthracene)Int-9

[0176]

[0177] Under a nitrogen atmosphere and at ambient temperature, 1,6-dibromohexane (39.02 g, 24.24 mL, 160.0 mmol, 4 equivalents) was added to a stirred solution of anthrone (7.768 g, 40.0 mmol) in 50.0 mL of acetone, followed by the addition of potassium carbonate (8.292 g, 60.0 mmol), and the mixture was then heated to 50 °C for 8 hours. The reaction was monitored by TLC until no SM-anthrone residue remained. 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 give a light brown crude product, which was purified by SiO2 column chromatography with eluent Hex:EA (9:1) to give 6.4 g Int-9 in 45% yield.

[0178] 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)

[0179] Synthesis of 9,9'-((((5-((7-(anthracene-9-yloxy)heptyl)oxy)-1,3-phenylene)bis(oxy))bis(hexane-6,1-diyl))bis(oxy))dianthracene

[0180]

[0181] 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 under an argon atmosphere for 16 hours. The cooled mixture was added to water (4 mL), acidified with 4N HCl, and extracted into EA (2 x 35 mL). The organic layers were combined, washed with water (2 x 10 mL), and 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 RM-5 as a viscous solid, in 15% yield.

[0182] 1 H NMR (400MHz, chloroform-d) δ8.36-8.24(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=6.6H z, 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).

[0183] LCMS(APCI-), calculated value (M-) for formula: C 67 H 68 O6: 969.28; Measured value: 969.

[0184] RM-6: 1,3,5-Tris(3-(Anthracene-9-yloxy)propoxy)benzene)

[0185]

[0186]

[0187] 2-Methyl-1,4-phenylenebis(4-acetoxybenzoate)Int-11

[0188]

[0189] 13.888 mL (0.194 mol) of thionyl chloride was added dropwise to 25.0 g (0.138 mol) of 4-acetoxybenzoic acid in a 100 mL single-necked round-bottom flask, and the mixture was stirred and gently refluxed for 8 hours. The initial heterogeneous mass was homogenized to obtain a pale yellow fluid. Excess thionyl chloride was removed by rotary evaporation at 26 °C. Toluene (15 mL) was added to the residue, and the resulting mixture was concentrated by rotary evaporation at 45 °C.

[0190] The crude acyl chloride was purified by double distillation under reduced pressure, yielding 27 g of a pale yellow liquid, 4-acetoxybenzoyl chloride, Int-10, which subsequently became a colorless solid. Yield: 99%.

[0191] 1 ¹H NMR (400 MHz, chloroform-d) δ 2.1 [3H, s], 7.1 [2H, d] and 8.0 [2H, d].

[0192] Step 2: A mixture of 4.96 g (0.04 mol) of 2-methylhydroquinone 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 acyl chloride solution was added to the 2-methylhydroquinone solution. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 48 hours. The reaction mixture was washed successively with 5% sodium carbonate solution, 5% hydrochloric acid, and distilled water. The 1,2-dichloroethane layer was evaporated to dryness on a rotary evaporator. The crude product was recrystallized from chloroform / petroleum ether (60:80). The product was filtered and dried in a vacuum oven at 80 °C for 4 h to give 15.24 g of light brown solid Int-11, 85% yield.

[0193] 1 ¹H NMR (400 MHz, chloroform-d) δ 2.2 (3H, s), 2.3 (6H, s), 7.4 (8H, d) and 8.4 (3H, d).

[0194] LCMS(APCI-), calculated value (M-) for formula: C 25 H 20 O8: 448.43; Measured value: 448.

[0195] 2-Methyl-1,4-phenylenebis(4-hydroxybenzoate).Int-12

[0196]

[0197] 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, stirred in a 1 L single-necked round-bottom flask. The resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was pale yellow. The solvent was removed under reduced pressure. The residue was washed with H2O and dried in a vacuum oven to give 11.0 g of a light brown solid. The product Int-11 was used in the next step without further purification. 99% yield.

[0198] 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=5.9 Hz, 1H), 7.23 (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).

[0199] LCMS(APCI-), calculated value (M-) for formula: C 21 H 16 O6: 364.35; Measured value: 364.

[0200] 1,3,5-Tris(3-(anthracite-9-yloxy)propoxy)benzene)RM-6

[0201]

[0202] Under a nitrogen atmosphere and at ambient temperature, 9-((6-bromohexyl)oxy)anthracene (3.572 g, 10.0 mmol) was added to a stirred solution of 2-methyl-1,4-phenylene bis(4-hydroxybenzoate) (1.45 g, 4.0 mmol) in 4.0 mL of anhydrous DMF, followed by the addition of potassium carbonate (1.658 g, 12.0 mmol). The mixture was then heated to 85 °C for 8 hours. LC-MS showed the formation of a di-coupled product plus a mono-coupled product and the SM residue. The reaction mixture was then stirred at 78 °C for 6 hours. 500 mL of CHCl3 was added to the RX mixture at room temperature, followed by 100 mL of cold water (ice + water). 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, eluting only with DCM followed by DCM:EtAcO (95:5). 3.0 g of light brown solid was obtained, and it was recrystallized with MeOH to obtain a colorless solid product of RM-6.

[0203] 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),7.54-7.41(m,8H),7.18(d,J=8.7 Hz,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=6.6 Hz, 4H), 4.12 (td, J = 6.6 Hz, 4H), 1.95 (p, J = 6.7 Hz, 4H), 1.79 (t, J = 8.1 Hz, 3H), 1.68 (p, J = 7.4, 6.9 Hz, 4H).

[0204] LCMS(APCI-), calculated value (M-) for formula: C 61 H 56 O8: 917.11; Measured value: 917.

[0205] RM-7: 1,3,5-Tris((5-(anthracene-9-yloxy)pentyl)oxy)benzene

[0206]

[0207] 9-((5-bromopentyl)oxy)anthracene.Int-13

[0208]

[0209] Under a nitrogen atmosphere and at ambient temperature, 1,3-dibromopentane (36.79 g, 21.9 mL, 160.0 mmol, 4 equivalents) was added to a stirred solution of anthrone (7.768 g, 40.0 mmol) in 50.0 mL of acetone, followed by the addition of potassium carbonate (8.292 g, 60.0 mmol). The mixture was then heated to 50 °C for 8 hours. The reaction was monitored by TLC until no anthrone residue remained. The reaction mixture was cooled to room temperature, and the solid was filtered off and washed with 100 mL of acetone. The filtrate was 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 followed by Hex:DCM (95:5) to give 4.5 g of a white solid, Int-13, which was dried in a vacuum oven and used for the next step without further purification. 32% yield.

[0210] 1 ¹H NMR (400MHz, 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).

[0211] LCMS(APCI-), calculated value (M-) for formula: C 19 H 19 BrO: 343.26; Measured value: 343.

[0212] 1,3,5-Tris((5-(anthracene-9-yloxy)pentyl)oxy)benzeneRM-7

[0213]

[0214] A mixture of Int-13 (1.132 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 (25 mL) was stirred at 85 °C under an argon atmosphere for 6 hours. The cooled mixture was filtered, the filtrate was concentrated, and the crude solid product was purified by SiO2 column chromatography using hexane:EA (9:1) as the eluent to obtain 98 mg of colorless RM-7 solid, in 10% yield.

[0215] 1H NMR (400MHz, chloroform-d) δ8.34-8.24(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=6.5Hz, 6H), 4.03 (t, J=6.2Hz, 6H), 2.12 (p, J=6.7Hz, 6H), 1.94 (q, J=6.7, 6.0Hz, 6H), 1.87 (q, J=8.7, 8.2Hz, 6H).

[0216] LCMS(APCI-), calculated value (M-) for formula: C 63 H 60 O6: 913.17; Measured value: 913.

[0217] RM-8: Synthesis of 1,3,5-tris((5-(anthracene-9-yloxy)pentyl)oxy)benzene

[0218]

[0219] Under a nitrogen atmosphere and at ambient temperature, 1643-81 (1.586 g, 4.62 mmol, 2.2 equivalences) was added to a stirred solution of 9-((5-bromopentyl)oxy)anthracene (0.765 g, 2.1 mmol) in 4.0 mL of anhydrous DMF, followed by the addition of potassium carbonate (0.58 g, 4.2 mmol), and then heated to 85 °C and held for 12 hours. LC-MS showed the formation of a double-coupled product plus a single-coupled product and the SM residue. The reaction mixture was cooled to room temperature and the solid was filtered off. The filtrates were combined and concentrated by rotary evaporation at 50 °C, and the residue was milled with water to obtain 1.5 g of a light brown solid product, which was purified by SiO2 column chromatography with hexane:EtAco (9:1 → 4:1) to obtain 0.42 g of RM-8 as a colorless solid, 22% yield.

[0220] 1 ¹H NMR (400MHz, chloroform-d) δ 8.35–8.26 (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 = 8.7 Hz, 1H), 7.14 (d, J = 2.7 Hz, 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, 3H), 2.16 (p, J = 6.8Hz, 4H), 2.02 (dd, J = 13.9, 6.7Hz, 4H), 1.92 (q, J = 8.3Hz, 4H).

[0221] LCMS(APCI-), calculated value (M-) for formula: C 59 H 52 O8: 889.06; Measured value: 889.

[0222] RM-9: 7,7′,7″-(((benzene-1,3,5-triyltri(oxy))tri(pentane-5,1-diyl))tri(oxy))tri Synthesis of (2H-benzopyran-2-one)

[0223]

[0224] 1,3,5-Tris((5-bromopentyl)oxy)benzene.Int-14

[0225]

[0226] Under a nitrogen atmosphere and at ambient temperature, 1,5-dibromopentane (55.184 g, 240 mmol, 12 equivalents) was added to a stirred solution of phloroglucinol (2.522 g, 20.0 mmol) in 120.0 mL of acetonitrile, followed by potassium carbonate (33.168 g, 240.0 mmol). The mixture was then heated to 85 °C and held for 16 hours. The reaction was monitored by TLC until no SM-reporoglucinol residue remained. 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 followed by Hex:EA (9:1) to give 4.58 g of colorless liquid Int-14; this compound could be used for the next step without further purification. 40% yield.

[0227] 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).

[0228] LCMS(APCI-), calculated value (M-) for formula: C 21 H 33 Br3O3: 573.2; Measured value: 573.

[0229] RM-9.7,7',7"-(((benzene-1,3,5-triyltri(oxy))tri(pentane-5,1-diyl))tri(oxy))tri(2H-benzopyran-2-one)

[0230]

[0231] Under a nitrogen atmosphere and at ambient temperature, 1643-85 (573.2 mg, 2 mmol, 1 equivalent) was added to a stirred solution of coumarin (973 mg, 6.0 mmol) in 12.0 mL of anhydrous DMF, followed by the addition of potassium carbonate (1.658 g, 12 mmol). The mixture was then heated to 85 °C for 6 hours. The reaction was monitored by TLC until no SM coumarin residue remained. The reaction mixture was cooled to room temperature and diluted with 50 mL of DMF. The solid was filtered and washed with 100 mL of acetone. The filtrates were combined and concentrated under reduced pressure to obtain a red-orange residue, which was milled with water (50 mL). The light brown solid product was loaded onto an 80 g SiO2 column, eluted with DCM, and then eluted with DCM:EA (4:1) to obtain 450 mg of RM-9 as a viscous, colorless solid in 27% yield.

[0232] 1 H NMR (400MHz, chloroform-d) δ7.63(d,J=9.5Hz,3H),7.36(d,J=8.5Hz,3H),6.87-6.81(m,3H),6.82-6.77(m,3H),6.25(d,J=9. 5Hz, 3H), 6.07 (s, 3H), 4.04 (t, J = 6.4Hz, 6H), 3.95 (t, J = 6.3Hz, 6H), 1.87 (tt, J = 14.5, 6.5Hz, 13H), 1.72-1.60 (m, 7H).

[0233] LCMS(APCI-), calculated value (M-) for formula: C 48 H 48 O 12 : 816.9; Measured value: 816.

[0234] RM-10: 7,7',7"-(((benzene-1,3,5-triyltri(oxy))tri(hexane-6,1-diyl))tri(oxy))tri Synthesis of 2H-benzopyran-2-one

[0235]

[0236]

[0237] 1,3,5-Tris((6-bromohexyl)oxy)benzene.Int-15

[0238]

[0239] Under a nitrogen atmosphere and at ambient temperature, 1,6-dibromohexane (29.276 g, 120 mmol, 12 equivalents) was added to a stirred solution of resorcinol (1.261 g, 10.0 mmol) in 50.0 mL of acetone, followed by potassium carbonate (16.584 g, 120.0 mmol). The mixture was then heated to 50 °C for 8 hours. The reaction was monitored by TLC until no resorcinol residue remained. The reaction mixture was cooled to room temperature, the solid was filtered off and washed with 100 mL of acetone, and the filtrates were combined and concentrated under reduced pressure to give a red-orange residue. This residue was loaded onto a 220 g SiO2 column and eluted with hexane followed by Hex:EA (9:1) to give 1.45 g of colorless liquid Int-15, which was dried in a vacuum oven and used for the next step without further purification. Yield: 23%

[0240] 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).

[0241] LCMS(APCI-), calculated value (M-) for formula: C 24 H 39 Br3O3: 615.29; Measured value: 615.

[0242] RM-10.7,7',7"-(((benzene-1,3,5-triyltri(oxy))tri(hexane-6,1-diyl))tri(oxy))tri(2H-benzopyran-2-one)

[0243]

[0244] Under a nitrogen atmosphere and at ambient temperature, Int-15 (473.4 mg, 0.768 mmol, 1 equivalent) was added to a stirred solution of coumarin (498.5 mg, 3.075 mmol, 4 equivalents) in 6.0 mL of anhydrous DMF, followed by potassium carbonate (0.424 g, 3.072 mmol, 4 equivalents). The mixture was then heated to 75 °C and held for 16 hours. The reaction was monitored by TLC until no SM coumarin residue remained. The reaction mixture was cooled to room temperature and diluted with 10 mL of DMF. The solid was filtered and washed with 50 mL of acetone, and the filtrates were combined and concentrated under reduced pressure to obtain a red-orange residue, which was then milled with water (50 mL). The light brown solid product was loaded onto an 80 g SiO2 column, eluted with DCM, and then eluted with DCM:EA (4:1) to give 0.47 g of colorless, viscous solid RM-10; yield 68%.

[0245] 1 H NMR (400MHz, chloroform-d) δ7.63(d,J=9.5Hz,3H),7.36(d,J=8.5Hz,3H),6.83(dd,J=8.5,2.5Hz,3H),6.80(d,J=2.4Hz,3H),6.24(d,J =9.5Hz, 3H), 6.06 (s, 3H), 4.02 (t, J = 6.4Hz, 6H), 3.93 (t, J = 6.4Hz, 6H), 1.82 (dt, J = 18.1, 6.6Hz, 12H), 1.54 (t, J = 3.9Hz, 12H).

[0246] LCMS(APCI-), calculated value (M-) for formula: C 51 H 54 O 12 : 858.98; Measured value: 858.

[0247] RM-11: 5-((3-((5-(anthracene-9-yloxy)pentyl)oxy)benzoyl)oxy)-1,3-phenylenebis(4- ((5-(anthracene-9-yloxy)pentyl)oxy)benzoate)

[0248]

[0249]

[0250] 4-((5-bromopentyl)oxy)methyl benzoate. Int-16

[0251]

[0252] Under a nitrogen atmosphere and at ambient temperature, 1,5-dibromopentane (24.833 g, 108 mmol) was added to a stirred solution of methyl 4-hydroxybenzoate (4.108 g, 27.0 mmol) in 20.0 mL of dimethylformamide, 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, and 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 with hexane:EA (9:1) to obtain 7.3 g of colorless liquid Int-16; yield 89%.

[0253] 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),3.8 8(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).

[0254] LCMS(APCI-), calculated value (M-) for formula: C 13 H 17 BrO3: 301.18; Measured value: 301.

[0255] 4-((5-(anthracene-9-yloxy)pentyl)oxy)methyl benzoate.Int-17

[0256]

[0257] Step 1: Under a nitrogen atmosphere and at ambient temperature, Int-16 (3.018 g, 10.0 mmol) was added to a stirred solution of anthrone (1.9423 g, 10.0 mmol) in 10.0 mL of dimethylformamide, 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. The insoluble matter was washed with ethyl acetate. The filtrates were combined and concentrated. The residue was washed with 1.01 mL of cold water, followed by 1.01 mL of heptane. The crude product was purified by SiO2 column chromatography using only hexane → hexane:DCM (1:1) to give 3.02 g of a light orange viscous liquid, Int-17; yield 72%. The product contained some anthrone SM and was used in the next step without further purification.

[0258] 1H NMR (400MHz, chloroform-d) δ8.32-8.24(m,2H),8.22(s,1H),8.10-8.03(m,2H),8.03-7.95(m,2H),7.52-7.41(m,4H),6.9 7(d,J=9.0Hz,2H),4.25(t,J=6.5Hz,2H),4.14(t,J=6.3Hz,2H),2.14(dt,J=14.1,6.7Hz,2H),2.05-1.85(m,5H).

[0259] LCMS(APCI-), calculated value (M-) for formula: C 27 H 26 O4: 414.5; Measured value: 414.

[0260] Step 2: A solution of 4N NaOH in H₂O (7.4 mL, 29.63 mmol, 3.2 equivalences) was added to a mixture of the product from the previous step (3.0 g, 7.2 mmol) in THF (50 mL) and MeOH (8 mL). The resulting mixture was stirred at 53 °C for 3 hours. The reaction was monitored by TLC. When complete, it was cooled to 0 °C and acidified with 6N HCl (~4 mL), then extracted with 100 mL EA. The organic layer was separated, dried with MgSO₄, and concentrated. The white solid was washed with water, filtered, and then dried in a vacuum oven to give 2.68 g of colorless solid Int-17, 95% yield.

[0261] 1 ¹H NMR (400MHz, chloroform-d) δ 8.33–8.25 (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 = 6.5 Hz, 2H), 4.14 (t, J = 6.2 Hz, 2H), 2.20–2.09 (m, 2H), 2.01 (dt, J = 13.4, 6.6 Hz, 2H)

[0262] LCMS(APCI-), calculated value (M-) for formula: C 26 H 24 O4: 400.47; Measured value: 400.

[0263] Benzene-1,3,5-triyltris(4-((5-(anthracene-9-yloxy)pentyl)oxy)benzoate).RM-11

[0264]

[0265] 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 added 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 at room temperature for 16 hours under an argon atmosphere. More 1643-92 (324 mg) and EDC.HCl (298 mg) were added. The resulting mixture was stirred for another 3 hours. H2O (10 mL) was added, and the mixture was stirred for another 15 minutes. The organic layer was separated, concentrated to a volume of 20 mL, loaded into a 40 g SiO2 column, and eluted with Hex-DCM (7 / 3), followed by gradual elution with DCM only. The pure fraction was collected, concentrated, and dried in a vacuum oven to give 470 mg of colorless solid RM-11; yield 37%.

[0266] 1 H 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).

[0267] LCMS(APCI-), calculated value (M-) for formula: C 84 H 72 O 12 : 1273.49; Measured value: 1273.

[0268] RM-12: 1,3,5-Tris(4-(Anthracene-9-yloxy)butoxy)benzene

[0269]

[0270]

[0271] 9-(4-bromobutoxy)anthracene.Int-18

[0272]

[0273] Under a nitrogen atmosphere and at ambient temperature, potassium carbonate (5.694 g, 41.2 mmol) was added to a stirred solution of anthrone (4.0 g, 20.6 mmol) in 20.0 mL of anhydrous DMF, followed by the addition of 1,4-dibromobutane (18 g, 83.36 mmol). The mixture was then heated to 65 °C for 8 hours. The reaction was monitored by TLC until no anthrone residue remained and the reaction mixture turned pale beige. 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 an orange product, which was loaded onto a 220 g SiO2 column and eluted with hexane, followed by Hex:DCM (95:5) to give 3.5 g of a white solid, Int-18, which was dried in a vacuum oven and used in the next step without further purification, in 51% yield.

[0274] 1 H NMR (400MHz, chloroform-d) δ8.29-8.25(m,1H),8.24(dt,J=2.8,1.0Hz,1H),8.22(s,1H),8.00(tt,J=2.2,1.4 Hz,1H),7.98(dd,J=1.9,1.2Hz,1H),7.51-7.41(m,4H),4.23(t,J=6.2 Hz,2H),3.61(t,J=6.6Hz,2H),2.39-2.26(m,2H),2.26-2.15(m,2H).

[0275] LCMS(APCI-), calculated value (M-) for formula: C 18 H 17 BrO: 329.24; Measured value: 329.

[0276] 1,3,5-Tris(4-(anthracite-9-yloxy)butoxy)benzene.RM-12

[0277]

[0278] 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 for 16 hours at 85 °C under an argon atmosphere. The cooled mixture was filtered, the filtrate was concentrated, and the crude solid product was washed with water and then loaded onto an 80 g SiO2 column, eluted with hexane:DCM / DCM only. Fractions 8-10 were collected and concentrated to give 1.2 g of colloidal solid, 68% yield. NMR showed some impurities. The above impure product was loaded onto a second 80 g SiO2 column and eluted with Hex:EA (100%→20%) to give a grayish-white solid, which was ground with ethyl acetate to give 0.85 g of colorless RM-12 solid, 48% yield.

[0279] 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).

[0280] LCMS(APCI-), calculated value (M-) for formula: C 60 H 54 O6: 871.09; Measured value: 871.

[0281] RM-13: Benzene-1,3,5-triyltris(4-(3-(anthracene-9-yloxy)propoxy)benzoate)

[0282]

[0283]

[0284] 4-((4-(anthracite-9-yloxy)butoxy)methyl)benzoic acid.Int-19

[0285]

[0286] Step 1: Under a nitrogen atmosphere and at ambient temperature, methyl 4-hydroxybenzoate (1.67 g, 11 mmol) was added to a stirred solution of Int-18 (3.29 g, 10.0 mmol) in 10.0 mL of dimethylformamide, 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. The insoluble matter was washed with ethyl acetate. The filtrates were combined and concentrated to dryness. The residue was washed with cold water, followed by hexane, to give 4.14 g of a grayish-white solid product, which was used in the next step without further purification.

[0287] Step 2: A solution of 4N NaOH in H₂O (10 mL, 40 mmol) was added to the above mixture (4.0 g) of THF (50 mL) and MeOH (5 mL). The resulting mixture was stirred at 45 °C for 12 hours. The reaction was monitored by TLC and LCMS. When the conversion was complete, the reaction mixture was poured into water (100 mL). The off-white solid product was washed with water. Acetone was added, followed by DCM, and then the mixture was dried in a vacuum oven to give 3.9 g of off-white solid Int-19, with an overall yield of 90% for both steps.

[0288] 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).

[0289] LCMS(APCI-), calculated value (M-) for formula: C 26 H 24 O4: 400.47; Measured value: 400.

[0290] Benzene-1,3,5-triyltris(4-(4-(anthracene-9-yloxy)butoxy)benzoate)RM-13

[0291]

[0292] 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 added 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 at room temperature under an argon atmosphere for 16 hours. The mixture was then stirred for another 3 hours. H2O (10 mL) was added, and the mixture was stirred for another 15 minutes. The organic layer was separated, concentrated to a volume of 20 mL, and loaded into an 80 g SiO2 column; eluted with Hex-DCM (7 / 3), then gradually reduced to DCM only. The pure fraction was collected, concentrated, and dried in a vacuum oven to give 570 mg of RM-13 as a colorless solid, in 77% yield.

[0293] 1 ¹H NMR (400MHz, chloroform-d) δ 8.34–8.25 (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 = 5.1 Hz, 2H), 4.28–4.19 (m, 2H), 2.27 (p, J = 3.0 Hz, 4H).

[0294] LCMS(APCI-), calculated value (M-) for formula: C 81 H 66 O 12 : 1231.4; Measured value: 1231.

[0295] RM-14: 2-Methyl-1,4-phenylenebis(4-(4-(anthracene-9-yloxy)butoxy)benzoate)

[0296]

[0297] 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 added with DCE:CHCl3 (1:1) (45 mL), followed by methylhydroquinone (0.124 g, 1 mmol, 1 equivalent). The resulting mixture was stirred at room temperature under an argon atmosphere for 16 hours. The mixture was then stirred for another 3 hours. H2O (10 mL) was added, and the mixture was stirred for another 15 minutes. The organic layer was separated, concentrated to a volume of 20 mL, and loaded into an 80 g SiO2 column; eluted with Hex-DCM (7 / 3), then gradually reduced to DCM only. The pure fraction was collected, concentrated, and dried in a vacuum oven to give 730 mg of RM-14 as a colorless solid, in 85% yield.

[0298] 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).

[0299] LCMS(APCI-), calculated value (M-) for formula: C 57 H 48 O8: 861.00; Measured value: 861.

[0300] RM-15: 5-(anthracene-9-yloxy)pentyl 2,4,6-tris((5-(anthracene-9-yloxy)pentyl)oxy)benzoate

[0301]

[0302] 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 under an argon atmosphere for 16 hours. The cooled mixture was filtered, and the filtrate was concentrated. The crude solid was washed with water and then loaded onto an 80 g SiO2 column, eluted with hexane:DCM→DCM only. Fractions 8–10 were collected and concentrated to a gel-like solid, which was then ground with ethyl acetate to obtain 0.250 g of RM-15 as a grayish-white solid, in 40% yield.

[0303] 1 ¹H NMR (400MHz, chloroform-d) δ 8.31–8.24 (m, 2H), 8.24–8.14 (m, 6H), 8.13 (d, J = 2.1 Hz, 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, 4H), 1.89 (tt, J=14.9, 7.5Hz, 10H), 1.79 (q, J=7.7Hz, 6H), 1.66-1.58 (m, 2H).

[0304] LCMS(APCI-), calculated value (M-) for formula: C 83 H 78 O9: 1219.53; Measured value: 1219.

[0305] RM-16: 5-(anthracene-9-yloxy)pentyl 2,4,6-tris((5-(anthracene-9-yloxy)pentyl)oxy)benzoate

[0306]

[0307] 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 for 16 hours at 75 °C under an argon atmosphere. The cooled mixture was filtered, and the filtrate was concentrated. The crude solid was washed with water and then loaded onto an 80 g SiO2 column, eluted with hexane:DCM→DCM only, to give a gelatinous solid. This solid was ground with ethyl acetate to give 0.275 g of RM-16 as a grayish-white solid; yield 47%.

[0308] 1 ¹H NMR (400MHz, chloroform-d) δ 8.32–8.25 (m, 2H), 8.24–8.16 (m, 5H), 8.15 (s, 2H), 8.12–8.07 (m, 2H), 8.05 (s, 1H), 8.02–7.90 (m, 6H), 7.84 (d, J = 8.4 Hz, 2H), 7.51–7.42 (m, 4H), 7.43–7.34 (m, 8H), 7.34 -7.28(m,2H),6.23(s,2H),4.41(d,J=5.9Hz,2H),4.26(s,2H),4.16(d,J=5.9Hz,2H),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),2.10(d,J=3.2Hz,4H).

[0309] LCMS(APCI-), calculated value (M-) for formula: C 83 H 78 O9: 1163; Measured value: 1163.

[0310] RM-17: 2-Methyl-1,4-phenylene bis(3,5-bis(4-(anthracene-9-yloxy)butoxy)benzoate)

[0311]

[0312] 3,5-Bis(4-(Anthracene-9-yloxy)butoxy)benzoic acid.Int-20

[0313]

[0314] 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, followed by stirring at 75 °C under argon for 8 hours. The cooled mixture was filtered, and the filtrate was concentrated. The crude solid was washed with water and then loaded onto an 80 g SiO2 column, eluted with hexane:DCM→DCM only, to give 1.1 g of a colorless, viscous solid in 82% yield.

[0315] 1 ¹H NMR (400MHz, chloroform-d)δ

[0316] 8.33-8.24(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).

[0317] LCMS(APCI-), calculated value (M-) for formula: C 44 H 40 O5: 664; Measured value: 664.

[0318] Step 2: Dissolve the mixture of the above compounds in 16 mL of THF / MeOH (15 / 1) and add 10 mL of 4N NaOH aqueous solution (40 mmol). Stir the resulting mixture at 45 °C for 5 hours. After cooling to 0 °C, acidify with 4N HCl. Extract the product into CHCl3. Separate the organic layer, wash with water, and concentrate to dryness. Purify the crude product by SiO2 column chromatography, eluting with DCM only, to give 1.0 g of colorless solid Int-20.

[0319] 1 H 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, 2H), 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).

[0320] LCMS(APCI-), calculated value (M-) for formula: C 43 H 38 O5: 650; Measured value: 650.

[0321] 2-Methyl-1,4-phenylene bis(3,5-bis(4-(anthracene-9-yloxy)butoxy)benzoate)RM-17,

[0322]

[0323] 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 added 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 for 6 hours under an argon atmosphere. An additional 250 mg of EDC.HCl was added, and the mixture was stirred further at room temperature for 3 hours. H2O (10 mL) was added, followed by stirring for another 15 minutes. The organic layer was separated and washed with 1N HCl aqueous solution. The organic layer was separated and concentrated, and the crude product was loaded into an 80 g SiO2 column; eluted with Hex-DCM, then gradually converted to DCM only. The pure fraction was collected, concentrated, and dried in a vacuum oven to give 570 mg of RM-17 as a colorless solid, with a yield of 72%.

[0324] 1 H 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).

[0325] LCMS(APCI-), calculated value (M-) for formula: C 93 H 50 O 12 : 1389; Measured value: 861.

[0326] RM-18: 1,3,5-trimethyltris(4-(3-(anthracene-9-yloxy)propoxy)benzoate)

[0327]

[0328] 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 added to DCE:CHCl3 (1:1) (45 mL), followed by phloroglucinol (0.0785 g, 0.622 mmol, 1 equivalent). The resulting mixture was stirred at room temperature for 16 hours under an argon atmosphere. H2O (10 mL) was added, followed by further stirring for 15 minutes. The organic layer was separated, concentrated to a volume of 20 mL, and loaded into an 80 g SiO2 column; eluted with Hex-DCM (7 / 3), then gradually reduced to DCM only. The pure fraction was collected, concentrated, and dried in a vacuum oven to give 570 mg of RM-18 as a colorless solid, in 77% yield.

[0329] 1 H 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).

[0330] LCMS(APCI-), calculated value (M-) for formula: C 78 H 60 O 12 : 1189.33; Measured value: 1189.

[0331] Manufacturing a liquid crystal-based dimmable device using the capillary method

[0332] A selectively tunable light-emitting device based on a heterocyclic liquid crystal compound with positive dielectric anisotropy is fabricated using a capillary method. For the capillary method, a homogeneous liquid crystal test cell (KSRO-10 / B107M1NSS05, EHC Co. Ltd, Tokyo, Japan) is used to manufacture the device. The test cell comprises two substrates with supports defining an effective alignment region between the two substrates. The glass / ITO substrate has dimensions of 20 mm × 25 mm, a sheet resistance of approximately 100 Ω / sq, and an active alignment region of approximately 10 mm × 10 mm, with a cell gap of 10 μm. The cell is pre-coated with a polyamide alignment layer (LX-1400, Hitachi-Kasei Shoji Co., Ltd., Tokyo, Japan), eliminating the need for applying an alignment layer. Because the cell geometry includes supports to ensure the cell gap is maintained, it is not necessary to insert separate spacers into the cell before applying the liquid crystal mixture.

[0333] First, a liquid crystal mixture is prepared by mixing fluorinated liquid crystal and reactive mesocrystalline material (e.g., one of RM-1 to RM-18) at a weight ratio of 95 wt% to 5 wt% using a vortex mixer to create a mixed formulation at 75°C. Next, the test cell is preheated for liquid crystal injection by heating the substrate on a hot plate at 75°C for 5 minutes. Then, a thermal coating formulation is injected near the opening of the test cell. The solution is then allowed to flow into the test cell via capillary action until it coats the entire active alignment region. In some embodiments, the test cell is placed on a hot plate after the coating formulation is injected to aid in complete and uniform coverage of the liquid crystal. The resulting coated substrate is then soft-baked on a hot plate at 75°C for approximately 3 minutes to remove any residue. After soft baking, the result is a layered unit assembly ready for ultraviolet radiation curing (UV curing).

[0334] The layered unit assembly was soldered to an indium-containing wire for subsequent haze measurement. The layered unit assembly was then placed in a UV chamber (365 nm, UWAVE, Villebon-sur-Yvette, France). The layered unit assembly was subjected to 187 mW / cm². 2 Curing at incident power for 1-20 minutes indicates 11-220 joules.

[0335] Next, the tunable assembly is placed in the electrical connection port and a conductive clip and wires are attached. An electric field is generated across the liquid crystal by applying an AC voltage. Then, the alignment of the reactive mesocrystalline material in the liquid crystal composite is changed, and the cell changes from transparent to opaque.

[0336] Haze measurement

[0337] Haze was measured using an HM-150 spectrophotometer manufactured by Murakami Color Research Laboratory, Tokyo, Japan, based on JIS K 7136.

[0338] Table 1 shows the haze of liquid crystal mixtures containing 5.0 wt.% photoreactive RMs (95% non-reactive LC) under various applied voltages.

[0339]

[0340]

[0341] Table 2 shows the haze of liquid crystal mixtures containing 5.0 wt.% photoreactive RMs (95% non-reactive LC) under various applied voltages.

[0342]

[0343] Table 3 shows the haze of liquid crystal mixtures containing 5.0 wt.% photoreactive RMs (95% non-reactive LC) under various applied voltages.

[0344]

[0345] Reversibility of photodimerization reaction Photodissociation test

[0346] Test I: Via UV365 nm UV 254 nm (dimerization) (Dissociated) Tunable assembly (LC / anthracene (95 / 5) mixture in ITO test unit)

[0347] Furthermore, by using a UV LED (254nm, Analytica, California, USA) at 9mW / cm², 2 The reversibility of driving voltage changes under specific haze conditions was examined by irradiating prepared tunable assemblies with an incident power of 187 mW / cm². First, each sample was placed under an incident power of 187 mW / cm². 2 Under UV LED (365nm, UWAVE, Villebon-sur-Yvette, France) for 0–60 min (approximately 673.2 J / cm²), 2 (The crosslinking density will increase during dimerization, and thus the driving voltage will increase). Then, the sample is irradiated with a UV LED (254nm) for 0–20 minutes (approximately 32.4 J / cm²). 2 (A cracking occurs and the drive voltage shifts to low), then the haze is tested. The results of the reversibility are shown in... Figure 5-6 middle.

[0348] Test II: Measurement of liquid crystal solution in THF via UV 365 nm (dimerization) / UV 254 nm (dissociation) by GPC

[0349] dimerization

[0350] 10–100 mg of RM-13 and 10 mL of THF were introduced into a stirred quartz vial attached to a condenser equipped with an argon inlet. The mixture was stirred at room temperature while argon was introduced for at least 30 minutes to remove oxygen from the reaction system. The vial, with a sealed cap, was then transferred to a UV 365 nm photoreactor (Photoreactor M2, Penn PHD, Sigma-Aldrich, Germany) for approximately 0–60 minutes to allow dimerization. After the reaction was stopped, a solution containing the dimer was obtained. The apparent molecular weight of the dimer solution was then determined by GPC (Hitachi Chromaster GPC system).

[0351] Table 4: 1 mg RM-13 / ml THF solution exposed to UV 365 at different times.

[0352]

[0353] Table 5: 1-10 mg RM-13 / ml THF solution exposed to UV 365 for 20 min.

[0354]

[0355]

[0356] See Figure 7 and Figure 8 .

[0357] dissociation

[0358] A dimerization solution of predetermined concentration was filled into a quartz cuvette with a 1 mm optical path and then exposed to a UV LED (254 nm, Anaritik Jena) for approximately 0–60 min. After exposure, a dissociated solution was obtained. The apparent molecular weight of the dissociated solution was then determined by GPC measurement (Hitachi Chromaster GPC system).

[0359] Table 6: 5 mg RM-13 / ml THF solution exposed to UV365 for 20 minutes, followed by exposure to UV254 at different exposure times.

[0360]

[0361] See Figure 9 and Figure 10 .

[0362] Unless otherwise stated, all figures used in the specification and claims to indicate the amount of an ingredient, properties such as molecular weight, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters listed in the specification and appended claims are approximate values ​​that may vary depending on the desired properties sought. At least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least based on the reported significant figures and by applying ordinary rounding techniques.

[0363] Unless otherwise stated herein or clearly contradicted by the context, the terms “a,” “an,” “the,” and similar designations used in the context of describing the invention (particularly in the context of the following claims) should be interpreted to cover both the singular and the plural. Unless otherwise stated herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order. The use of any and all examples or representative language (e.g., “for example”) provided herein is intended only to better illustrate the invention and does not constitute a limitation on the scope of any claim. No language in the specification should be construed as indicating any unclaimed element essential to the practice of the invention.

[0364] The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Each member of a group may be mentioned and claimed individually or in any combination with other members of that group or other elements found herein. It is contemplated that one or more members of a group may be included in or removed from the group for convenience and / or patentability reasons. When any such inclusion or removal occurs, this specification is deemed to contain the modified group, thereby satisfying the written description of all Markush groups used in the appended claims.

[0365] This document describes certain embodiments, including the best mode known to the inventors for carrying out the invention. Of course, variations of these described embodiments will become apparent to those skilled in the art after reading the foregoing description. The inventors expect those skilled in the art to appropriately employ such variations, and the inventors intend to practice the invention in ways different from those specifically described herein. Therefore, the claims include all modifications and equivalents of the subject matter recited in the claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, any combination of the foregoing elements in all their possible variations is contemplated.

[0366] Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the claims. Other modifications may be made within the scope of the claims. Therefore, alternative embodiments may be utilized in accordance with the teachings of this document, as examples rather than limitations. Consequently, the claims are not limited to the embodiments shown and described precisely as illustrated herein.

Claims

1. Photoreactive liquid crystal compounds according to the following formula: R7 is selected from bonds, hydrogen, or C1-C3 alkyl groups; L1, L3, L4, and L5 are independently selected from C2-C8 diether linking units or C2-C8 ether acetate linking units; and R1, R3, R4 and R5 are independently selected from anthracene, coumarin, cinnamic acid, stilbene or terliyl.

2. The photoreactive liquid crystal compound according to claim 1, wherein L1, L3, L4 and L5 are independently selected from: Where n or m is an integer from 1 to 10.

3. The photoreactive liquid crystal compound according to claim 1, wherein R1, R3, R4 and R5 are independently selected from:

4. The photoreactive liquid crystal compound according to claim 1, having one of the following structures:

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

6. A liquid crystal element comprising a polymer-dispersed liquid crystal composition according to claim 5.

7. A method, comprising: Provide oligomers or polymers comprising one or more compounds according to any one of claims 1-4; and The oligomer or polymer is irradiated with crosslinking ultraviolet radiation to provide a crosslinked oligomer or polymer.

8. The method of claim 7, wherein the crosslinked ultraviolet radiation comprises wavelengths in the range of about 305 nm to about 395 nm.

9. The method according to claim 7 or 8, wherein the irradiation comprises 0.1 to 2500 J / cm². 2 The cross-linked ultraviolet radiation mentioned above.

10. The method of claim 7, further comprising irradiating the crosslinked oligomer or polymer with pyrolysis ultraviolet radiation.

11. The method of claim 10, wherein the pyrolysis ultraviolet radiation comprises wavelengths in the range of about 254 nm to about 280 nm.

12. The method of claim 10, wherein the irradiation with the pyrolysis ultraviolet radiation comprises 0.1 to 2500 J / cm². 2 The aforementioned split ultraviolet radiation.

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