WO2024206924A1

WO2024206924A1 - Liquid crystal composition containing a reversibly photopolymerizable compound or monomer, pattern rewritable polymer dispersed liquid crystal element, and associated selectively dimmable device

Info

Publication number: WO2024206924A1
Application number: PCT/US2024/022373
Authority: WO
Inventors: Hiep Luu; Chih-Hsun Lee; Mai NITTA; Yufen HU; Peng Wang
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2023-03-30
Filing date: 2024-03-29
Publication date: 2024-10-03
Anticipated expiration: 2025-09-30
Also published as: KR20250166173A; CN121002147A; TW202503027A

Abstract

Photoreactive liquid crystal compounds having reversible photodimerization functional groups and devices containing the same are described. Liquid crystal compositions containing the reversibly photodimerizable liquid crystal compounds can allow for changing the depicted display under the application of an electric field.

Description

LIQUID CRYSTAL COMPOSITION CONTAINING A REVERSIBLY PHOTOPOLYMERIZABLE COMPOUND OR MONOMER, PATTERN REWRITABLE POLYMER DISPERSED LIQUID CRYSTAL ELEMENT, AND ASSOCIATED SELECTIVELY DIMMABLE DEVICE

Inventors: Hiep Luu, Chih-Hsun Lee, Mai Nitta, Yufen Hu, and Peng Wang

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application No. 63/493,132, filed March 30, 2023, the content of which is incorporated herein by reference in its entirety.

BACKGROUND

The present disclosure relates to reversibly polymerizable compounds or compositions, as well as to elements or devices which include reversibly polymerizable compounds or compositions.

For window shading, smart windows may be attractive alternatives to conventional mechanical shutters, blinds, or hydraulic methods of shading. Technologies for smart window applications include: suspended particle displays (SPD), Polymer Dispersed Liquid Crystals (PDLCs), and electrochromics (ECs). 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: Polymer Physics 257-62 (2011). Regarding PDLCs, after a PDLC image is created, the image is fixed and altering or changing the image can require reloading of a new image upon or within the device.

Thus, there is a need for additional contributions in this area of technology.

SUMMARY

In one embodiment, a material which can be used in rewritable PDLC dimmable devices is described herein. The material may be integral to a window or applied as a coating to provide a changeable image by incorporating photoreactive compounds described herein, although other applications are possible and contemplated.

1

SUBSTITUTE SHEET (RULE 26) In one embodiment, a photoreactive liquid crystal composition may be photoreversible by application of irradiation to the composition to provide selective polymerization and/or depolymerization of a crosslinking entity such as a reversible photodimerizable functional group. In some embodiments, the photoreactive liquid crystal composition includes at least one photoreactive compound which may include at least two photodimerizable functional groups.

In some embodiments, a photoreactive liquid crystal compound includes a structure or substructure according to the following general formula:

In this formula, Ri, R3, R4, Rs and/or R7 may be independently selected from an anthracenyl, a coumarinyl, a cinnamyl acid, a stilbenyl, or a thyminyl group, R7 may be selected from a bond, hydrogen or a C1-C3 alkyl, and

Li, L3, L4, and L5 may be independently selected from a C1-C10 diether linker or a

C1-C10 ether acetate linker. In some embodiments, the linkers Li, L3, L4, and L5 may independently be selected

SUBSTITUTE SHEET (RULE 26) In some embodiments, a photoreactive liquid crystal compound or mesogen may include a reversible photodimerization R functional group. In some embodiments, the reversible photodimerization R functional group may include R groups Ri, R3, R4, and/or Rs. In some embodiments, the Ri, R3, R4, or R5 groups may be independently selected

Thymine |_{n some} embodiments, a photoreactive liquid crystal compound may have one of the following structures:

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

In some embodiments, a polymer dispersed liquid crystal (PDLC) composition may include a photoreactive liquid crystal compound described herein. In some embodiments, the photoreactive compound may include at least two reversible photodimerization functional groups described herein. In some embodiments, a polymer dispersed liquid crystal element may include a polymer dispersed liquid crystal composition described herein.

In some embodiments, a method for reversibly crosslinking a polymer network includes providing a monomer, oligomer or polymer including a liquid crystal composition. In one form, the liquid crystal composition may include one or more photoreactive liquid crystal compounds each having at least two photodimerization functional groups. For example, in one form the liquid crystal composition may include two photoreactive liquid crystal compounds, as described herein. The method further 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 to about 395 nm, e.g., about 365 nm, to reversibly crosslink and photodimerize the terminal R groups which may be, e.g., an anthracenyl, a coumarinyl, a cinnamyl acid, a stilbenyl, or a thyminyl groupfs] disposed at the terminal ends of the linkers L. In some embodiments, the method may also include irradiating the crosslinked oligomer or polymer with

SUBSTITUTE SHEET (RULE 26) ultraviolet radiation including a second cleaving wavelength between about 254 nm to about 280 nm. In some embodiments, a liquid crystal element may include a transparency changing layer defining two opposing surfaces, a composition described herein, and at least two alignment layers where the transparency changing layer can be bounded on both opposing surfaces by respective ones of the at least two alignment layers.

In some embodiments, a selectively dimmable device includes a first conductive substrate and a second conductive substrate, a liquid crystal element described herein disposed between the first conductive substrate and the second conductive substrate, and a voltage source. The first conductive substrate, the second conductive substrate, the liquid crystal element, and the voltage source are all in electrical communication such that when a voltage is applied from the voltage source an electric field is applied across the element.

In some forms, the selectively dimmable device may be characterized as having a haze of at most 10% when there is no voltage applied but a haze of at least 35% when a voltage of less than 40 volts is applied across the device. In some embodiments, the substrates may be flexible, and the device is in the form of a flexible sheet.

These and other embodiments are described in greater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1A illustrates a liquid crystal element with a liquid crystal with positive dielectric anisotropy.

Fig. IB illustrates a liquid crystal element with a liquid crystal with negative dielectric anisotropy.

Fig. 2 illustrates one non-limiting form of a selectively dimmable device with a positive dielectric anisotropic polymer dispersed liquid crystal.

Fig. 3 illustrates one non-limiting form of a selectively dimmable device with a negative dielectric anisotropic polymer dispersed liquid crystal.

Fig. 4 illustrates another non-limiting form of a selectively dimmable device.

Fig. 5 is a graphical illustration showing haze results between various selectively dimmable devices.

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SUBSTITUTE SHEET (RULE 26) Fig. 6 is another graphical illustration showing haze results between various selectively dimmable devices.

Fig. 7 is a graphical illustration showing dimerization (molecular weight) as a function of UV 365 exposure time.

Fig. 8 is a graphical illustration showing the dimerization (molecular weight) as a function of RM-13 concentration.

Fig. 9 is a graphical illustration showing cleaving (molecular weight) as a function of UV 254 exposure time.

Fig. 10 is a graphical illustration showing the effect on the measure of molecular weight of cleaving (molecular weight) as a function of UV 365 20-minute exposure time and of a function of UV 254 60 minute exposure time.

DETAILED DESCRIPTION

As used herein, the term "CX-Y" refers to a carbon chain having from X to Y carbon atoms. For example, C3-8 alkyl includes alkyl or cycloalkyl containing 3, 4, 5, 6, 7, or 8 carbon atoms.

The term "alkyl" as used herein refers to a moiety comprising carbon and hydrogen containing no double or triple bonds. An alkyl may be linear, branched, cyclic, or a combination thereof, and contain from one to thirty-five carbon atoms. Examples of alkyl groups include but are not limited to C3 alkyl; C4 alkyl, such as -(CH2)3CH3 C5 alkyl, such as -(CH2)3CH3 C6 alkyl; C7 alkyl; C8 alkyl; etc.

The terms "positive dielectric anisotropy", "negative dielectric anisotropy", and "neutral dielectric anisotropy" as used herein all have meanings known by those of ordinary skill in the art. The dielectric anisotropy is related to dielectric properties as well as optical properties depending on the direction, either along the length of the molecule (or molecular axis), or perpendicular to the length of the molecule (or molecular axis). The dielectric properties depend on the molecular shape and substituent moieties and their locations on a given molecule.

A molecule is said to have a positive dielectric anisotropy if the dielectric constant parallel to the length of the molecule is greaterthan the dielectric constant perpendicular

10

SUBSTITUTE SHEET (RULE 26) to the length of the molecule, where the length of a molecule is defined as vector between the two farthest moieties.

A molecule is said to have a negative dielectric anisotropy if the dielectric constant perpendicular to the length molecule is greater than the dielectric constant parallel to the length of the molecule, where the length of a molecule is defined as vector between the two farthest moieties.

A molecule is said to have a neutral dielectric anisotropy if the dielectric constant perpendicular to the length molecule is approximately the same (i.e., less than a 1% difference between the dielectric constants) as the dielectric constant parallel to the length of the molecule, where the length of a molecule is defined as vector between the two farthest moieties.

The term "opposing surfaces" as used herein refers to a group of two surfaces or sides of a shape or polygon that are on the opposite side of the shape or polygon with respect to each other (e.g., the top and bottom of a layer, the front and back of a shape). When used in singular, the term "opposing surface" refers to one of the two surfaces.

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

The current disclosure relates to a reversible crosslinkable monomer, oligomer and/or polymer, a liquid crystal composition, a polymer dispersed liquid crystal (PDLC) element, and/or a selectively dimmable device including a polymer dispersed liquid crystal (PDLC) element.

The current disclosure also relates to a display device that may repeatedly record (write) and erase visible information. For example, in one form writing patterns can be written via irradiation with light (phototpolymerization) dimerization including a crosslinking wavelength between about 305 nm to about 395 nm and erasing patterns can be achieved via irradiation with light of a shorter wavelength (e.g., between about 250nm to about 280 nm) or heat.

The current disclosure also relates to an electrically switchable and optically rewritable display based on the photopolymerization/photo-depolymerization of photoreactive liquid crystal (LC) compounds. In some embodiments, the photoreactive liquid crystal compounds include one or more reversible photodimerizable functional

11

SUBSTITUTE SHEET (RULE 26) groups. Without the use of lithographic or holographic implements, optically rewritable patterns may be produced by employing nematic LCs as reaction solvents and spatially nonuniform electric fields. The nematic mixture, containing 5.0 wt.% RMs (95% LC) and sandwiched between electrodes, was exposed to spatially uniform reaction-initiating radiation. The spatially nonuniform electric field induced optical patterns in the reaction template with spatially varying elastic deformations. The resulting polymerized liquid crystal networks were both spatially and optically patterned, with good fidelity with respect to the electrode pattern and subsequent periodic director profiles. The pattern can be erased by dissociating the polymerized liquid crystal networks with irradiation of ultraviolet light having a wavelength between about 250nm to about 280 nm.

The display device may repeatedly record (write) and erase visible information. For example, it may write patterns via irradiation, e.g., with light having a wavelength between about 305 nm to about 395 nm for (phototpolymerization) dimerization, and erase patterns via irradiation with light having a shorter wavelength (between about 250nm to about 280 nm) or heat (dimer dissociation leading to erasure). The technology- used herein may also be useful to incorporate LED light sources into laminated glass panels or for a holographic storage system to repeatedly create distinctive patterns, images, and logos, although other applications are possible and contemplated.

Liquid Crystal Composition

In some embodiments, a composition includes 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 mesogenic liquid crystal phase. In some embodiments, the liquid crystal composition may include a compound with positive dielectric anisotropy, and in some embodiments, the liquid crystal composition may include a compound with negative dielectric anisotropy. In some embodiments, the liquid crystal composition may include a compound with positive dielectric anisotropy and a compound with negative dielectric anisotropy.

In some embodiments, the liquid crystal composition may further include 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

12

SUBSTITUTE SHEET (RULE 26) 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).

Photoreactive Liquid Crystal compound

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 photodimerization functional groups. In some embodiments, a monomer may be capable of forming a reversibly crosslinked oligomer or polymer, and the monomer may include a substituted benzyl derivative. In some embodiments, the substituted benzyl derivative may include at least two linked 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 substituents arms.

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

where Ti, T2, T3, T4, T5, or T6 can be a bond, hydrogen, a C1-C3 alkyl and/or an L-R functional group, where L can be an C1-C10 diether linker or a C1-C10 ether acetate linker and where R can be a reversible photodimerizable functional group, e.g., an anthracenyl, a coumarinyl, a cinnamyl acid, a stilbenyl, and/or a thyminyl group.

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SUBSTITUTE SHEET (RULE 26) In some embodiments, the substituted benzyl derivative may have the following general structure:

In some embodiments, R7 may be a bond, hydrogen or C1-C3 alkyl. In some embodiments, the liquid crystal compound and/or monomer that may be capable of forming a reversibly crosslinked oligomer or polymer, may include an R group disposed at the terminal end of the linker opposite the benzyl core group. In some embodiments, the R group may include an Ri, R2, R3, R4, Rs and/or R6 group. In some embodiments, the Ri, R2, R3, R4, Rs and/or Re groups may be independently selected from an anthracenyl, e.g., anthracenel, a coumarinyl, e.g., coumarin, a cinnamyl acid, e.g., cinnamic acid/ester, a stilbenyl, e.g., a stilbene, or a thyminyl. e.g., thymine. In some embodiments, an anthracenyl, a coumarinyl, a cinnamyl acid, a stilbenyl, or a thyminyl groups may be of the following general formula:

,

In some embodiments, the respective R groups may include the same substituent group, e.g., all R groups may be anthracenyl. In some embodiments, the respective R

14

SUBSTITUTE SHEET (RULE 26) groups may include any permutation of the aforementioned substituent group, e.g., one arm may be functionalized with one of the aforementioned substituent groups and another may be functionalized with another of the aforementioned substituent groups. Thus, the plural arms may be a mixture of an anthracene, a coumarin, a cinnamic acid, a stilbene, and/or a thymine functionalized arm. In some embodiments, at least one of the respective R groups can dimerize, covalently bond or link with a similar R group, e.g., an anthracenyl terminal end group can dimerize or covalently bond or link with another anthracenyl terminal end 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:

SUBSTITUTE SHEET (RULE 26)

It is believed that the photoreversible dimerization or covalent bonding described above is an example of the bonding of the respective terminal R groups enabling linkage creation. In some embodiments, the respective change in structure may be determined by proton NMR. It is believed that the photoreversible dimerization allows the rewriting and erasing characteristics of the current material.

In some embodiments, the liquid crystal compound and/or monomer that may be capable of forming a photoreactive reversibly dimerized or crosslinked oligomer or polymer may include a linker L between the benzyl core group and the R group. In some embodiments, the linker L may include Li, L2, L3, L4, L5 and/or L6 and/or any further similar arms. In some embodiments, the linker L may be selected from a C2-C8 diether linker or a C2-C8 ether acetate linker. In some embodiments, L can be an C1-C10 diether linker (e.g., C2 diether linker, C3 diether linker, C4 diether linker, C5 diether linker, C6 diether linker, C7 diether linker, C8 diether linker, C9 diether linker and/or C10 diether linker) or a C1-C10 ether acetate linker (e.g., Ci ether acetate linker, C2 ether acetate linker, C3 ether acetate linker, C4 ether acetate linker, C5 ether acetate linker, C6 ether acetate linker, C7 ether

SUBSTITUTE SHEET (RULE 26) acetate linker, C8 ether acetate linker, C9 ether acetate linker, and/or C10 ether acetate linker). In some embodiments, the linker L may be independently selected from:

, , , , , In some embodiments, the monomer that may be capable of forming a photoreactive reversibly dimerizable oligomer or polymer, may include a compound or may include at least two compounds, selected from:

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

20

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

In some embodiments,

monomer, oligomer or polymer may include a substructure that may include the monomers and/or photoreactive liquid crystal compounds described above.

In some embodiments, a polymer dispersed liquid crystal formulation may include a liquid crystal compound described herein and/or a monomeric, oligomeric and/or polymeric dispersed liquid crystal composition described herein. In some embodiments, a polymer dispersed liquid crystal element may include a monomeric, oligomeric and/or polymeric liquid crystal composition described herein.

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SUBSTITUTE SHEET (RULE 26) In some embodiments, a method for reversibly crosslinking a polymer network may include providing an oligomer or polymer including photoreactive monomers, oligomers and/or polymers described herein. In one form of the method, the oligomer or polymer is irradiated with crosslinking ultraviolet radiation having a crosslinking wavelength between about 305 nm to about 395 nm to provide a crosslinked oligomer or polymer. In some embodiments, the irradiating of at least an R group described above may covalently bond the like R groups to another. In some embodiments, the bonding may be selected from those described herein. The method may also include irradiating the oligomer or polymer with ultraviolet radiation having a cleaving wavelength between about 220 nm to about 280 nm, e.g., 254 nm. In some embodiments, irradiating an R group described above, e.g., the anthracene or the coumarin, results in cleavage from the like R group. In some embodiments, the bonding may be selected from those described herein.

The method may include repeated irradiating steps of applying crosslinking and cleaving ultraviolet radiation. Liquid Crystal Element

As shown in Figure 1A or Figure IB for example, a 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 is bounded on both opposing surfaces by respective first and second ones of the alignment layers 120. In some embodiments, any of the above aforementioned layers may further include dispersants, plasticizers, binders, and/or solvents.

In the illustrated form, the transparency changing layer 110 includes a liquid crystal composition 111 as described herein. In some embodiments, the liquid crystal composition 111 in the transparency changing layer 110 may include any of the liquid crystal mixture compounds described herein. Those skilled in the art will recognize that additional PDLC materials may be present in the PDLC matrix, including for example a positive dielectric anisotropic compound, a negative dielectric anisotropic compound, and/or a polymer. Non-limiting examples of positive dielectric anisotropic compounds can be as 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, as shown in Figure IB, the composition may include a

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SUBSTITUTE SHEET (RULE 26) negative dielectric anisotropic compound 114 whereas the embodiment of Figure 1A includes a positive dielectric anisotropic compound 113. In some embodiments, the 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 the composition 111 may be dispersed in the polymer. In the form shown in Figure 1, the composition 111 is dispersed within the transparency changing layer such that the composition forms droplets which are suspended within the polymer 112. The transparency changing layer 110 may be considered a polymer dispersed liquid crystal (PDLC). In the form illustrated in Figures 1A and IB, the transparency changing layer llOincludes spacersll5, although forms in which the spacers 115 are not present are also contemplated. 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 turn transparent upon the application of an electric field, or a normal mode PDLC. In some embodiments, the liquid crystal element 100 may be transparent to visual light but opaque upon the application of an electric field, or a reverse mode element.

In some embodiments, the transparency changing layer 110 may be a polymer dispersed liquid crystal layer, where the liquid crystal composition forms droplets within the polymer matrix. In some embodiments, the liquid crystal droplets form as a suspended precipitate during the polymerization of polymer precursors. In some embodiments, the droplets may have a uniform distribution, a gradient distribution, or a random distribution within the polymer matrix. In some embodiments, the transparency changing layer 110 may further include a base material with transparent electrode layers disposed on both sides of the polymer-dispersed liquid crystal layer.

Selectively Dimmable Device

Referring now to Figures 2 and 3, a selectively dimmable device 200 is illustrated. The device 200 includes two conductive substrates (or electrode layers), 210 the liquid crystal element 100, and a voltage source. In the illustrated form, the first and second conductive substrates 210 define a gap therebetween where the liquid crystal element 100 is disposed between the first and second conductive substrates 210 within the gap.

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SUBSTITUTE SHEET (RULE 26) In some embodiments, a polymer matrix including one or more photoreactive compounds as described herein may be disposed within a flexible membrane including the materials described herein. In some embodiments, a polymer matrix including the photoreactive compounds described herein may be disposed within a polymeric liquid crystal composition including the materials described herein. In some embodiments, the liquid crystal element 100, the conductive substrates 210, and the voltage source are all in electrical communication such that upon the application of a voltage from the voltage source, an electric field is applied across the liquid crystal element 100. In some embodiments, application of a voltage from the voltage source provides a discernable image when viewing the liquid crystal composition and/or device 200.

As shown in Figures 2 and 3, the liquid crystal element 100 integrated into the device 200 includes a polymer matrix 112 in which polymer dispersed liquid crystal droplets are suspended and bound 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 the device 200, as shown in Figure 2 for example, the liquid crystal droplets may include a positive dielectric anisotropic compound, 113. In other embodiments of the device 200, as shown in Figure 3 for example, the liquid crystal droplets may include a negative dielectric anisotropic compound 114. In still other embodiments, the liquid crystal droplets may include a combination of positive and negative dielectric anisotropic compounds.

In some embodiments of the device 200, the liquid crystal element 100 may be chosen such that under a condition where no induced electric field is present within the transparency changing layer 110, the index of refraction of the liquid crystal composition 111 and the index of refraction of the polymer 112 are similar relative to each other so that the total transmission of visible light allowed to pass through the device 200 can 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 there is an electric field present, e.g. due to a voltage applied to the electrical circuit, the index of refraction of the liquid crystal composition 111 and the index of refraction of the polymer 112 can vary relative to each other so 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

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SUBSTITUTE SHEET (RULE 26) about 15%, only about 10%, or only about 5% of visible light is allowed to pass through the device 200. In some embodiments, the magnitude of the electric field necessary to achieve scattering corresponds to applying a voltage of less than 120 V, less than 110 V, less than 50 V, less than 40 V, less than 20 V, less than 15 V, less than 12 V, less than 10 V, or less than 5V across the device 200. In some embodiments, the electric field across the device 200 is less than about 500 kV/m, less than about 1,000 kV/m, less than about 5,000 kV/m, less than about 10,000 kV/m, less than about 20,000 kV/m, less than about 40,000 kV/m or less than about 80,000 kV/m. It is believed that the effectiveness of dimming of the device 200 can also be depicted in terms of percentage of haze, which generally can be defined as:

where the total light transmitted is the light from a known source and the diffuse light transmitted is the light transmitted through the element 100. In some embodiments, the haze of the device 200 may be a maximum of about 5%, about 10%, about 15%, about 20%, about 25%, or about 30% when no voltage is applied to the device. In some embodiments, 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% when a voltage of about 40 volts or less is applied to achieve scattering. In some embodiments, the amount of haze change between a voltage applied state and a voltage unapplied state can be changed by a reversible photodimerization reaction of the photoreactive liquid crystal composition.

In some embodiments, the device 200 can be semi-rigid or rigid. In some embodiments, the device 200 can be flexible. In some embodiments, a selectively dimmable device 200 can form a flexible sheet, as shown in Figure 4, which can be applied between or on the surface of preexisting windows. In some embodiments, the conductive substrates 210 may be formed of flexible materials so that the aforementioned device may be a flexible film. In some embodiments, the flexible device may be placed in between or one side of pre-existing window glass to provide a dimming capability. In other embodiments, the device can be rigid including materials which are not flexible.

In some embodiments, the conductive substrates 210 may include a base 211, which in some forms, may be formed of a conductive material.

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SUBSTITUTE SHEET (RULE 26) In some embodiments, each conductive substrate 210 may further include an electron conduction layer 212where the layer is in physical communication with the base 211. In some embodiments, the electron conduction layer is placed in direct physical communication with the base 211, such as a layer on top of the base 211. In other embodiments, the electron conduction layer may be impregnated directly into the base (e.g., ITO glass, ITO PET, or ITO PEN), or sandwiched in between two bases 211 to form a single conductive substrate. In some embodiments, where there is an electron conduction layer present the base 211 may be formed of a non-conductive material. In some embodiments, as shown in Figures 2 and 3 for example, the selectively dimmable device 200 may also include a sealant 250. In some embodiments, the sealant 250 may encapsulate the liquid crystal element 110 between the conductive substrates 210 to protect the element 110 from the environment. In some embodiments, the sealant 250 may include a two-part real time cure epoxy, 3-Bond 2087, or the like. In some embodiments, the sealant 250may include a UV-curable photopolymer, such as NOA-61, or the like. In some embodiments, as shown in Figure 4, the selectively dimmable device 200 may also include an adhesive layer 260. In some embodiments, the adhesive layer 260 will allow a flexible sheet embodiment of the aforementioned device 200 to be installed on pre-existing windows. In some embodiments, the adhesive may include an optically clear adhesive (OCA). In some embodiments, the OCA may include OCA products commercially available and known to those skilled in the art (e.g., Nitto OCA tape, Scapa OCA tape). In some embodiments, the selectively dimmable device 200 may also include a removable carrier substrate 261to protect the adhesive layer 260 from contamination which will be peeled away before the device's application.

In one or more embodiments, a method for using a polymer-dispersed liquid crystal composition or a film including the same includes a fixing process for generating a liquid crystal polymer by a photodimerization reaction of a photoreactive liquid crystal compound and a resetting process for generating the photoreactive liquid crystal compound by depolymerization reaction of the liquid crystal polymer. In some embodiments, the fixing process is performed again after the resetting process. In some embodiments, the fixing process and/or the resetting process are repeated. In some embodiments, an area in which the liquid crystal polymer is generated in a second or

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SUBSTITUTE SHEET (RULE 26) subsequent fixing process is different from an area in which the liquid crystal polymer is generated in the preceding fixing process.

In one or more embodiments, a method for reversibly crosslinking a polymer network may include providing an oligomer or polymer including one or more photoreactive liquid crystal compounds described herein; and irradiating the oligomer or polymer with 0.1-2500.0 J/cm2, e.g., 32.4 J/cm² or 673.2 J/cm², of ultraviolet radiation, with the UV radiation having a first crosslinking wavelength greater than about 350 nm, about 300 nm, about 320 nm, about 270 nm, and/or about 300 nm and less than about 425 nm, about 420 nm, about 415 nm, about 410 nm, about 405 nm, about 400 nm and/or about 395 nm. In some forms, first crosslinking wavelength is between about305 nm and about 395 nm. In some embodiments, the method for reversibly crosslinking a polymer network may further include irradiating the crosslinked oligomer or polymer with 0.1-2500.0 J/cm2, e.g., 32.4 J/cm² or 673.2 J/cm2 of ultraviolet radiation, with the UV radiation having a second cleaving wavelength less than 300 nm, 260 nm, 280 nm, 249 nm, and/or 280 nm. In one form, the second cleaving wavelength is between about 200 nm to about 300 nm, about 220 nm to about 300 nm, about 240 nm to about 290 nm and about 250 nm to about 280 nm. In some embodiments, the crosslinking wavelength is greater than the cleaving wavelength. For example, as previously described, the crosslinking wavelengths of the various R functional groups can be greater than 350 nm (anthracene), 300 nm (cinnamic acid), 320 nm (coumarin), 270 nm (thymine), and or 300 nm (stilbene); and the depolymerizing wavelengths can be less than 300 nm (anthracene), 260 nm (cinnamic acid), 280 nm (coumarin), 249 nm (thymine), and or 280 nm (stilbene).

EXAMPLES

It should be appreciated that the following Examples are for illustration purposes and are not intended to be construed as limiting the subject matter disclosed in this document to only the embodiments disclosed in these examples.

The compounds in the following examples are photoreactive liquid crystal compounds including at least two reversible photodimerization functional groups that were synthesized and evaluated for PDLC properties.

EXAMPLE 1: Synthesis of the liquid crystal compounds and/or monomers

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SUBSTITUTE SHEET (RULE 26) In general, the preparation of the compounds was performed in an argon atmosphere (Airgas, San Marcos, CA USA) inside of a fume-hood. In addition, where degassing is mentioned, it can be performed by bubbling of argon (Airgas) through the compound or other similar methods. RM-1: Synthesis 2-methyl-l,4-phenylene bis(4-(3-((2-oxo-2H-chromen-7- yl)oxy)propoxy)benzoate)

methyl 4-(3-chloropropoxy) benzoate. Int-l

methyl 4-hydroxybenzoate methyl 4-(3-chloropropoxy)benzoate

To a solution of methyl 4-hydroxybenzoate (15.215 g, 0.1 mol) in acetone (230 ml) added K₂CO₃ (MW: 138.21) (20.73 g, 0.15 mol, 1.5 eq) following by l-bromo-3- chloropropane (MW: 157.44, d= 1.592 g/ml) (34.62g, 21.74 ml, 0.11 mol, 1.1 eq) was o added and stirred at 76 C for 8 hours, then 16 hours at RT, and the precipitate filtered. The filtrate was concentrated to gain (22.5 g, 0.098 mmol) a light yellowish green clear oil, yield 98%; the product lnt-1 was used next step without further purification.

SUBSTITUTE SHEET (RULE 26) ^XH NMR (400 MHz, 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- ), calcd (M-) for Formula: C11H13CIO3: 228.6; foimd:228. methyl 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate. lnt-2

methyl 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate A mixture of lnt-1 (2.285 g, 10.0 mmol), 7-hydroxy-coumarin (2.21 g, 13.36 mmol, 1.36 eq), anhydrous potassium carbonate (2.75 g, 19.895 mmol, 1.98 eq), and DMF o anhydrous (20 ml) was stirred at 90 C under Argon atm for 16 hrs. The cooled mixture was added to water (100 ml), the precipitate was filtered, washed with water (2 x 50 ml) and MeOH (50 mLx2) and then dried in vacuo-oven to gain 3.31 g of an off-white solid methyl 4-(3-((2-oxo-2H-chromen-7-yl) oxy) propoxy) benzoate, yield 93.4%. The product lnt-2 was kept in an amber vial.

¹H NMR (400 MHz, Chloroform-d) 6 8.06 - 7.92 (m, 2H), 7.63 (d, J = 9.5 Hz, 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).

LCMS (APCI-), calcd (M-) for Formula: C₂0H₁₈O₆: 35436; found:354.

4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoic acid, lnt-3

4-(3-((2-oxo-2H-chromen-7- yl)oxy)propoxy)benzoic acid

SUBSTITUTE SHEET (RULE 26) A solution of 4 N NaOH in H₂O (4 mL, 16 mmol, 3.2 eq) was added to a mixture of methyl 4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate lnt-2 (1.7718 g, 5.0 mmol), o in THF (25 mL), and (4 mL) MeOH and the resulting mixture was stirred at 53 C for 3 hours. The reaction was monitored by TLC and LCMS. When the conversion was completed the reaction mixture was poured into ice-water (100 mL), and 100 mL EA was o added. Water layer was cooled to 0 C and acidified with 6N HCI (4 mL), diluted with water (100 mL), and the white solid was filtered, washed with water, then dried in vacuo-oven to gain 1.701 g of lnt-3 as an off-white solid, quantitative yield.

¹H NMR (400 MHz, DMSO-d₆) δ 12.58 (s, 1H), 7.99 (d, J = 9.5 Hz, 1H), 7.91 - 7.85 (m, 2H), 7.63 (d, J = 8.6 Hz, 1H), 7.04 (dd, J = 9.3, 2.4 Hz, 3H), 6.98 (dd, J = 8.6, 2.4 Hz, 1H), 6.29 (d, J = 9.5 Hz, 1H), 4.24 (dt, J = 13.8, 6.2 Hz, 4H), 2.23 (p, J = 6.2 Hz, 2H).

LCMS (APCI-), calcd (M-) for Formula: C₁₉H₁₆O_6.: 340.33; found:340.

2-methyl-l,4-phenylene bis(4-(3-((2-oxo-2H-chromen-7-yl)oxy)propoxy)benzoate)

RM-1

A solution of lnt-3 (0.628 g, 1.846 mmol), methyl hydroquinone (0.114 g, 0.923 mmol), EDC (0.389 g, 2.031 mmol) and DMAP (33.8 mg, 0.277 mmol) in 10.0 mL of THF anhydrous + 5 mL of DCM anhydrous + 5 mL of Me₂CO was stirred at room temperature under Argon atmosphere for 48 h. LCMS showed > 60% desired diester product and 10% mono ester product; added an additional 25mg 1643-49, 11 mg EDC, and continued stirring overnight.

33

SUBSTITUTE SHEET (RULE 26) The next day, the mixture was poured into a solution of NH₄CI (0.3 g in 20 mL of water) and extracted 2 times with CH₂CI₂; the combined organic layers were washed with water and dried over MgSO₄, then filtered and evaporated under reduced pressure to gain a crude product of 660 mg as off-white solid after washing with MeOH. Purification of the crude by 80 g SiO2 with 2.5 % EA in DCM as eluant, gained 319 mg of a colorless solid of RM-1, yield 45%

^XH NMR (400 MHz, TCE-d8) 6 8.15 - 8.08 (m, 2H), 8.08 - 8.00 (m, 2H), 7.59 (d, J = 9.5 Hz, 2H), 7.33 (d, J = 8.6 Hz, 2H), 7.10 (d, J = 8.7 Hz, 1H), 7.06 (d, J = 2.7 Hz, 1H), 7.01 (dd, J = 8.6, 2.8 Hz, 1H), 6.98 - 6.91 (m, 4H), 6.81 (dd, J = 8.6, 2.4 Hz, 2H), 6.77 (d, J = 2.4 Hz, 2H), 6.16 (d, J = 9.5 Hz, 2H), 4.25 - 4.11 (m, 8H), 2.35 - 2.22 (m, 4H), 2.15 (s, 3H).

LCMS (APCI-), calcd (M ) for Formula: C₄₅H₃₆O₁₂: 768.77; found:768.

RM-2: 2-methyl-l,4-phenylene bis(4-(3-(anthracen-9-yloxy)propoxy)benzoate)

4-[3-(anthracen-9-yloxy) propoxy] benzoic acid, lnt-4

34

SUBSTITUTE SHEET (RULE 26)

Step 1: A mixture of methyl lnt-1 (4.57 g, 20.0 mmol), anthrone (3.885 g, 20.0 mmol, 1 eq), anhydrous potassium carbonate (5.52 g, 40.0mmol, 2 eq), and DMF anhydrous (40 ml) was stirred at 85 C under Argon atm for 16 hrs. The cooled mixture was added to water (350 ml), acidified with 4N HCI, extracted into EA (2x 350 mL) and the organic layers were combined, washed with water (2 x 100 ml) and then concentrated to dryness. The yellow solid crude product was used in the next step without further purification, gained 7.5 g, yield 97 %. The product was kept in amber vial.

Step 2: A solution of 4 N NaOH in H₂O (10 mL, 40mmol), (2 ml, 8 mmol) was added to a mixture of the above step (5.28g, 20.0 mmol), in THF (75 mL), and (25mL) MeOH; the o resulting mixture was stirred at 53 C for 3 hours. The reaction was monitored by TLC and LCMS. When the conversion was completed the reaction mixture was poured in to ice- o water (100 mL), and 100 mL EA was added. The water layer was cooled to 0 C and acidified with 6N HCI (10 mL) and diluted with water (100 mL), and the white solid was filtered, washed with water and MeOH and then dried in vacuo-oven to gain 2.887 g of lnt-4 as an off-white solid, yield 38% overall two steps.

¹H NMR (400 MHz, TCE-d8)) 6 8.16 (s, 1H), 8.13 (d, J = 8.8 Hz, 2H), 8.03 (d, J = 8.6 Hz, 2H), 7.92 (d, J = 8.5 Hz, 2H), 7.41 - 7.36 (m, 2H), 7.35 - 7.29 (m, 2H), 7.02 (d, J = 8.7 Hz, 2H), 4.45 (t, J = 5.9 Hz, 2H), 4.34 (t, J = 6.0 Hz, 2H), 2.46 (t, J = 6.0 Hz, 2H).

LCMS (APCI-), calcd (M-) for Formula: C₂₄H₂₀O₄: 372.4; found:372.

2-methyl-l,4-phenylene bis(4-(3-(anthracen-9-yloxy) propoxy) benzoate) RM-2:

SUBSTITUTE SHEET (RULE 26)

A solution of lnt-4 (2.188 g, 5.876 mmol, 2.06 eq), methyl hydroquinone (0.354 g, 2.851 mmol, leq), EDC (1.238 g, 6.463 mmol, 2.26 eq) and DMAP (107.6 mg, 0.881 mmol, 0.309 eq) was stirred in 50.0 mL of THF anhydrous and 30 mL of DCM anhydrous at room temperature under Argon atmosphere for 48 h. LCMS showed > 60% of the desired diester product and 10% of the mono ester product; An 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 a solution of NH4CI (0.9 g in 60 mL of water) and extracted 2 times with CH2CI2 (2 x 250 ml), and the combined organic layers were washed with water and dried over MgSCU, filtered and evaporated under reduced pressure to gained crude product of 2.02 g of an off-white solid after washing with MeOH. Purification of the crude by 80 g SiO2 with 2.5 % EA in DCM as eluant, gained 0.83 g of RM-2 as a colorless solid, yield 35%.

^TH NMR (400 MHz, TCE-d8) 6 8.16 (dt, J = 8.9, 5.2 Hz, 10H), 7.93 (d, J = 8.3 Hz, 4H), 7.40 (t, J = 7.0 Hz, 4H), 7.36 (dt, J = 8.3, 5.1 Hz, 4H), 7.15 (d, J = 8.7 Hz, 1H), 7.08 (qd, J = 8.7, 7.2, 2.8 Hz, 6H), 4.49 (t, J = 6.0 Hz, 4H), 4.36 (t, J = 6.0 Hz, 4H), 2.55 - 2.43 (m, 4H), 2.20 (s, 3H).

LCMS (APCI-), calcd (M-) for Formula: C₅₅H₄₄O₈: 832.95; found: 832.

RM-3: Synthesis 2-methyl-1,4henylene bis(4-(3-(4"((E)-3-butoxy-3-oxoprop-1-en---

36

SUBSTITUTE SHEET (RULE 26)

4-(3-(4-iodophenoxy) propoxy) benzoic acid. Int~6

SUBSTITUTE SHEET (RULE 26)

Step 1: A mixture of lnt-1 (2.285 g, 10.0 mmol, leq), 4-iodophenol (2.972 g, 13.51 mmol, 1.31 eq), anhydrous potassium carbonate (2.75 g, 19.895 mmol, 1.99 eq), and DMF o anhydrous (20 ml) was stirred at 90 C under Argon atm for 4 hrs. The solid was filtered, and the crude solid product methyl 4-(3-(4-iodophenoxy) propoxy) benzoate was washed o with Hexanes and dried in vacuo-oven at 65 C for 3 hours to gain 3.8173 g of an off-white solid of methyl 4-(3-(4-iodophenoxy) propoxy) benzoate, 92.6 % yield.

¹H NMR (400 MHz, Chloroform-d) 6 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).

Step 2: A solution of 4 N NaOH in H₂O (7.4 mL, 29.63 mmol, 3.2 eq) was added to a mixture of the product from the above step (3.8173 g, 9.26 mmol), in THF (50 mL), and o

(8 mL) MeOH and the resulting mixture was stirred at 53 C for 3 hours. The reaction was o monitored by TLC and when complete, it was cooled to 0 C and acidified with 6N HCI (~4 mL), and then extracted 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 vacuo-oven to gain 3.68 g of a colorless solid lnt-6, quantitative yield.

LCMS (APCI-), calcd (M ) for Formula: C₁₆H₁₅IO₄: 398.2; found: 398.

4-((4-(3-((4-iodocyclohexa-13-dien-1-yl oxy) propoxy) benzoyl oxy)-2”methylphenyl 4-(3-(4-Lodopoenoxy) propoxy) benzoate, lnt-7

SUBSTITUTE SHEET (RULE 26)

A mixture of I nt-6 (2.339 g, 5.876 mmol, 2.06 eq), EDC (1.238 g, 6.463 mmol, 2.26 eq) in 50.0 ml of DCM anhydrous was stirred at room temperature under Argon atmosphere for 10 minutes. The mixture turned to light yellow solution. A mixture of methyi hydroquinone (0.354 g, 2.851 mmol, leq), EDC and DMAP (107.6 mg, 0.881 mmol,

0.309 eq) in 10.0 mb of THF anhydrous was added at room temperature via syringe and needle. The resulting mixture was stirred under Argon atmosphere for 24 h. LCMS showed > 60% of the desired diester product and 10% of the mono ester product. An 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 a solution of NH4CI (0.9 g in 60 mL of water), stirred for

10 minutes and a white solid was collected by filtering. The filtrate was extracted 2 time with CHCh(150 ml). The crude solid from filtering and filtrate were combined and purified by 80 g SiO? column, running with 2.5 % EA in DCM as eluant to gain 3.5 g of a colorless solid of lnt-7, 85 % yield.

¹H NMR (400 MHz, Chloroform-d) 6 8.23 - 8.04 (m, 4H), 7.60 - 7.47 (m, 4H), 7.17

(d, J = 8.6 Hz, 1H), 7.13 (d, J = 2.5 Hz, 1H), 7.08 (dd, J = 8.6, 2.7 Hz, 1H), 7.04 - 6.92 (m,

4H), 6.76 - 6.65 (m, 4H), 4.25 (td, J = 6.1, 2.2 Hz, 4H), 4.15 (t, J = 6.0 Hz, 4H), 2.30 (h, J =

5.7 Hz, 4H), 2.24 (s, 3H).

LCMS (APCI-), calcd (M-) for Formula: C₃₉H₃₆I₂O₈ 884.5; found: 884.

2-methyl-l_;4-phenylene b!s(4-(3-(4-((E)-3-butoxy-3-oxoprop-l-en-l~yl) phenoxy) propoxy) benzoate) (1643-59)

39

SUBSTITUTE SHEET (RULE 26)

A mixture of 2-methyl-l,4-phenylene bis(4-(3-(4-iodophenoxy) propoxy) benzoate) (886 mg, 1 mmol, 1 eq), n-Butyl acrylate (769 mg, 6 mmol, 6 eq), Et₃N (506 mg, 0.696 mL, 5 mmol, 5 eq), 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). The reaction mixture turned to a clear brown solution o o when the temperature reached 65 C, the mixture was then stirred at 110 C under Argon atmosphere 16 hours. After cooling to RT, the mixture was quenched with IM HCI aq. (1 mL) and extracted into CHCI₃ (3x10 mL). The organic phase was washed with water, dried with Na₂SO₄, filtered and concentrated in vacuo to yield the crude product. Purification

40

SUBSTITUTE SHEET (RULE 26) by SiO2 column chromatography, eluting with Hex: DCM (1:1) to gain 0.454 g colorless solid of RM-3, yield 55%.

^TH NMR (400 MHz, Chloroform-d) 6 8.21 - 8.10 (m, 4H), 7.63 (d, J = 15.9 Hz, 2H), 7.51 - 7.42 (m, 4H), 7.17 (d, J = 8.7 Hz, 1H), 7.13 (d, J = 2.7 Hz, 1H), 7.08 (dd, J = 8.7, 2.8 Hz, 1H), 7.04 - 6.96 (m, 4H), 6.95 - 6.88 (m, 4H), 6.31 (d, J = 15.9 Hz, 2H), 4.26 (td, J = 6.0, 2.3 Hz, 4H), 4.21 (dt, J = 8.9, 6.3 Hz, 8H), 2.33 (p, J = 6.0 Hz, 4H), 1.68 (dq, J = 8.6, 6.8 Hz, 4H), 1.49 - 1.38 (m, 4H), 0.96 (t, J = 7.4 Hz, 6H).

LCMS (APCI-), calcd (M-) for Formula: C₅₃H₅₆O 885.02; found: 885.

9-(3-chlsropropoxy) anthracene, Int-8

41

SUBSTITUTE SHEET (RULE 26)

To a solution of Anthrone (7.768 g, 40 mmol) in 50.0 mL of Acetone under nitrogen atmosphere at ambient temperature was addedl-bromo-3-chloropropane (12.58 g, 80 mmol) followed by K₂CO₃ (MW: 138.21) (8.312 g, 60.0 mmol) and stirred at 75 C for 8 hours, then cooled to RT, and filtered. The filtrate was concentrated to gain 14.69 g of a dark yellow semi-solid which was washed with hexanes to gain 11.7 g of a light yellow solid, yield 48%; the product lnt-8 was used next step without further purification.

¹H NMR (400 MHz, Chloroform-d) 6 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).

LCMS (APCI-), cak'd (M-) for Formula: C₁₇H₁₅CIO 270.76 found: 270.

Synthesis of 13#5-tris(3-(anthracen-9-y!oxy) propoxy) benzene) RM-4

A mixture of lnt-8 (0.894 g, 3.3 mmol, 3.3 eq), phloroglucinol (0.126 g, 1.0 mmol,

1 eq), anhydrous potassium carbonate (0.552 g, 4.0mmol, 4 eq), and DMF anhydrous (4

SUBSTITUTE SHEET (RULE 26) ml) was stirred at 85 C under Argon atm for 16 hrs. The cooled mixture was added to water (4 ml), acidified with 4N HCI, and extracted into EA (2x 35 mL), and the organic layers were combined, washed with water (2 x 10 ml) and then concentrated to dryness. The yellow solid crude product was purified by SiCh column chromatography with Hexanes: EA (9:1) as eluant, to gain 265 mg of a colorless solid of RM-4 yield 32 %. The product was kept in an amber vial.

^TH NMR (400 MHz, Chloroform-d) 6 8.32 - 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 = 5.9 Hz, 6H), 4.42 (t, J = 6.1 Hz, 6H), 2.52 (p, J = 6.0 Hz, 6H). LCMS (APCI-), cak'd (M-) for Formula: C57H48 829.01; found: 829. zene) (1843-29)

9-(6-bromohexyl) oxy) anthracene) Int-9

43

SUBSTITUTE SHEET (RULE 26)

io a stirred solution of Anthrone (7.768g, 40.0 mmol) in 50.0 mL Acetone under nitrogen atmosphere at ambient temperature was added 1,6 dibromohexanes (39.02 g,

24.24 mL, 160.0 mmol, 4 eq) followed by potassium carbonate (8.292 g, 60.0 mmol) and the mixture was subsequently heated to 50 °C for 8 hrs. The reaction was monitored by

TLC until no more SM Anthrone remained. The reaction mixture was concentrated under reduced pressure to remove solvents. 150 mL of water was added to the residue and stirred at RT for 30 min. The precipitate was filtered and washed with 100 mL of hexanes to gain a light brown crude product which was purified by SiCh column chromatography with eluant Hex: EA (9:1) to gain 6.4 g lnt-9, 45 % yield.

^TH NMR (400 MHz, Chloroform-d) 6 8.32 - 8.25 (m, 2H), 8.22 (s, 1H), 8.05 - 7.95

(m, 2H), 7.50 - 7.40 (m, 4H), 4.21 (t, J = 6.6 Hz, 2H), 3.48 (t, J = 6.7 Hz, 2H), 2.07 (dt, J =

14.6, 6.7 Hz, 2H), 1.98 (dt, J = 14.3, 6.9 Hz, 2H), 1.77 - 1.69 (m, 2H), 1.66 - 1.58 (m, 2H)

Synthesis of 9,9'-((((5'((7~(anthracen-9-yioxy) heptyi) axy)-l,3~phenyiene) bis(oxy)) bis(hexane~6,i~diyn) bis(oxy)) diarsthracerse

Step 1: A mixture of lnt-9 (2.358 g, 6.6 mmol, 3.3 eq), phloroglucinol (0.252 g, 2.0 mmol, 1 eq), anhydrous potassium carbonate (0.552 g, 4.0mmol, 4 eq), and DMF anhydrous (4 ml) was stirred at 85 °C under Argon atm for 16 hrs. The cooled mixture

44

SUBSTITUTE SHEET (RULE 26) was added to water (4 ml), acidified with 4N HCI, and extracted into EA (2x 35 mL). The organic layers were combined, washed with water (2 x 10 ml) and then concentrated to dryness. A brown sticky solid crude product was purified by SiO2 column chromatography with Hexanes: EA (9:1) as eluant, to gain 286 mg of a sticky solid of RM-5, yield 15 %. TH NMR (400 MHz, Chloroform-d) 6 8.36 - 8.24 (m, 6H), 8.20 (s, 3H), 8.05 - 7.88

(m, 6H), 7.57 - 7.39 (m, 12H), 6.11 (s, 3H), 4.20 (t, J = 6.6 Hz, 6H), 3.96 (t, J = 6.4 Hz, 6H), 2.11 - 2.03 (m, 6H), 1.86 (p, J = 6.5 Hz, 6H), 1.73 (q, J = 7.7, 7.1 Hz, 6H), 1.62 (q, J = 8.0 Hz, 6H).

LCMS (APCI-), calcd (M-) for Formula: C₆₇H₆₈O₆: 969.28; found: 969. RM-6: i3,5~tr8s(3"(anthracen-9-ylaxy)propoxy)benzene)

SUBSTITUTE SHEET (RULE 26) 2-methyl-l,4-phenylene bis(4-acetoxybenzoate) lnt-11

4-acetoxybenzoi

MW: 180.16

lnt-10

Thionyl chloride, 13.888 ml (0.194 mol) was added drop wise to 4- acetoxybenzoic acid, 25.0 g (0.138 mol) which was stirred in a single-necked 100 ml round bottom flask and the resulting mixture was refluxed gently for 8 h. The initial heterogeneous mass homogenized to obtain a yellowish fluid. Excess thionyl chloride was removed by o rotavapor with a temperature of water bath of 26 C. Toluene (15 mL) was added to the o residue, and the resulting mixture was concentrated by rotavapor at 45 C water bath.

Purification of the crude acid chloride by double distillation under reduced pressure provided 27 g of a light yellow liquid 4-acetoxybenzoyl chloride, lnt-10 which turned to a colorless solid later. Yield 99%.

^XH NMR (400 MHz, Chloroform-d) 6 2.1 [3H, s], 7.1 [2H, d] and 8.0 [2H, d].

Step 2: A mixture of 2-methyl hydroquinone (4.96 g, 0.04 mol) and 25 ml pyridine (0.3 mol) was added to the mixture of 23.82 g of 4-acetoxybenzoyl chloride (0.12 mol) in 300 ml of dry 1,2- dichloroethane. An acid chloride solution was added to the 2- methylhydroquinone solution. This reaction mixture was stirred under nitrogen blanket for 48 h at room temperature. The reaction mixture was washed sequentially with 5% sodium carbonate solution, 5% hydrochloric acid and distilled water. The 1,2-dichloroethane layer was evaporated to dryness on a rotavapor. The crude product was recrystallized from chloroform/petroleum ether (60: 80). The product was filtered and dried in vacuum oven at 80 °C for 4 h to achieve 15.24 g of light brown solid lnt-11. 85% yield.

¹H NMR (400 MHz, Chloroform-d) 6 2.2 (3H, s), 2.3 (6H, s), 7.4 (8H, d) and 8.4 (3H, d).

LCMS (APCI-), calcd (M-) for Formula: C₂₅H₂₀O₈: 448.43; found: 448.

46

SUBSTITUTE SHEET (RULE 26) 2-methyl-l,4-phenylene bis(4-hydroxybenzoate). I nt- 12

A solution of NH₄OAc (9.68 g, 0.125 mol, 4 eq) in 100 mL H₂O was added to a mixture of 2-methyl-l,4-phenylene bis(4-acetoxybenzoate) (14.1g, 0.0314 mol, 1 eq), MeOH 250 mL, and THF 250 mL which was stirring in a single-necked 1 L round bottom flask. The resulting mixture was stirred at RT for 16 hours. The reaction mixture was yellowish. Solvents were removed under reduced pressure. The residue was washed with H₂O to gain 11.0 g of a light brown solid after drying in vacuo oven. The product lnt-11 was used next step without further purification. 99% yield.

¹H NMR (400 MHz, DMSO-d₆) 6 10.54 (s, 2H), 8.02 (d, J = 8.8 Hz, 2H), 7.99 (d, J = 8.8 Hz, 2H), 7.24 (d, J = 5.9 Hz, 1H), 7.23 (s, 1H), 7.16 - 7.11 (m, 1H), 6.95 (d, J = 4.0 Hz, 2H), 6.93 (d, J = 3.9 Hz, 2H), 2.16 (s, 3H).

LCMS (APCI-), calcd (M-) for Formula: C₂₁H₁₆O₆: 364.35; found: 364. l,3,5-tris(3-(anthracen-9-y^oxy) propoxy) benzene) RM-6

SUBSTITUTE SHEET (RULE 26) To a stirred solution of 2-methyl-l,4-phenylene bis(4-hydroxybenzoate) (1.45 g, 4.0 mmol) in 4.0 mL DMF anhydrous under nitrogen atmosphere at ambient temperature was added 9-((6-bromohexyl) oxy) anthracene (3.572 g, 10.0 mmol) followed by potassium carbonate (1.658 g, 12.0 mmol). The mixture was subsequently heated to 85 °C for 8 hrs. LCMS showed di-coupling product was formed plus mono-coupling and SM o remaining. The reaction mixture was then stirred at 78 C for 6 hrs. 500 mL CHCI₃ was added followed by 100 mL of cold water (ice + water)) to the RX mixture at RT. The resulting mixture was stirred at RT for 10 min. The organic layer was washed with 50 mL of water, separated, dried with MgSO₄, filtered, and concentrated to dryness. The crude product was purified by SiO₂ column chromatography, and eluted with DCM only and then DCM: EtAcO (95:5). Gained 3.0 g of a light brown solid which was recrystallization with MeOH gained colorless solid product of RM-6.

¹H NMR (400 MHz, Chloroform-d) 6 8.29 (ddd, J = 6.6, 2.4, 1.4 Hz, 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 = 2.7 Hz, 1H), 7.08 (dd, J = 8.6, 2.7 Hz, 1H), 7.03 - 6.97 (m, 4H), 4.23 (t, J = 6.6 Hz, 4H), 4.12 (td, J = 6.5, 2.1 Hz, 4H), 2.25 (s, 3H), 2.12 (q, J = 7.7, 7.2 Hz, 4H), 1.95 (p, J = 6.7 Hz, 4H), 1.79 (t, J = 8.1 Hz, 3H), 1.68 (p, J = 7 A, 6.9 Hz, 4H).

LCMS (APCI-), calcd (M-) for Formula: C₆₁H₅₆O₈: 917.11; found: 917.

RM-7: l,3,5-tris((5-(anthracen-9-yloxy) pentyl) oxy) benzene

SUBSTITUTE SHEET (RULE 26)

9-((5-br«3nwpentyl) oxy) anthracene.

To a stirred solution of Anthrone (7.768g, 40.0 mmol) in 50.0 mL of Acetone under nitrogen atmosphere at ambient temperature was added 1,3 dibromo pentane (36.79 g, 21.9 mL, 160.0 mmol, 4 eq) followed by potassium carbonate (8.292 g, 60.0 mmol). The mixture was subsequently heated to 50 °C for 8 hrs. The reaction was monitored by TLC until no more anthrone remained. The reaction mixture was cooled to RT, and the solid was filtered and washed with 100 mL acetone. The filtrates were combined and concentrated under reduced pressure to gain the red orange color residue, which was loaded onto 220 g SiO₂ column, eluting with Hexanes then Hex: DCM (95:5) to gain 4.5g off a white solid lnt-13, dried in Vacuo-oven and used next step without further purification. 32 % yield.

¹H NMR (400 MHz, Chloroform-d) 6 8.33 - 8.24 (m, 2H), 8.22 (s, 1H), 8.06 - 7.93 (m, 2H), 7.54 - 7.41 (m, 4H), 4.22 (t, J = 6.5 Hz, 2H), 3.52 (t, J = 6.7 Hz, 2H), 2.07 (ddt, J = 14.9, 12.4, 6.8 Hz, 4H), 1.91 - 1.82 (m, 2H).

LCMS (APCI-), calcd (M ) for Formula: C₁₉H₁₉BrO 343.26; found: 343.

49

SUBSTITUTE SHEET (RULE 26) l,3,5-tris((5-(anthracen-9-yloxy) pentyl) oxy) benzene RM-7

A mixture of lnt-13 (1.132 g, 3.3 mmol, 3.3 eq), phloroglucinol (0.126 g, 1.0 mmol, 1 eq), anhydrous potassium carbonate (0.552 g, 4.0mmol, 4 eq), and DMF anhydrous (25 o ml) was stirred at 85 C under Argon atm for 6 hrs. The cooled mixture was filtered, the filtrate was concentrated, and the solid crude product was purified by SiO₂ column chromatography with Hexanes: EA (9:1) as eluant, to gain 98 mg of a colorless solid of RM-7, yield 10 %.

^TH NMR (400 MHz, Chloroform-d) 6 8.34 - 8.24 (m, 6H), 8.20 (s, 3H), 8.03 - 7.92 (m, 6H), 7.55 - 7.37 (m, 12H), 6.16 (s, 3H), 4.22 (t, J = 6.5 Hz, 6H), 4.03 (t, J = 6.2 Hz, 6H), 2.12 (p, J = 6.7 Hz, 6H), 1.94 (q, J = 6.7, 6.0 Hz, 6H), 1.87 (q, J = 8.7, 8.2 Hz, 6H). LCMS (APCI-), calcd (M-) for Formula: C₆₃H₆₀: 913.17; found: 913.

RM-8: Synthesis of l,3,5-tris((5-(anthracen-9-yloxy) pentyl) oxy) benzene

SUBSTITUTE SHEET (RULE 26) lnt-13

To a stirred solution of 9-((5-bromopentyl) oxy) anthracene (0.765 g, 2.1 mmol) in 4.0 mL DMF anhydrous under nitrogen atmosphere at ambient temperature was added 1643-81 (1.586 g, 4.62 mmol, 2.2 eq) followed by potassium carbonate (0.58 g, 4.2 mmol) and was subsequently heated to 85 °C for 12 hrs. LCMS showed di coupling product was formed plus mono coupling and SM remaining. The reaction mixture was cooled to RT and the solid was filtered off. The filtrates were combined and concentrated by rotavapor at 50 °C, and the residue was triturated with Water to gain 1.5 g of a light brown solid product which was purified by SiO₂ column, eluant Hex: EtAco (9:1->4:1), to gain 0.42 g colorless solid of RM-8, 22% yield.

^TH NMR (400 MHz, Chloroform-d) 6 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 = 6.5 Hz, 4H), 4.17 (td, J = 6.2,

2.3 Hz, 4H), 2.25 (s, 3H), 2.16 (p, J = 6.8 Hz, 4H), 2.02 (dd, J = 13.9, 6.7 Hz, 4H), 1.92 (q, J =

8.3 Hz, 4H).

LCMS (APCI-), calcd (M-) for Formula: C59H52O8: 889.06; found: 889.

RM-9: Synthesis of 7,7',7"-(((benzene-l,3,5-triyltris(oxy)) tris(pentane-5,l-diyl)) tris(oxy)) tris(2H-chromen-2-one)

51

SUBSTITUTE SHEET (RULE 26)

DMF anhydrous, K₂CO₃, 85°C, 6 hr

l,3,5-tris((5-bromopentyl) oxy) benzene, lnt-14

SUBSTITUTE SHEET (RULE 26) To a stirred solution of Phloroglucinol (2.522g, 20.0 mmol) in 120.0 mL Acetonitrile under nitrogen atmosphere at ambient temperature was added 1,5 dibromo pentane (55.184 g, 240 mmol, 12eq) followed by potassium carbonate (33.168 g, 240.0 mmol). The mixture was subsequently heated to 85 °C for 16 hrs. The reaction was monitored by TLC until no more SM Phloroglucinol remained. The reaction mixture was cooled to RT, the solid was filtered and washed with 100 mL acetone, the filtrates were combined and concentrated under reduced pressure to gain a red orange color residue which was loaded onto a 220 g SiO₂ column, eluting with Hexanes then Hex: EA (9:1) to gain 4.58 g of colorless liquid lnt-14; the compound was used next step without further purification. 40 % yield.

¹H NMR (400 MHz, Chloroform-d) 6 6.05 (s, 3H), 3.92 (t, J = 6.3 Hz, 6H), 3.44 (t, J = 6.8 Hz, 6H), 1.98 - 1.89 (m, 6H), 1.84 - 1.75 (m, 6H), 1.66 - 1.57 (m, 6H).

LCMS (APCI-), calcd (M-) for Formula: C₂1H₃₃Br ₃O₃: 573.2; found: 573.

RM-9. 7,7',7"-(((benzene-l,3,5-triyltris(oxy)) tris(pentane-5,l-diyl)) tris(oxy)) tris(2H- chromen-2-one)

To a stirred solution of coumarin (973 mg, 6.0 mmol) in 12.0 mL DMF anhydrous under nitrogen atmosphere at ambient temperature was added 1643-85(573.2 mg, 2 mmol, leq) followed by potassium carbonate (1.658g, 12 mmol). The mixture was subsequently heated to 85 °C for 6 hrs. The reaction was monitored by TLC until no more

53

SUBSTITUTE SHEET (RULE 26) SM coumarin remained. The reaction mixture was cooled to RT and diluted with 50 mL DMF, and the solid was filtered and washed with 100 mL of acetone. The filtrates were combined and concentrated under reduced pressure to gain a red orange color residue which was triturated with water (50 ml), and the light brow solid product was loaded onto 80 g SiO2 column, eluting with DCM then DCM: EA (4:1) to gain 450 mg of a sticky colorless solid of RM-9, 27% yield,

¹H NMR (400 MHz, Chloroform-d) δ 7.63 (d, J = 9.5 Hz, 3H), 7.36 (d, J = 8.5 Hz, 3H), 6.87 - 6.81 (m, 3H), 6.82 - 6.77 (m, 3H), 6.25 (d, J = 9.5 Hz, 3H), 6.07 (s, 3H), 4.04 (t, J = 6.4 Hz, 6H), 3.95 (t, J = 6.3 Hz, 6H), 1.87 (tt, J = 14.5, 6.5 Hz, 13H), 1.72 - 1.60 (m, 7H). LCMS (APCI-), calcd (M-) for Formula: C₄₈H₄₈O₁₂: 816.9; found: 816.

RM-10: Synthesis of 7,7',7"-(((benzene-l,3,5-triyltris(oxy)) tris(hexane-6,l-diyl)) tris(oxy)) tris (2H-chromen-2-one

SUBSTITUTE SHEET (RULE 26) l,3,5-tris((6-bromohexyl) oxy) benzene, lnt-15

HO

OH

To a stirred solution of Phloroglucinol (1.261g, 10.0 mmol) in 50.0 mL Acetone under nitrogen atmosphere at ambient temperature was added 1,6 dibromo hexane

(29.276 g, 120 mmol, 12eq) followed by potassium carbonate (16.584 g, 120.0 mmol).

The mixture was subsequently heated to 50 °C for 8 hrs. The reaction was monitored by

TLC until no more Phloroglucinol remained. The reaction mixture was cooled to RT, solid was filtered and washed with 100 mL acetone, and filtrates were combined and concentrated under reduced pressure to gain a red orange color residue which was loaded onto 220 g SiO₂ column, eluting with Hexanes then Hex: EA (9:1) to gain 1.45 g of a colorless liquid lnt-15, dried in Vacuo-oven and used next step without further purification. Yield 23 %

¹H NMR (400 MHz, Chloroform-d) 6 6.05 (s, 3H), 3.91 (t, J = 6.4 Hz, 6H), 3.42 (t, J

= 6.8 Hz, 6H), 1.89 (p, J = 6.9 Hz, 6H), 1.77 (p, J = 6.4 Hz, 7H), 1.55 - 1.39 (m, 12H).

LCMS (APCI-), calcd (M-) for Formula: C₂₄H₃O₉Br 615.29; found: 615.

RM-10. 7,7',7"-(((benzene-l,3,5-triyltris(oxy)) tris(hexane-6,l-diyl)) tris(oxy)) tris(2H- chromen-2-one)

SUBSTITUTE SHEET (RULE 26)

To a stirred solution of coumarin (498.5 mg, 3.075 mmol, 4 eq) in 6.0 mL DMF anhydrous under nitrogen atmosphere at ambient temperature was added lnt-15 (473.4 mg, 0.768 mmol, leq) followed by potassium carbonate (0.424g, 3.072 mmol, 4 eq). The mixture was subsequently heated to 75 °C for 16 hrs. The reaction was monitored by TLC until no more SM coumarin remained. The reaction mixture was cooled to RT and diluted with 10 mL DMF. The solid was filtered and washed with 50 mL acetone, and filtrates were combined and concentrated under reduced pressure to gain a red orange color residue which was triturated with water (50 ml). A light brown solid product was loaded onto 80 g SiO₂ column, eluting with DCM then DCM : EA (4:1) to gain 0.47 g of a colorless sticky solid RM-10; yield 68 %.

¹H NMR (400 MHz, Chloroform-d) 67.63 (d, J = 9.5 Hz, 3H), 7.36 (d, J = 8.5 Hz, 3H), 6.83 (dd, J = 8.5, 2.5 Hz, 3H), 6.80 (d, J = 2.4 Hz, 3H), 6.24 (d, J = 9.5 Hz, 3H), 6.06 (s, 3H), 4.02 (t, J = 6.4 Hz, 6H), 3.93 (t, J = 6.4 Hz, 6H), 1.82 (dt, J = 18.1, 6.6 Hz, 12H), 1.54 (t, J = 3.9 Hz, 12H).

LCMS (APCI-), calcd (M-) for Formula: C₅₁H₅₄O₁₂: 858.98; found: 858.

RM-11: 5-((3-((5-(anthracen-9-yloxy) pentyl) oxy) benzoyl) oxy)-l,3-phenylene bis(4- ((5-(anthracen-9-yloxy) pentyl) oxy) benzoate)

56

SUBSTITUTE SHEET (RULE 26)

5 methyl 4-((5-bromopentyl) oxy) benzoate, lnt-16

57

SUBSTITUTE SHEET (RULE 26)

methyl 4-hydroxybenzoate

To a stirred solution of methyl 4-hydroxybenzoate (4.108 g, 27.0 mmol) in 20.0 mL of dimethylformamide under nitrogen atmosphere at ambient temperature was added 1,5 dibromopentane (24.833g, 108 mmol) followed by potassium carbonate (7.463g, 54 mmol). The reaction mixture was stirred at 56 °C for 16 hr. After cooling to RT, the reaction mixture was filtered. The filtrate was concentrated, and the residue was dissolved into DCM (250ml) then washed with 100 mLcold water, dried with MgSO4, and concentrated. The crude product was purified by SiC>2 column chromatography with Hexanes: EA (9:1), to gain 7.3g of a colorless liquid of lnt-16; yield 89 %

¹H NMR (400 MHz, Chloroform-d) 67.98 (d, J = 8.9 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 4.02 (t, J = 6.3 Hz, 2H), 3.88 (s, 3H), 3.43 (t, J = 6.7 Hz, 2H), 2.00 - 1.89 (m, 2H), 1.87 - 1.78 (m, 2H), 1.63 (t, J = 7.9 Hz, 2H).

LCMS (APCI-), calcd (M-) for Formula: C1₃H1₇BrO₃: 301.18; found: 301. methyl 4-((5-(anthracen-9-yloxy) pentyl) oxy) benzoate, kit-17

SUBSTITUTE SHEET (RULE 26)

O

Chemical Formula;

Molecular Weight 400 47

Step 1: To a stirred solution of anthrone (1.9423 g, 10.0 mmol) in 10.0 mL dimethylformamide under nitrogen atmosphere at ambient temperature was added Int- 16 (3.018g, 10.0 mmol) followed by potassium carbonate (2.764 g, 20 mmol). The o reaction mixture was stirred at 85 C for 16 hr. The reaction mixture was filtered. The insoluble material was washed with Ethyl acetate. The filtrates were combined and concentrated. The residue was washed with 1.01 cold water followed by 1.01 heptane. The crude product was purified by SiC>2 column chromatography with Hexane only --> Hexanes: DCM (1:1), to gain 3.02 g of a light orange sticky liquid lnt-17; yield 72 %. The product contained some anthrone SM, and was carried on next step without further purification.

^TH NMR (400 MHz, Chloroform-d) 6 8.32 - 8.24 (m, 2H), 8.22 (s, 1H), 8.10 - 8.03 (m, 2H), 8.03 - 7.95 (m, 2H), 7.52 - 7.41 (m, 4H), 6.97 (d, J = 9.0 Hz, 2H), 4.25 (t, J = 6.5 Hz, 2H), 4.14 (t, J = 6.3 Hz, 2H), 2.14 (dt, J = 14.1, 6.7 Hz, 2H), 2.05 - 1.85 (m, 5H).

LCMS (APCI-), calcd (M-) for Formula: C₂₇H₂₄O₄:: 414.5; found: 4:14.

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

59

SUBSTITUTE SHEET (RULE 26) ^XH NMR (400 MHz, 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)

LCMS (APCI-), caicd (M-) for Formula: C₂₆H₂₄O₄: 400.47; found: 400. benzene- 1, 3, 5-triyl tris(4-((5-(anthracen-9-yloxy) pentyl) oxy) benzoate). RM-11

To a mixture of RM-17 (lg, 2.49 mmol, 4eq), DMAP-pTSA (1.467 g, 4.99 mmol, 8eq), EDC.HCI (1.431 mg, 7.47 mmol, 12 eq) was added DCE: CHCI₃ (1:1) (45 mL) following phloroglucinol (0.0785 g, 0.622 mmol, 1 eq). The resulting mixture was stirred at RT for 16 hrs under argon atmosphere. Added more 1643-92 (324 mg) and EDC.HCI (298 mg). The resulting mixture was stirred further 3 hours. Added H₂O (10 mL) then stirred further 15 minutes. The organic layer was separated, concentrated to the volume of 20 ml and loaded into 40 g SiO₂ column and eluting with Hex-DCM (7/3), then gradually to DCM only. The pure fractions were collected, concentrated, and dried in vacuo-oven to gain 470 mg of a colorless solid RM-11; yield 37%.

^TH NMR (400 MHz, Chloroform-d) 6 8.34 - 8.24 (m, 6H), 8.22 (s, 3H), 8.14 (d, J = 8.9 Hz, 6H), 8.04 - 7.94 (m, 6H), 7.54 - 7.40 (m, 12H), 7.13 (s, 3H), 7.00 (d, J = 9.0 Hz, 6H),

60

SUBSTITUTE SHEET (RULE 26) 4.25 (t, J = 6.5 Hz, 6H), 4.16 (t, J = 6.3 Hz, 6H), 2.15 (p, J = 6.7 Hz, 6H), 2.02 (p, J = 6.4 Hz, 6H), 1.95 - 1.85 (m, 6H).

LCMS (APCI-), calcd (M-) for Formula:

1273.49; found: 1273. RM-12: l,3,5-tris(4-(anthracen-9-yloxy) butoxy) benzene

To a stirred solution of Anthrone (4.0g, 20.6 mmol) in 20.0 mL DMF anhydrous under nitrogen atmosphere at ambient temperature was added potassium carbonate (5.694 g, 41.2 mmol) followed byl,4 dibromo butane (18 g, 83.36 mmol). The mixture

61

SUBSTITUTE SHEET (RULE 26) was subsequently heated to 65 °C for 8 hrs. The reaction was monitored by TLC until no more anthrone remained and the reaction mixture turned into a light beige color. The reaction mixture was cooled to RT and the solid was filtered and washed with 100 mL acetone. The filtrates were combined, and concentrated under reduced pressure to gain orange color products which were loaded onto 220 g SiO₂ column, eluting with Hexanes then Hex: DCM (95:5) to gain 3.5g of a white solid lnt-18, dried in Vacuo-oven and used next step without further purification, yield 51 %.

^TH NMR (400 MHz, Chloroform-d) 6 8.29 - 8.25 (m, 1H), 8.24 (dt, J = 2.8, 1.0 Hz, 1H), 8.22 (s, 1H), 8.00 (tt, J = 2.2, 1.4 Hz, 1H), 7.98 (dd, J = 1.9, 1.2 Hz, 1H), 7.51 - 7.41 (m, 4H), 4.23 (t, J = 6.2 Hz, 2H), 3.61 (t, J = 6.6 Hz, 2H), 2.39 - 2.26 (m, 2H), 2.26 - 2.15 (m, 2H).

LCMS (APCI-), calcd (M-) for Formula: C₁₃H₁₇BRO 329.24; found: 329. l,3,5-tris(4-(anthracen-9-yloxy) butoxy) benzene. RM-12

A mixture of lnt-18 (2.43 g, 7.38 mmol, 3.69 eq), phloroglucinol (0.250 g, 2.0 mmol, 1 eq), anhydrous potassium carbonate (1.104 g, 8.0mmol, 4 eq), and DMF anhydrous (25 ml) was stirred at 85 °C under Argon atm for 16 hrs. The cooled mixture was filtered, the filtrate was concentrated, and the solid crude product was washed with water then loaded onto 80g SiO₂ column, eluting with Hexanes: DCM-> DCM only as eluant. Fractions 8-10 were collected and concentrated to gain 1.2 g of a gummy solid,

SUBSTITUTE SHEET (RULE 26) yield 68 %. NMR showed some impurities. The above impure product was loaded into second column 80 g SiO2, eluting with Hex: EA (100% -> 20%) to gain an off white solid which was triturated with Ethyl acetate to gain 0.85 g of a colorless solid of RM-12, yield 48% 1H NMR (400 MHz, Chloroform-d) 6 8.33 - 8.25 (m, 6H), 8.21 (s, 3H), 8.03 - 7.94

(m, 6H), 7.51 - 7.40 (m, 13H), 6.19 (s, 3H), 4.31 - 4.24 (m, 6H), 4.15 - 4.08 (m, 6H), 2.32 - 2.16 (m, 12H).

LCMS (APCI-), calcd (M-) for Formula: C₆₀H₅₄O ₆71.09; found: 871. RM-13: benzene-l,3,5-triyl tris(4-(3-(anthracen-9-yloxy) propoxy) benzoate)

4-((4-(anthracen-9-yloxy) butoxy) methyl) benzoic acid, lnt-19

SUBSTITUTE SHEET (RULE 26)

Step 1: To a stirred solution of lnt-18 (3.29 g, 10.0 mmol) in 10.0 mL dimethylformamide under nitrogen atmosphere at ambient temperature was added methyl 4-hydroxy benzoate (1.67 g, 11 mmol) followed by potassium carbonate (2.764 g, 20 mmol). The reaction mixture was stirred at 85 °C for 16 hr. The reaction mixture was filtered. The insoluble material was washed with Ethyl acetate. The filtrates were combined and concentrated to dryness. The residue was washed with cold water followed by hexane to gain 4.14 g of an off white solid product which was carried on to the next step without further purification.

Step2: A solution of 4 N NaOH in H₂O (10 mL, 40 mmol) was added to the above mixture (4.0 g) in THF (50 mL) and (5 mL) MeOH. The resulting mixture was stirred at 45 °C for 12 hours. The reaction was monitored by TLC and LCMS. When the conversion was completed the reaction mixture was poured to water (100 mL). The off-white solid product was washed with water. Acetone, then DCM were added, and then drying in vacuo-oven to gain 3.9 g of an off-white solid lnt-19, overall yield of two steps was 90%.

¹H NMR (400 MHz, DMSO-d₆) 6 8.38 (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 = 6.2 Hz, 2H), 4.13 (t, J = 6.1 Hz, 2H), 2.26 - 2.13 (m, 2H), 2.13 - 2.00 (m, 2H).

LCMS (APCI-), calcd (M-) for Formula: C2₅H2₄O₄: 400.47; found: 400. benzene- 1, 3, 5-triyl tris(4-(4-(anthracen-9-yloxy) butoxy) benzoate) RM-13

64

SUBSTITUTE SHEET (RULE 26)

To a mixture of lnt-19 (1.082g, 2.8 mmol, 4.5 eq), DMAP-pTSA (1.467 g, 4.99 mmol, 8eq), EDC.HCI (1.431g, 7.47 mmol, 12 eq) was added DCE: CHCI₃ (1:1) (45 mL) following phloroglucinol (0.0785 g, 0.622 mmol, 1 eq). The resulting mixture was stirred at RT for 16 hrs under argon atmosphere. The resulting mixture was stirred further for 3 hours. Added H₂O (10 mL) then stirred further 15 minutes. The organic layer was separated, concentrated to the volume of 20 ml, and loaded into 80 g SiO₂ column; eluting with Hex- DCM (7/3), then gradually change to DCM only. The pure fractions were collected, concentrated, and dried in vacuo-oven to gain 570 mg of a colorless solid of RM-13, yield 77 % yield.

¹H NMR (400 MHz, Chloroform-d) 6 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). LCMS (APCI-), calcd (M-) for Formula: C₈₁H₆₆O₁₂ 1231.4; found: 1231.

RM-14: 2-methyl-l,4-phenylene bis(4-(4-(anthracen-9-yloxy) butoxy) benzoate)

65

SUBSTITUTE SHEET (RULE 26) lnt-19

DCE: CHCI3 (1 :1)

DMAP-pTSA , EDC. HCI

To a mixture of lnt-19 (0.932g, 2.4 mmol, 2.4 eq), DMAP-pTSA (1.47 g, 5.0 mmol, 5 eq), EDC. HCI (1.437 g, 7.5 mmol, 7.5 eq) was added DCE: CHCU (1:1) (45 ml) following methylhydroquinone (0.124 g, Immol, 1 eq). The resulting mixture was stirred at RT for 16 hrs under argon atmosphere. The mixture was stirred further for 3 hours. Added H₂O

(10 ml) then stirred further for 15 minutes. The organic layer was separated, concentrated to the volume of 20 ml, and loaded Into 80 g SiO? column; eluting with Hex- DCM (7/3), then gradually change to DCM only. The pure fractions were collected, concentrated, dried in vacuo oven to gain 730 mg of a colorless solid of RM-14, yield 85 %.

^TH NMR (400 MHz, Chloroform-d) 5 8.37 - 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, 3.3 Hz, 8H), 7.19 (d, J = 8.7 Hz, 1H), 7.14 (d, J = 2.8 Hz, 1H), 7.09 (dd, J = 8.6, 2.8 Hz, 1H), 7.06 - 6.97 (m, 4H), 4.30 (q, J = 4.3, 3.1 Hz, 4H), 4.25 (h, J = 2.5 Hz, 4H), 2.36 - 2.19 (m, 11H). LCMS (APCI-), calcd (M-) for Formula: C₅₇H₄₈ 861.00; found: 861.

RM-15: 5-(anthracen-9-yloxy)pentyl 2,4,6-tris((5-(anthracen-9- yloxy)pentyl)oxy)benzoate

SUBSTITUTE SHEET (RULE 26)

A mixture of lnt-18 (0.799 g, 2.345 mmol, 4.69 eq), 2,4,6-trihydroxybenzoic acid (85 mg, 0.5 mmol, 1 eq), anhydrous potassium carbonate (0.276 g, 2.0mmol, 4 eq), and DMF anhydrous (15 ml) was stirred at 75 °C under Argon atm for 16 hrs. The cooled mixture was filtered, and the filtrate was concentrated. The solid crude product was washed with water then loaded onto 80g SiO₂ column, eluting with Hexanes: DCM-> DCM only as eluant. Fractions 8-10 were collected and concentrated to a gummy solid which was triturated with Ethyl acetate to gain 0.250 g of an off white solid of RM-15, yield 40% TH NMR (400 MHz, Chloroform-d) 6 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 = 6.7 Hz, 2H), 4.22 (t, J = 6.4 Hz, 2H), 4.12 (t, J = 6.5 Hz, 4H), 4.05 (t, J = 6.2 Hz, 6H), 3.95 (t, J = 6.5 Hz, 2H), 2.11 (q, J = 7.0 Hz, 2H), 2.01 (q, J = 6.9 Hz, 4H), 1.89 (tt, J = 14.9, 7.5 Hz, 10H), 1.79 (q, J = 7.7 Hz, 6H), 1.66 - 1.58 (m, 2H).

LCMS (APCI-), calcd (M-) for Formula:

1219.53; found: 1219.

RM-16: 5-(anthracen-9-yloxy)pentyl 2,4,6-tris((5-(anthracen-9- yloxy)pentyl)oxy)benzoate

SUBSTITUTE SHEET (RULE 26)

A mixture of lnt-18 (0.823 g, 2.5 mmol, 5 eq), 2,4,6-trihydroxybenzoic acid (85 mg, 0.5 mmol, 1 eq), anhydrous potassium carbonate (0.345 g, 2.5 mmol, 5 eq), and DMF anhydrous (15 ml) was stirred at 75 °C under Argon atm for 16 hrs. The cooled mixture was filtered, and the filtrate was concentrated. The solid crude product was washed with water then loaded onto 80g SiO₂ column, eluting with Hexanes: DCM-> DCM only as eluant to gain a gummy solid which was triturated with Ethyl acetate to gain 0.275 g of an off white solid of RM-16; yield 47%

^TH NMR (400 MHz, Chloroform-d) 6 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), 7.25 - 7.20 (m, 2H), 6.23 (s, 2H), 4.41 (d, J = 5.9 Hz, 2H), 4.26 (s, 2H), 4.16 (d, J = 4.6 Hz, 10H), 4.09 (d, J = 5.8 Hz, 2H), 2.20 (s, 4H), 2.16 (d, J = 1.2 Hz, 8H), 2.10 (d, J = 3.2 Hz, 4H).

LCMS (APCI-), calcd (M ) for Formula: G₈₃H₇₈O₉ 1163; found: 1163.

RM-17: 2-methyl-l,4-phenylene bis(3,5-bis(4-(anthracen-9-yloxy) butoxy)benzoate)

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SUBSTITUTE SHEET (RULE 26)

3,5-bis(4-(anthracen-9-yloxy) butoxy) benzoic acid, lnt-20

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SUBSTITUTE SHEET (RULE 26)

Step 1: A mixture of lnt-18(1.9754 g, 6.0 mmol, 3 eq), methyl 3,5- di hydroxy benzoate (336.3 mg, 2.0 mmol, 1 eq), anhydrous potassium carbonate (1.104 g, 8.0mmol, 4 eq), and MeCN anhydrous (25 ml) was stirred at 65 °C for 8 hrs then 75 °C under Argon for 8 hrs. The cooled mixture was filtered, and the filtrate was concentrated. The solid crude product was washed with water then loaded onto 80g SiO₂ column, eluting with Hexanes: DCM-> DCM only as eluant, to gain 1.1 g colorless of a sticky solid, yield 82 %.

^TH NMR (400 MHz, Chloroform-d) 6 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, 1.3 Hz, 1H), 7.13 (dd, J = 2.4, 1.3 Hz, 1H), 6.64 (t, J = 2.3 Hz, 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, 2.2 Hz, 4H).

LCMS (APCI-), calcd (M-) for Formula:

664; found: 664.

Step 2: A mixture of the above compound was dissolved into 16 mL of THF/MeOH (15/1), and lOmL of 4N NaOH aq. (40 mmol) was added. The resulting mixture was stirred at 45 °C for 5 hours. After cooling to 0 °C and being acidified with 4N HCI. The products were extracted into CHCL The organic layer was separated, washed with water, concentrated to dryness. The crude product was purified by SiCh column chromatography, eluting with DCM only to gain 1.0 g of a colorless solid lnt-20.

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SUBSTITUTE SHEET (RULE 26) ¹H NMR (400 MHz, Chloroform-d) 6 8.34 - 8.26 (m, 4H), 8.22 (s, 2H), 8.03 - 7.95

(m, 4H), 7.54 - 7.40 (m, 8H), 7.29 (d, J = 2.3 Hz, 2H), 6.79 (t, J = 2.3 Hz, 1H), 4.33 - 4.25

(m, 4H), 4.18 (d, J = 5.1 Hz, 4H), 2.24 (t, J = 3.0 Hz, 7H).

LCMS (APCI-), caicd (M-) for Formula: C₄₃H₃₈O₅: 650; found: 650.

2-methyl-l,4-phenylene bis(3,5-bis(4-(anthracen-9-yloxy) butoxy) benzoate) RM-17,

To a mixture of Int-20 (0.88g, 1.352 mmol, 2.5 eq), DMAP-pTSA (0.635 g, 4.99 mmol 2.16mmol, 4 eq), EDC.HCI (0.62g, 3.24 mmol, 6 eq) was added DCE: CHCI₃ (1:1) (45 mL) following methyl hydroquinone (0.067 g, 0.54 mmol, 1 eq). The resulting mixture was stirred at RT for 6 hours under argon atmosphere. An additional 250 mg of EDC.HCI was added, and the resulting mixture was stirred further at RT 3 hours. H₂O (10 mL) was added and then stirred further 15 minutes. The organic layer was separated, and washed with

IN aq HCI. The organic layer was separated and concentrated, and the crude product was loaded into 80 g SiO₂ column; eluting with Hex-DCM then gradually change to DCM only.

The pure fractions were collected, concentrated, and dried in vacuo-oven to gain 570 mg of a colorless solid of RM-17, yield 72 %.

¹H NMR (400 MHz, Chloroform-d) 6 8.34 - 8.26 (m, 9H), 8.22 (s, 4H), 8.03 - 7.95

(m, 9H), 7.50 - 7.43 (m, 16H), 7.43 (d, J = 2.4 Hz, 2H), 7.40 (d, J = 2.3 Hz, 2H), 7.22 - 7.07

(m, 4H), 6.83 (dt, J = 4.7, 2.3 Hz, 2H), 5.29 (s, 3H), 4.29 (d, J = 5.6 Hz, 8H), 4.25 - 4.18 (m,

8H), 2.26 (s, 19H).

SUBSTITUTE SHEET (RULE 26) LCMS (APCI-), calcd (M-) for Formula: C₉₃H₅₀O_12: 1389; found: 861.

RM-18:l,3,5-triyl tris(4-(3-(anthracen-9-yloxy) propoxy) benzoate) lnt-4

EDC, pTSA-DMAP, CHCI3-DCE

To a mixture of lnt-4 (1.042g, 2.8 mmol, 4.5 eq), DMAP-pTSA (1.467 g, 4.99 mmol, 8eq), EDC. HCI (1.431 mg, 7.47 mmol, 12 eq) was added DCE: CHCI₃ (1:1) (45 mL) following phloroglucinol (0.0785 g, 0.622 mmol, 1 eq). The resulting mixture was stirred at RT for 16 hrs under argon atmosphere. H₂O (10 mL) was added then stirred further for 15 minutes. The organic layer was separated, concentrated to the volume of 20mL and loaded into 80 g SiO₂ column; eluting with Hex-DCM (7/3), then gradually change to DCM only. The pure fractions were collected, concentrated, and dried in vacuo-oven to gain 570 mg of a colorless solid of RM-18, yield 77 % yield.

¹H NMR (400 MHz, Chloroform-d) 6 8.22 (ddd, J = 8.9, 7.6, 1.6 Hz, 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 = 6.0 Hz, 6H), 4.43 (t, J = 6.0 Hz, 6H), 2.55 (p, J = 6.0 Hz, 6H).

LCMS (APCI-), calcd (M-) for Formula: C₇₈H₆₀O₁₂: 1189.33; found: 1189.

Fabrication of liquid crystal based dimmable device using capillary method

A selectively dimmable device based on a heterocyclic base liquid crystal compound with positive dielectric anisotropy was fabricated using a capillary method.

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SUBSTITUTE SHEET (RULE 26) For the capillary method, a homogeneous-type liquid crystal test cell (KSRO- 10/B107M1NSS05, E.H.C Co. Ltd, Tokyo, Japan) was used for making the device. The test cell included two substrates with supports that defined an active alignment area in between the two substrates. The size of the glass/ITO substrate was 20 mm x 25 mm with a sheet resistance about 100 Q/sq and the active alignment area was about 10 mm x 10 mm with a cell gap of 10 pm. The cell was procured pre-coated with a polyamide alignment layer (LX-1400, Hitachi-Kasei Shoji Co., Ltd., Tokyo, Japan) so that no application of the alignment layers was necessary. Since the geometry of the cell included supports to ensure preservation of the cell gap, separate spacers were not required to be inserted into the cell before application of the liquid crystal mixture.

First, a liquid crystal mixture was prepared by mixing a fluorinated liquid crystal and a reactive mesogen, e.g., one of RM-1 to RM-18, with a weight ratio of 95 wt% to 5 wt% respectively using a vortex mixer to mix the formulation at 75 °C. Next, the test cells were preheated for the liquid crystal injection by warming the substrates at 75 °C for 5 minutes on a hot plate. Then, the hot coating formulation was injected near the opening of the test cell. The solution was then allowed to flow into the test cell by capillary action until it coated the entire active alignment area. In some embodiments, the test cell was put on the hot plate after the injection of coating formulation to help homogenous coverage of the liquid crystal completely. The resulting coated substrates were then soft baked at 75 °C for about 3 minutes on the hot plate to remove any residuals. After the soft baking, the result was a layered cell assembly ready for ultraviolet radiation curing (UV-curing).

The layered cell assembly was soldered to conductive wires with indium for later haze measurement. Then, the layered cell assembly was placed into a UV chamber (365 nm, UWAVE, Villebon-sur-Yvette, France). The layered cell assembly was cured at 187 mW/cm² incident power for 1-20 minutes which indicates 11-220 joules.

Next, the dimmable assembly was placed in electrical communication port and conductive clips and wires attached. An electric field was derived across the liquid crystal by applying an AC voltage. Then, the alignment of the reactive mesogen in the liquid crystal composite was changed and the cell showed opaque from transparent.

Haze measurement

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SUBSTITUTE SHEET (RULE 26) A haze was measured based on JIS K 7136 through use HM-150 (spectrophotometer) manufactured by Murakami Color Research Laboratory, Tokyo, Japan.

Table 1 Haziness of liquid crystal mixtures, containing 5.0 wt.% photoreactive RMs (95% nonreactive LC) at the time of application of various voltage.

Table 2 Haziness of liquid crystal mixtures, containing 5.0 wt.% photoreactive RMs (95% nonreactive LC) at the time of application of various voltage.

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SUBSTITUTE SHEET (RULE 26)

Table 3 Haziness of liquid crystal mixtures, containing 5.0 wt.% photoreactive RMs

(95% nonreactive LC) at the time of application of various voltage.

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SUBSTITUTE SHEET (RULE 26)

Test I : Dimmable assembly (mixture of LC/Anthracene (95/5) in ITO test cell) via UV365 nm<->UV254 nm (Dimerization <-> Dissociation)

Furthermore, a reversibility of the driven voltage change at a specific haziness was examined by irradiating a prepared dimmable assembly sample under UV LED (254 nm, Analytik Jena, California, USA) at an incident power of 9 mW/cm². First, each sample was placed under UV LED (365 nm, UWAVE, Villebon-sur-Yvette, France) at an incident power of 187 mW/cm²for 0~60 min (about 673.2 J/cm2). (The crosslink density would increase upon dimerization process, and thus increase the driven voltage). Then, the sample was irradiated with the UV LED (254 nm) for 0~20 min (about 32.4 J/cm2)(cleavage occurred and the driven voltage shift to low) and then tested for haziness. The result of the reversibility is shown in Figs. 5-6.

Test II : Liquid Crystal's solution in THF via UV365 nm (dimerization)/UV 254 nm (dissociation) by GPC measurements Dimerization

10~100 mg of RM-13 and 10 ml of THF were introduced into a stirring quartz vial attached to a condenser that was equipped with an Argon gas inlet. The mixture was stirred at room temperature while introducing the Argon gas for at least 30 min to remove oxygen from the reaction system and then the vial attached with a sealing cap was transferred to UV 365 nm photoreactor (Photoreactor M2, Penn PHD, Sigma-Aldrich, Germany) for about 0~60 min for dimerization. After stopping the reaction, a dimmer-

76

SUBSTITUTE SHEET (RULE 26) containing solution was obtained. Next, the apparent molecular weight of the dimmer solution was determined via GPC measurement (Hitachi Chromaster GPC system)

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

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

See Figures 7 and 8.

Dissociation

A dimerized solution with a predetermined concentration was filled into a quartz cuvette having a 1 mm light path and then exposed to the UV LED (254 nm, Analytik Jena) for about 0~60 min. After exposure, a dissociated solution was obtained. Next, the apparent molecular weight of the dissociated solution was determined via GPC measurement (Hitachi Chromaster GPC system).

Table 6: 5 mg RM-13 / ml THF solution exposed to UV365 for 20 min followed by UV 254 at different exposure times.

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SUBSTITUTE SHEET (RULE 26)

See Figures 9 and 10.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

The terms "a," "an," "the" and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or representative language (e.g., "such as") provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of any claim. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion

SUBSTITUTE SHEET (RULE 26) or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, the claims include all modifications and equivalents of the subject matter recited in the claims as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context.

In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the claims. Other modifications that may be employed are within the scope of the claims. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the claims are not limited to embodiments precisely as shown and described.

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SUBSTITUTE SHEET (RULE 26)

Claims

CLAIMS What is claimed is:

1. A photoreactive liquid crystal compound according to the following formula:

wherein R? is selected from a bond, a hydrogen or a C1-C3 alkyl; wherein Li, L3, L4, and L5 are independently selected from a C2-C8 diether linker or a C2-C8 ether acetate linker; and

Ri, R3, R4 and Rs are independently selected from an anthracenyl, a coumarinyl, a cinnamicyl acid, a stilbenyl, or a thymyl.

2. The photoreactive liquid crystal compound of claim 1, wherein Li, L3, L4, and Ls are independently selected from:

wherein n or m is an integer from 1-10.

SUBSTITUTE SHEET (RULE 26)

3. The photoreactive liquid crystal compound of claim 1, wherein Ri, R3, R4, and Rs are independently selected from

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

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

SUBSTITUTE SHEET (RULE 26)

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

6. A liquid crystal element, comprising the polymer dispersed liquid crystal composition of claim 5.

7. A method, comprising:

SUBSTITUTE SHEET (RULE 26) providing an oligomer or polymer comprising one or more compounds of any one of claims 1-4; and irradiating the oligomer or polymer with crosslinking ultraviolet radiation to provide a crosslinked oligomer or polymer.

8. The method of claim 7, wherein the crosslinking ultraviolet radiation includes a wavelength in the range of about 305 nm to about 395 nm.

9. The method of claims 7 or 8, wherein the irradiating includes 0.1 to 2500 J/cm2 of the crosslinking ultraviolet radiation.

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

11. The method of claim 10, wherein the cleaving ultraviolet radiation includes a wavelength in the range of about 254 nm to about 280 nm.

12. The method of claim 10, wherein the irradiating with the cleaving ultraviolet radiation includes 0.1 to 2500 J/cm2 of the cleaving ultraviolet radiation.

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SUBSTITUTE SHEET (RULE 26)