JP5388097B2 - Liquid crystal material, liquid crystal material film, coating material, and liquid crystal material film manufacturing method - Google Patents

Description

The present invention relates to a liquid crystal material, a compound, a piezochromic light emitting material, a liquid crystal material film, a coating material, and a liquid crystal material film manufacturing method.

In recent years, piezochromic light-emitting materials have attracted attention as stimuli-responsive light-emitting materials that change the aggregate structure of molecules in response to pressure or mechanical shear and change their emission color for applications in memory and sensors. ing. Until now, such materials have been reported mainly in systems in which organic crystals and pigments are dispersed in polymers (for example, Non-Patent Document 6).

Here, the piezochromic light emitting material reported so far will be described with reference to examples. However, the description will be focused on compounds in which the change in emission color is not the change in the molecular skeleton itself but the change in the molecular assembly structure. There are very few reported examples of the piezochromic luminescent material itself, including examples in which crystals alone or pigments are dispersed in a polymer. In addition, as far as liquid crystals are concerned, the present inventors' report described below is the first.

There are several examples of compounds in which the molecular skeleton of the compound itself is changed by a mechanical stimulus and the emission color is changed. However, since a compound in which the molecular skeleton itself changes is broken and becomes a radical, a material whose emission color changes due to a change in the molecular assembly structure can be said to be more excellent in durability.

dyes and pigments, 1993, 23, 73-78

As far as the present inventors know, the following compounds are the first examples showing piezochromic emission characteristics with organic materials (limited to materials whose emission color changes due to changes in the molecular assembly structure).

Adv. Mater. 2002. 14. 1625-1629

Figure 16 shows a study by C. Weder's group. This is the first paper in which a dye is mixed with a polymer and the emission color is changed by stretching or temperature. Since this paper, research has been conducted to date on oligophenylene vinylene (OPV) having a cyano group such as Compound 1 and Compound 2 in the figure.

Chem. Mater. 2003, 15, 4717-4724

This is a C. Weder group study. This is a slightly expanded version of the above story. However, there is no change in the system in which the pigment is mixed with the polymer. Since then, several papers have been published on the system of mixing pigments with polymers.

Chem. Mater. 2005, 17, 50-56

Figure 17 shows the research of the group of the National Institute of Advanced Industrial Science and Technology. This is a report example that the light emission color changes due to the crystal structure changing by rubbing the right compound.

J. Mater. Chem., 2007, 17, 783-790

FIG. 18 shows a system in which a dye is mixed with a polymer, although it is not a group of C. Weder. As shown in the figure, the emission color changes only in the stretched portion.

J. AM. CHEM. SOC. 2007, 129, 1520-1521

Figure 19 shows a study by Araki Lab., Institute of Industrial Science, University of Tokyo. The tetraphenylpyrene derivative exhibits blue light emission under ultraviolet light irradiation before rubbing with a mortar or the like, but exhibits blue-green light emission after rubbing. By rubbing, the stable aggregate state controlled by hydrogen bonds changes to a metastable aggregate state with disordered hydrogen bonds. This metastable state can be restored to the original stable state by heating, and blue light emission is restored.

Adv. Mater. 2008, 20, 119-122

FIG. 20 shows an example in which the C. Weder group started with a single compound without using a polymer. The luminescent color changes by rubbing the oligophenylene vinylene derivative mixed in the polymer. Although it seems to show liquid crystallinity in the high temperature region, there is no description to rub in that temperature region.

Angew. Chem. Int. Ed. 2008, 47, 5175 -5178

FIG. 21 shows a report example of the present inventors. This is the first piezochromic luminescent material in liquid crystals. However, there were drawbacks such as the need for a high temperature treatment of 200 ° C. to restore the original color.

This document will be described in detail. In this document, the present inventors have reported a liquid crystalline pyrene derivative that exhibits a cubic phase-columnar phase transition in response to shear and whose emission color changes from yellow to blue-green (a → c in the figure). . Liquid crystals are functional soft materials that combine order and dynamic properties, and have many advantages not found in organic crystals, such as being able to be applied in large areas. However, with the previously reported pyrene derivatives, once the emission color becomes bluish green due to the application of shear, it was necessary to heat to near 200 ° C and go through an isotropic phase (c → b in the figure) to return to the yellow emission color. → a). When a practical material such as a memory or a sensor is intended, it is desirable that the emission color change be achieved reversibly in a highly viscous liquid crystal state. In addition, the pyrene derivative was confirmed to decompose in the high temperature region (160 ° C. or higher), and the phenomenon that the quantum yield dropped visibly.

Angew. Chem. Int. Ed. 2008, 47, 6286 -6289

As shown below, it is a report example of a light-emitting liquid crystal containing a metal, but there is a description that the emission color changes when rubbed in the latter half of the paper. This is the second report example of the liquid crystal piezochromic light emitting material after the present inventors. However, there is little description of what kind of molecular aggregate structure changes are responsible for the change in light emission, and the main theme of the paper is "I made a shining liquid crystal using a rigid part containing metal" Is the subject.

J. AM. CHEM. SOC. 2008, 130, 10044-10045

Figure 22 shows a study of a Hokkaido University group in Japan. This is a report example of a piezochromic luminescent material with a compound containing Au. The emission color changes from blue to yellow by rubbing the following compounds. In addition, the original emission color is restored by exposure to a solvent. Other than that, there is a description that there is a report example that the emission color changes when rubbing with an organometallic complex containing Au, etc., but it is almost certainly not a liquid crystal but a crystal powder. It seems to be a story.

The present invention has been made in view of the above-described background art, and an object thereof is to provide a useful functional liquid crystal material and the like.

According to this invention, in order to achieve the above-mentioned object, the configuration as described in the claims is adopted. Hereinafter, the present invention will be described in detail.

The first aspect of the present invention is
A core that is a light emitting site;
A dendron skeleton bonded to the core ;
A branched alkyl group bonded to the outer edge of the dendron skeleton , and
In response to an external stimulus, it shows a luminescent color change by direct phase transition between the two phases in the liquid crystal state,
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. Either a dye or a derivative thereof,
The dendron skeleton is poly (aryl
ether) type or aromatic polymer,
The branched alkyl group is an alkyl group represented by the following chemical formula or 3,7,11-trimethyldodecane .
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen. )
It is in.
The second aspect of the present invention is
A core that is a light emitting site;
A dendron skeleton bonded to the core ;
A branched alkyl group bonded to the outer edge of the dendron skeleton , and
In response to an external stimulus, it shows a luminescent color change by direct phase transition between the two phases in the liquid crystal state,
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. Either a dye or a derivative thereof,
The dendron skeleton is poly (aryl
ether) type or aromatic polymer,
The branched alkyl group is one of an alkyl group represented by the following chemical formula and 3,7,11-trimethyldodecane .
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen. )
It is in.
The third aspect of the present invention is
A core that is a light emitting site;
A dendron skeleton bonded to the core ;
A branched alkyl group bonded to the outer edge of the dendron skeleton , and
In response to an external stimulus, it shows a luminescent color change by direct phase transition between the two phases in the liquid crystal state,
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. Either a dye or a derivative thereof,
The dendron skeleton is poly (aryl
ether) type or aromatic polymer,
The branched alkyl group is an alkyl group represented by the following chemical formula or 3,7,11-trimethyldodecane .
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen. )
It is in.
The fourth aspect of the present invention is
It comprises a core that is a light emitting site, a dendron skeleton bonded to the core, and a branched alkyl group that is bonded to an outer edge of the dendron skeleton, and between two phases in a liquid crystal state according to an external stimulus. Emission color change is shown by direct phase transition, and the core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylene vinylene, oligophenylene It is any one of ethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine dyes, or derivatives thereof, and the dendron skeleton is either poly (aryl ether) type or aromatic polymer And the branched alkyl group has the following formula: A step of the liquid crystal material to form a solution as a solute or an alkyl group or 3,7,11-trimethyl-dodecane formula,
Applying the solution onto a substrate to form a liquid crystal material film.
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen.)
It is in.
Other aspects of the present invention may be as follows.
The other first aspect is
A core that is a light emitting site;
A dendron skeleton bonded to the core,
A liquid crystal material that exhibits a color change in light emission by direct phase transition between two phases in a liquid crystal state in response to an external stimulus.
It is in.

According to this configuration, a useful functional liquid crystal material capable of returning the emission color in the liquid crystal state can be obtained.

The other second aspect is
2. The liquid crystal material according to claim 1, further comprising a branched alkyl group bonded to an outer edge portion of the dendron skeleton.
It is in.

According to this configuration, a more stable liquid crystal material can be obtained in the liquid crystal state.

The other third aspect is
3. The liquid crystal material according to claim 2, wherein the branched alkyl group is any one of alkyl groups represented by the following chemical formulas.

According to this configuration, a more stable liquid crystal material can be obtained in the liquid crystal state.

The other fourth aspect is
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. 2. The liquid crystal material according to claim 1, wherein the liquid crystal material is either a system dye or a derivative thereof.
It is in.

According to this configuration, a liquid crystal material that emits light stably by excimer formation can be obtained.

The other fifth aspect is
2. The liquid crystal material according to claim 1, wherein the dendron skeleton is either a poly (aryl ether) type or a poly (aryl ester) type.
It is in.

According to this configuration, a liquid crystal material that is easier to emit light can be obtained.

The other sixth aspect is
Any compound represented by Formula 1, Formula 2, Formula 3, or Formula 4.
It is in.

According to this structure, the compound which shows a reversible luminescent color change in a liquid crystal state according to an external stimulus is obtained.

The other seventh aspect is
Any compound represented by Formula 1, Formula 2, Formula 3, or Formula 4.
It is in.

According to this structure, the compound which shows a reversible luminescent color change in a liquid crystal state according to an external stimulus is obtained.

The other eighth aspect is
A piezochromic luminescent material containing a compound represented by formula 1,
A piezochromic luminescent material characterized by exhibiting a luminescent color change by direct phase transition between two phases in a liquid crystal state by application of shear.
It is in.

The other ninth aspect is
A core that is a light emitting site;
A liquid crystal material comprising a dendron skeleton bonded to the core,
A liquid crystal material film characterized by exhibiting a luminescent color change by a direct phase transition between two phases in a liquid crystal state in response to an external stimulus.
It is in.

According to this configuration, a useful functional liquid crystal material film capable of returning the emitted color can be obtained.

The other tenth aspect is
A core that is a light emitting site;
A liquid crystal material comprising a dendron skeleton bonded to the core,
A coating material characterized by exhibiting a luminescent color change by a direct phase transition between two phases in a liquid crystal state in response to an external stimulus.
It is in.

According to this structure, the useful coating material which can return luminescent color is obtained.

The other eleventh aspect is
A liquid crystal comprising a core that is a light emitting site and a dendron skeleton bonded to the core, and exhibiting a color change of light emission by direct phase transition between two phases in a liquid crystal state in response to an external stimulus Forming a solution containing the material as a solute;
Applying the solution onto a substrate to form a liquid crystal material film.
It is in.

According to this configuration, it is possible to obtain a useful liquid crystal material film that can restore the emission color by a simple method.

Here, in order to clarify the binding site of the side chain, it is indicated by a dotted line.

According to the present invention, a useful functional liquid crystal material or the like can be obtained.

Other objects, features, or advantages of the present invention will become apparent from the detailed description based on the embodiments of the present invention described later and the accompanying drawings.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[Introduction]

A material that changes its emission color in response to a mechanical stimulus (pressure, shear stress, etc.) is called a piezochromic luminescent material, and its emission can be easily detected, so it can be applied to sensing devices and memories. However, there are still few reports. In particular, there are almost no reports of liquid crystal materials despite the advantages that they can be solubilized in a solvent by being introduced with an appropriate side chain, can be applied over a large area, and are flexible.

This phenomenon of piezochromic luminescence is important to create a metastable state well, and is manifested by the competition of intermolecular interactions such as hydrogen bonding, π-π stack, side chain steric hindrance to some extent. The inventors paid attention.

FIG. 1 is a diagram showing a liquid crystal material whose luminescent color changes in response to a stimulus. In the published literature (Angew. Chem. Int. Ed., 2008, 47, 5175), the present inventors have shown that the cubic phase is metastable and the columnar phase developed by applying shear is the most stable liquid crystal phase. Reported that there is.

However, as described above, in this system, once the emission color becomes bluish green by applying shear, it is necessary to heat to near 200 ° C. and to go through an isotropic phase in order to return to the yellow emission color. .

[Overview]

The inventors of the present invention have found that when shear is applied to a compound having a large number of branched chains in the side chain at room temperature, the phase changes from a cubic phase to another intermediate phase and the emission color changes from yellow to green. In addition, it was found that the green intermediate phase can be returned to the original yellow light emission without passing through the melting step by heating at 80 ° C. for about 30 seconds.

In the following, for example, a reversible functional liquid crystal whose luminescence color (photoluminescence) changes in response to shearing at room temperature and can be restored to its original luminescence color by performing relatively mild heating at 80 ° C. for a short time. The material will be described. Such a liquid crystal material is a highly practical material that can be used for sensing of external stimuli and a recording material because the emission color changes in response to the stimulus.

FIG. 2 is a diagram showing a liquid crystalline pyrene derivative showing a reversible emission color change and an application example thereof. The above compound can be uniformly dispersed in an alkane-based organic solvent and can be applied onto a glass substrate. If the substrate is rubbed, the emission color changes from yellow to green, and the original yellow emission color can be restored by heating.

A branched alkyl group or the like is introduced into the side chain of the compound of the present embodiment, and the cubic phase is considered to be stabilized by the bulkiness of the side chain. As a result, the cubic phase is more stable than the intermediate phase developed by applying shear in the high-temperature region, and returns to the cubic phase from the intermediate phase, and reversible emission color change can be achieved in the bulk state without passing through the isotropic phase. It is thought.

Next, other compounds, causes of changes in emission color, molecular design, conditions of external stimulation for inducing emission color changes, use as a coating agent, and the like will be described.

[Other compounds]

In the above-mentioned outline, the following compound 1 was explained, but the stimuli-responsive liquid crystal material that shows reversible emission color change even with three compounds of compound 2, compound 3, and compound 4 having an anthracene skeleton or naphthalene skeleton in the core Can be used as These compounds, like compound 1, change the emission color upon irradiation with ultraviolet light by applying shear at room temperature, and can be restored to the original emission color without passing through an isotropic phase by heating. FIG. 3 is a diagram showing changes in emission color of each compound.

[Cause of change in emission color]

FIG. 4 is a diagram showing observation with a polarizing microscope before and after applying shearing of compound 1. Each compound exhibits a micellar cubic phase that is optically isotropic (not birefringent) at room temperature. By applying shearing to this at room temperature, it transitions to another intermediate phase exhibiting birefringence. For example, as shown in the figure, it can be seen that when the compound 1 is observed with a polarizing microscope, it clearly changes from a dark state to a bright state (having birefringence, that is, having optical anisotropy). That is, the liquid crystal phase-liquid crystal phase transition occurs due to shear.

FIG. 5 is a diagram showing the concept of excimer luminescence. The cause of the change in the luminescent color is due to the change in the aggregate state of the molecules in each liquid crystal phase, and the excimer formation is inhibited by shearing. An excimer is a state in which a molecule in an excited state forms an aggregate with a molecule in a ground state, and light emission when the excimer returns to the ground state is significantly different from the emission color of a single molecule.

FIG. 6 is a diagram showing an assembled state of molecules in the liquid crystal phase. As shown in the upper diagram, in the micellar cubic phase, molecules are assembled in a state where the light emitting sites are overlapped with each other, and thus the emission color caused by the excimer is observed. On the other hand, as shown in the figure below, when shear is applied, the molecule forms a hydrogen bond (confirmed by IR measurement), but forms an aggregate that cannot form an excimer, and the emission color changes. .

[About molecular design]

All newly developed compounds caused a change in emission color due to shear. Therefore, it is considered that not only pyrene, anthracene, and naphthalene skeletons but also a luminescent site capable of forming an excimer can achieve a similar phenomenon by introducing it into the molecular core.

Further, regarding the side chain, it is considered that the same piezochromic luminescence can be achieved if the side chain is somewhat bulky so as to form a metastable liquid crystal phase and induces liquid crystallinity. Perhaps the side chain branching may be increased and the alkyl chain may be lengthened. However, if it is too bulky, the cubic phase is completely stabilized, and even if shear is applied, it is considered that the cubic phase remains as it is without phase transition. On the other hand, if it is not too bulky, it is considered that the cubic phase does not appear and only the liquid crystal phase such as columnar phase appears.

[External stimulus to induce luminescent color change]

<Applying shear>
As the external stimulus for transition from the cubic phase to the intermediate phase, shear is preferable to pressure. However, it is expected that no phase transition will occur when the liquid crystal is pressed from above. Furthermore, since the shear stress applied to one micellar aggregate in the cubic phase is inversely proportional to the film thickness applied to the substrate, if the applied sample is thick, it does not transfer even if it is rubbed strongly. However, when actually used as a sensing material, fluorescence can be detected very easily, the coating film applied to the substrate may be thin, and there is no problem with respect to the thickness.

<Heat treatment>
The original luminescent color is restored by subjecting the sample after applying shear to a certain degree of heat treatment. Since the balance between metastable and most stable liquid crystal phase changes depending on the molecular skeleton, the temperature at which the luminescent color recovers depends on the molecule. For example, Compound 1 and Compound 2 described above recovered the original emission color by heat treatment at 80 ° C. for about 30 seconds, but Compound 4 did not return to the original emission color unless heated at about 120 ° C. for 30 seconds.

[When used as a coating agent]

FIG. 7 is a view showing a coating agent using the liquid crystal compound of this embodiment. When a compound expressing a micelle cubic phase was dissolved in hexane, a solution exhibiting luminescence due to excimer luminescence was obtained. As shown in the figure, this solution was dropped on a glass substrate, spread with a spatula or the like, and allowed to dry naturally under the conditions of room temperature air, whereby a thin film could be easily prepared.

<Solvent type>
Although hexane was used here, it can be dissolved in another solvent, for example, alkane-based solvents such as pentane and octane, while maintaining the micellar aggregate, as long as hydrogen bonds for forming micelles are not broken. I believe. Conversely, solvents such as chloroform, toluene, benzene, tetrahydrofuran, and ethylene glycol break hydrogen bonds between molecules, and the molecules do not form micellar aggregates in the solution, making them difficult to use. Moreover, this compound did not melt | dissolve in alcohol, such as methanol and ethanol, under normal temperature normal pressure.

<Concentration conditions>
Here, the coating agent was prepared at a concentration of about 10 ⁻³ or more and 10 ⁻⁵ or less, but the concentration may not be in this range. However, if the concentration is too low, it seems that it takes time to dry the solvent in order to obtain a certain film thickness.

<Substrate conditions>
Here, a glass substrate was used. However, there is no problem with any substrate as long as it is compatible with the solvent used.

<Application conditions>
Here, a coating film was prepared by dropping and extending on a glass substrate, but a coating film can also be prepared by spin coating.

[Luminescent site]

The synthesized compounds have pyrene, anthracene, and naphthalene skeletons as light emitting sites, and what we want to pay attention to is whether or not to form an excimer. In general, the luminescent properties of molecular assemblies are largely dependent on their aggregate structure. In addition to excimer formation, the luminescent properties change due to exciton interactions and changes in the conformation of the molecular skeleton itself. Even when molecules with low planarity that do not form are introduced, the emission color of the material may change due to changes in the exciton interaction or the conformation of the molecular skeleton itself by applying shear. . Therefore, a synthetic route capable of introducing two dendron-type side chains in roughly opposite directions can be established, and any light emitting site of a certain size can be used.

Next, the molecules are listed in order, divided into two groups, from molecules that are likely to form excimers to those that simply shine (having some quantum yield).

1) A luminescent molecule that is likely to form an excimer (the same phenomenon as the above-mentioned compound is considered to occur)
Derivatives of planar π-conjugated molecules such as pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine. Derivatives such as rhodamine, coumarin, fluorescein, and cyanine dyes that are often used in fluorescent probes and laser dyes.

2) Molecules that do not form excimers but can induce some change in luminescence properties if introduced (changes in luminescent color are due to exciton interactions and changes in the conformation of the molecular structure of the luminescent site)
Derivatives of luminescent molecules with low planarity such as rubrene, fluorene, thiophene, bipyridine, terpyridine, and BODIPY dyes.

[Side chain]

FIG. 8 is a conceptual diagram of a side chain of a compound applicable to this embodiment. An example of an actually introduced side chain is as follows. The side chain of the compound applicable to this embodiment may be a structure in which, for example, an amide group for hydrogen bonding is introduced at the base of the bulky side chain to some extent, and the outer edge of the side chain has liquid crystallinity. An alkyl chain having a certain length for inducing may be introduced.

For example, the side chain actually introduced into the compound by the present inventors is not bulky but has a certain bulkiness. If the side chain is too bulky, only the cubic phase appears, and if it is not bulky at all, only the columnar phase appears. In other words, when a side chain is introduced that has an exquisite height and is somewhat inflexible (so that the fan does not easily have a thin structure), a metastable liquid crystal phase appears and is rubbed. The phase transitions to a stable liquid crystal phase, and the emission color changes.

In order to induce liquid crystallinity, for example, it is desirable to introduce a certain long alkyl chain.

Specific molecular skeletons that may cause this phenomenon are listed as examples. For example, this phenomenon can be manifested by appropriately selecting the alkyl group or alkoxy group introduced below and the dendron skeleton and synthesizing the fan-shaped side chain.

First, an alkyl chain introduced into the outer edge is exemplified.
○ Linear alkyl group (for example, the number of C is preferably 8 or more and 18 or less)
○ Linear alkoxy group (for example, the number of C is preferably 8 or more and 18 or less)

In addition, the molecular skeleton already reported in the paper (Angew. Chem. Int. Ed. 2008, 47, 5175.5178) has an alkoxy chain with 12 carbon atoms introduced, and a high temperature of 200 ° C is required to restore the original emission color. However, depending on the molecular skeleton, even with a straight-chain alkoxy group, it is considered that a change in emission color can be achieved by heating to some extent.

○ The following branched alkyl group (for example, the number of C is preferably 6 or more and 18 or less)

It is considered that other branched alkyl chains may have a certain length. In particular, in the case of a branched alkyl chain, it has been found that the synthesized compound can easily reversibly undergo a phase transition in a liquid crystal state.

○ The following branched alkoxy group (for example, the number of C is preferably 6 or more and 18 or less)

It is considered that other branched alkoxy groups may be used.

Furthermore, the following side chain may be sufficient.
For example, the carbon number of the longer carbon chain is 6 or more and 18 or less.
For example, the carbon number of the longer carbon chain is 6 or more and 18 or less.
R may be hydrogen or an alkyl chain, and may have different carbon numbers depending on the location.

Next, a dendron skeleton into which an alkyl group is introduced is exemplified.

This is shown in the order in which this phenomenon is likely to occur to some extent. Of the molecular skeletons listed below, the latter half is an excerpt from a review paper (Chem. Rev. 2001, 101, 3819-3867) by J. M. J. Frechet et al. That mainly deals with dendrimers. For this reason, some molecular structures have no alkyl chain at the outer edge, but in principle, the alkyl chain is introduced to the outside.

○ poly (aryl ether) type
The dendron skeleton of the compounds described above is of this type. This skeleton itself has been reported by JMJ Frechet et al. V. Percec et al. Have reported a large amount of researches in which an alkyl chain is introduced at the outer edge to develop liquid crystallinity (for example, J. Am Chem. Soc. 2001, 123, 1302-1315). However, by synthesizing various structures of dendron skeletons and examining the liquid crystallinity, it does not give mechanical stimuli such as shearing, and does not observe the liquid crystal phase-liquid crystal phase transition. Changes are not involved at all. Various dendron structures (for example, those described in the document J. Am. Chem. Soc. 2001, 123, 1302-1315) can be constructed by changing the branched structure or the number of alkyl chains introduced into the outer edge.

○ poly (aryl ester) type
Since it has a structure similar to the poly (aryl ether) type described above, it can be said that this type is the structure that is likely to induce this phenomenon next. As in the previous case, various changes in the dendron structure can be considered by changing the substitution position.

○ poly (phenylene) type, poly (aryl alkyne) type, poly (aryl alkene) type
Like the above two types, various fine dendron structure changes can be considered, and this phenomenon may occur depending on the structure.

○ poly (alkyl ether) type, poly (alkyl ester) type
It may be applicable depending on the alkyl chain introduced into the outer edge portion. Of course, this type can also be considered for various fine dendron structure changes.

There are various other types of dendron skeletons. Of these types, the molecular skeleton similar to the poly (aryl ether) type and poly (aryl ester) type can be used to develop this phenomenon. Particularly preferred.

[Synthesis of compounds]

Hereinafter, the synthesis scheme will be described. Here, the following compound 1, compound 2, compound 3, and compound 4 are taken as examples.

<Synthesis of side chain>
3,7,11-trimethyl-dodecane-1-ol can be synthesized by the method described in Reference 1, for example.

<Synthesis of light emitting site (core portion)>
Among the luminescent cores before the side chain is attached, 1,6-diethynylpyrene, 1,5-diethynylnaphtharene, and 9,10-diethynylanthracene can be synthesized by, for example, the method described in Reference 2, 3, or 4.

<Synthesis of final compound>

The following are detailed synthesis methods and identification data. Reagents and the like were purchased from Aldrich, Tokyo Kasei or Wako (the company name is a trademark or a registered trademark). If necessary, it was purified and used in the reaction. Silica gel 60 (spherical, 40-50 μm) from Kanto Chemical was used for silica gel column chromatography.

3,7,11-Trimethyldodecyl bromide (5): Magnetic stir bar, 3,7,11-trimethyl-dodecane-1-ol (8.90 g, 39.0 mmnol), triphenylphosphine (12.3 g, 46.8 mmol) in a 500 ml eggplant flask ), 150 ml of methylene chloride was added and immersed in an ice bath under an argon atmosphere. While stirring this solution, NBS (N-Bromosuccinimide) (8.32 g, 46.8 mmol) dissolved in 20 ml of methylene chloride was slowly added dropwise, and then the ice bath was removed, followed by stirring at room temperature for 1 hour. Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator, the residue was dispersed in hexane and purified by flash silica column chromatography, and colorless and transparent liquid 5 (10.2 g, 35.0 mmol; yield 90%) was obtained. Obtained.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.84-0.90 (m, 12H), 1.01-1.38 (m, 13H), 1.48-1.58 (m, 1H), 1.59-1.73 (m, 2H), 1.82 -1.93 (m, 1H), 3.37-3.50 (m, 2H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 18.93, 18.99, 19.65, 19.72, 22.62, 22.72, 24.21, 24.79, 24.80, 27.97, 31.62, 31.66, 32.22, 32.72, 32.75, 36.76, 36.82, 37.21, 37.24 , 37.26, 37.34, 39.33, 40.02, 40.10.
Elemental analysis: Calcd. (%) For C ₁₅ H ₃₁ Br: C, 61.84; H, 10.73. Found: C, 61.67; H, 10.74.

4- (3,7,11-Trimethyldodecyloxy) benzoic acid methyl ester (6): Magnetic stir bar, 5 (10.2 g, 35.0 mmol), 4-hydroxybenzoic acid methyl ester (5.86 g, 38.5 mmol) in a 500 ml eggplant flask ), K ₂ CO ₃ (14.5 g, 105 mmol), and 50 ml of DMF are added and stirred at 70 ° C. for 12 hours. After cooling the reaction solution to room temperature, 150 ml each of water and chloroform are added to extract the organic layer. The organic layer is washed 3 times with a saturated aqueous ammonium chloride solution and then once with a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified by flash silica column chromatography to obtain a colorless transparent liquid 6 (12.0 g, 33.1 mmol; 94% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.88 (m, 9H), 0.94-0.95 (d, J = 6.4 Hz, 3H), 1.05-1.41 (m, 12H), 1.47-1.72 (m, 4H ), 1.80-1.87 (m, 1H), 3.88 (s, 3H), 4.00-4.08 (m, 2H), 6.90 (d, J = 8.8 Hz, 2H), 7.98 (d, J = 8.8 Hz, 2H) .
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.59, 19.65, 19.71, 22.60, 22.69, 24.30, 24.77, 24.79, 27.95, 29.77, 29.78, 32.75, 35.95, 36.03, 37.23, 37.25, 37.29, 37.33, 39.32 , 51.78, 66.48, 114.02, 122.25, 131.53, 162.90, 166.87.
MS (MALDI): m / z: 363.30 (calcd [M] + = 362.28).
Elemental analysis: Calcd. (%) For C ₂₃ H ₃₈ O ₃ : C, 76.20; H, 10.56. Found: C, 75.90; H, 10.69.

4- (3,7,11-Trimethyldodecyloxy) benzyl alcohol (7): Add a magnetic stir bar, LiAlH4 (1.88 g, 49.6 mmol), and THF (100 ml) to a 500 ml eggplant flask and stir in an ice bath. To this solution, 30 ml of a THF solution of 6 (12.0 g, 33.1 mmol) is slowly added dropwise. After the addition is complete, remove the ice bath and stir at room temperature for an additional 2 hours. 1 ml of water is added to the reaction solution, the solvent is distilled off under reduced pressure using a rotary evaporator, and 150 ml of 5% hydrochloric acid and chloroform are added to the residue to extract the organic layer. Then, the organic layer is washed once with water and saturated saline. Next, magnesium sulfate was added, dried and filtered, and then the solvent was distilled off under reduced pressure with a rotary evaporator to obtain a colorless and transparent liquid 7 (10.6 g, 31.7 mmol; yield 96%).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 9H), 0.94 (d, J = 6.0 Hz, 3H), 1.05-1.37 (m, 12H), 1.47-1.71 (m, 4H), 1.78-1.86 (m, 1H), 3.94-4.03 (m, 2H), 4.45 (s, 2H), 6.87 (d, J = 8.8 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.62, 19.66, 19.68, 19.73, 22.62, 22.71, 24.32, 24.79, 24.80, 27.96, 29.82, 32.77, 36.15, 36.23, 37.25, 37.29, 37.33, 37.35, 37.39 , 39.33, 66.32, 71.44, 114.36, 129.39, 130.21, 158.71.

4- (3,7,11-Trimethyldodecyloxy) benzyl chloride (8): Add a magnetic stir bar, 7 (10.61 g, 31.7 mmol) and CH ₂ Cl ₂ (100 ml) to a 500 ml eggplant flask and place in an ice bath. Stir. To this solution, SOCl ₂ (4.53 g, 38.1 mmol) is slowly added dropwise, the ice bath is removed and the mixture is stirred at room temperature for another 30 minutes. Thereafter, 100 ml of a saturated aqueous solution of sodium bicarbonate is slowly added while stirring the reaction solution. The organic layer was washed once each with water and saturated brine, dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure with a rotary evaporator to obtain a residue containing 8, and further purification was performed. Used for the next reaction.

3,4,5-Tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzoic acid methyl ester (9): 500 ml eggplant flask with magnetic stirrer, 8 (11.2 g, 31.7 mmol), 3, 4,5-trihydroxybenzoic acid methyl ester (1.67 g, 9.06 mmol), K ₂ CO ₃ (14.5 g, 105 mmol) and DMF 50 ml are added and stirred at 70 ° C. for 12 hours. After cooling the reaction solution to room temperature, 150 ml each of water and chloroform are added to extract the organic layer. The organic layer is washed 3 times with a saturated aqueous ammonium chloride solution and then once with a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified by flash silica column chromatography to give white waxy 9 (6.70 g, 5.91 mmol; 65% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 27H), 0.93-0.95 (m, 9H), 1.01-1.37 (m, 36H), 1.47-1.70 (m, 12H), 1.79-1.86 (m, 3H), 3.89 (s, 3H), 3.93-4.05 (m, 6H), 5.01 (s, 2H), 5.04 (s, 4H), 6.76 (d, J = 8.8 Hz, 2H), 6.90 ( d, J = 8.0 Hz, 4H), 7.25 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.8 Hz, 4H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.62, 19.66, 19.74, 22.62, 22.71, 24.34, 24.81, 27.97, 29.86, 32.78, 36.18, 36.26, 37.25, 37.31, 37.34, 37.36, 37.39, 37.43, 39.34 , 52.17, 66.25, 66.33, 71.06, 74.64, 109.14, 114.06, 114.44, 124.97, 128.53, 129.24, 129.40, 130.24, 142.40, 152.62, 158.96, 159.00, 166.72.
MS (MALDI): m / z: 1156.01 (calcd [M + Na] + = 1155.87).
Elemental analysis: Calcd. (%) For C ₇₄ H ₁₁₆ O ₈ : C, 78.40; H, 10.31.Found: C, 78.19; H, 10.41.

3,4,5-Tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzyl alcohol (10): Magnetic stir bar, LiAlH ₄ (326 mg, 8.60 mmol), THF (100 ml), put in an ice bath and stir. To this solution is slowly added dropwise 30 ml of 9 (6.50 g, 5.73 mmol) in THF. After the addition is complete, remove the ice bath and stir at room temperature for an additional 2 hours. 1 ml of water is added to the reaction solution, the solvent is distilled off under reduced pressure using a rotary evaporator, and 150 ml of 5% hydrochloric acid and chloroform are added to the residue to extract the organic layer. The organic layer is washed once with water and saturated brine. Next, magnesium sulfate was added, dried and filtered, and then the solvent was distilled off under reduced pressure using a rotary evaporator to obtain white waxy 10 (5.7 g, 5.16 mmol; yield 90%).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 27H), 0.93-0.95 (m, 9H), 1.03-1.41 (m, 36H), 1.47-1.72 (m, 12H), 1.78-1.88 (m, 3H), 3.91-4.04 (m, 6H), 4.58 (d, J = 6.0 Hz, 2H), 4.94 (s, 2H), 5.02 (s, 4H), 6.66 (s, 2H), 6.77 ( d, J = 8.4 Hz, 2H), 6.89 (d, J = 8.8 Hz, 4H), 7.29 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.8 Hz, 4H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.62, 19.66, 19.74, 22.62, 22.71, 24.34, 24.81, 27.96, 29.86, 32.78, 36.18, 36.27, 37.26, 37.36, 37.40, 37.43, 39.34, 65.47, 66.27 , 66.34, 71.05, 74.76, 106.60, 114.07, 114.41, 128.98, 129.09, 129.85, 130.26, 136.36, 137.82, 153.05, 158.86, 158.89.
MS (MALDI): m / z: 1128.26 (calcd [M + Na] + = 1127.87).
Elemental analysis: Calcd. (%) For C ₇₃ H ₁₁₆ O ₇ : C, 79.30; H, 10.57. Found: C, 79.03; H, 10.70.

3,4,5-Tris [4- (3,7,11-Trimethyldodecyloxy) benzyloxy] benzyl chloride (11): 500 ml eggplant flask with magnetic stirring bar, 10 (5.50 g, 4.97 mmol), 2,6- Add di-tert-buthyl-4-methylpyridine (2.24 g, 10.9 mmol) and CH ₂ Cl ₂ (100 ml), stir in an ice bath. To this solution, SOCl ₂ (651 mg, 5.47 mmol) is slowly added dropwise, the ice bath is removed, and the mixture is further stirred at room temperature for 30 minutes. After confirming the completion of the reaction, 100 ml of saturated aqueous sodium hydrogen carbonate solution is slowly added while stirring the reaction solution. The organic layer was washed once each with water and saturated brine, dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure with a rotary evaporator to obtain a residue containing 11, and further purification was performed. Used for the next reaction.

3,5-Bis {3 ', 4', 5'-tris [4- (3,7,11-Trimethyldodecyloxy) benzyloxy] benzyloxy} benzoic acid methyl ester (12): magnetic stir bar in 500 ml eggplant flask, Add 11 (5.58 g, 4.97 mmol), 3,5-dihydroxybenzoic acid methyl ester (411 mg, 2.26 mmol), K ₂ CO ₃ (1.56 g, 11.3 mmol), and 50 ml of DMF, and stir at 70 ° C for 12 hours. . After cooling the reaction solution to room temperature, 150 ml each of water and chloroform are added to extract the organic layer. The organic layer is washed 3 times with a saturated aqueous ammonium chloride solution and then once with a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified by flash silica column chromatography to obtain colorless waxy 12 (3.30 g, 1.41 mmol; 62% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 54H), 0.94 (d, J = 6.4 Hz, 18H), 1.03-1.40 (m, 72H), 1.47-1.71 (m, 24H), 1.80-1.86 (m, 6H), 3.92 (s, 3H), 3.94-4.02 (m, 12H), 4.93 (s, 4H), 4.96 (s, 4H), 5.02 (s, 8H), 6.73 (s, 4H), 6.77 (d, J = 8.8 Hz, 4H), 6.80 (t, J = 2.4 Hz, 1H), 6.88 (d, J = 8.8 Hz, 8H), 7.27-7.33 (m, 14H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.61, 19.66, 19.73, 22.62, 22.71, 24.34, 24.79, 27.96, 29.86, 32.77, 36.19, 36.28, 37.25, 37.32, 37.36, 37.42, 37.44, 39.34, 52.29 , 66.26, 66.32, 70.45, 71.14, 74.79, 107.16, 107.40, 108.36, 114.08, 114.40, 128.86, 129.16, 129.83, 130.23, 131.69, 132.01, 138.34, 153.14, 158.87, 158.92, 159.70, 166.72.
MS (MALDI): m / z: 2381.60 (calcd [M + K] + = 2380.77).
Elemental analysis: Calcd. (%) For C ₁₅₄ H ₂₃₆ O ₁₆ : C, 78.93; H, 10.15.Found: C, 78.74; H, 10.27.

3,5-Bis {3 ', 4', 5'-tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzyloxy} benzoic acid (13): A magnetic stir bar, 12 ( 3.10 g, 1.32 mmol), KOH (222 mg, 3.97 mmol), ethanol 100 ml, THF 50 ml are added, water 2 ml is added, and the mixture is refluxed at 70 ° C. for 6 hours under an argon atmosphere. After the solvent is distilled off under reduced pressure by a rotary evaporator, 5% hydrochloric acid and chloroform are added. Next, the organic layer was washed with saturated brine, magnesium sulfate was added, dried and filtered, and then the medium was distilled off under reduced pressure with a rotary evaporator to obtain colorless waxy 13 (2.90 g, 1.24 mmol; yield 95%) )
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 54H), 0.94 (d, J = 6.4 Hz, 18H), 1.01-1.40 (m, 72H), 1.47-1.70 (m, 24H), 1.79-1.86 (m, 6H), 3.95-4.01 (m, 12H), 4.93 (s, 4H), 4.96 (s, 4H), 5.02 (s, 8H), 6.73 (s, 4H), 6.77 (d, J = 8.8 Hz, 4H), 6.83 (t, J = 2.4 Hz, 1H), 6.88 (d, J = 8.8 Hz, 8H), 7.27-7.33 (m, 14H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.61, 19.66, 19.73, 22.62, 22.72, 24.35, 27.96, 29.86, 32.77, 36.19, 36.28, 37.25, 37.32, 37.37, 37.43, 37.45, 39.34, 66.27, 66.33 , 70.52, 71.17, 74.81, 107.45, 107.95, 108.88, 114.09, 114.41, 128.85, 129.17, 129.83, 130.23, 130.99, 131.58, 138.41, 153.17, 158.87, 158.94, 159.78, 164.84.
MS (MALDI): m / z: 2351.17 (calcd [M + Na] + = 2350.75).
Elemental analysis: Calcd. (%) For C ₁₅₃ H ₂₃₄ O ₁₆ : C, 78.89; H, 10.12. Found: C, 78.62; H, 10.27.

N-4-Iodophenyl 3,5-bis {3 ', 4', 5'-tris [4- (3,7,11-trimethyldodecyloxy)] benzyloxy} benzamide (14): Magnetic stir bar in a 100 ml eggplant flask , 13 (2.70 g, 1.16 mmol), 4-iodoaniline (254 mg, 1.16 mmol), DMAP (28.4 mg, 0.232 mmol), EDC (445 mg, 2.32 mmol), CH ₂ Cl ₂ Stir for 12 hours. Thereafter, 100 ml of chloroform is added to the reaction solution, washed 3 times with water, washed once with saturated brine, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified by flash silica column chromatography to give white waxy 14 (1.50 g, 0.593 mmol; 51% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 54H), 0.94 (d, J = 6.4 Hz, 18H), 1.03-1.37 (m, 72H), 1.47-1.71 (m, 24H), 1.78-1.85 (m, 6H), 3.91-4.03 (m, 12H), 4.94 (s, 4H), 4.97 (s, 4H), 5.02 (s, 8H), 6.71 (s, 4H), 6.74 (t, J = 2.0 Hz, 1H), 6.77 (d, J = 8.0 Hz, 4H), 6.87 (d, J = 8.0 Hz, 8H), 7.00 (d, J = 2.4 Hz, 2H), 7.26-7.32 (m, 12H), 7.42 (d, J = 8.8 Hz, 2H), 7.65 (d, J = 8.8 Hz, 2H), 7.74 (s, 1H),.
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.60, 19.66, 19.73, 22.62, 22.71, 24.35, 24.79, 24.80, 27.96, 29.86, 32.77, 36.19, 36.28, 37.25, 37.36, 37.42, 37.45, 39.33, 66.26 , 66.35, 70.50, 71.14, 74.81, 87.73, 105.37, 106.14, 107.35, 114.08, 114.40, 121.78, 128.81, 129.12, 129.77, 130.23, 131.54, 136.90, 137.67, 138.00,
138.38, 153.15, 158.89, 160.02, 165.35.
MS (MALDI): m / z: 2552.41 (calcd [M + Na] + = 2551.69).
Elemental analysis: Calcd. (%) For C ₁₅₉ H ₂₃₈ INO ₁₅ : C, 75.47; H, 9.48; N, 0.55.Found: C, 75.27; H, 9.42; N, 0.61.

2,6-Bis (trimethylsilylethynyl) anthracene (15). 100 ml 2,6-dibromoanthracene (400 mg, 1.19 mmol), toluene (70 mL), distilled purified diethylamine (15 mL), trimethylsilylacetylene (257 mg) in a Schlenk tube , 2.62 mmol). Pd (PPh ₃ ) ₄ (138 mg, 0.119 mmol) and CuI (22.7 mg, 0.119 mmol) are added to this mixture, and the mixture is stirred with heating at 75 ° C. for 12 hours. Thereafter, the reaction solution is cooled to room temperature, 5% hydrochloric acid and chloroform are added, and the organic layer is washed once with each of a saturated aqueous sodium hydrogen carbonate solution and saturated brine. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was recrystallized from hexane to obtain yellow flaky crystals 15 (297 mg, 0.801 mmol; yield 67%).
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.30 (s, 18H), 7.46 (dd, J = 8.8, 1.6 Hz, 2H), 7.91 (d, J = 8.8 Hz, 2H), 8.15 (s, . 2H), 8.30 (s, 2H) 13 C NMR (CDCl 3, 100 MHz):. δ = 0.00, 95.63, 105.48, 120.33, 126.29, 128.10, 128.22, 131.08, 131.43, 132.41 MS (MALDI): m / z: 369.99 (calcd [M] = 370.16). Elemental analysis: Calcd. (%) for C ₂₄ H ₂₆ Si ₂ : C, 77.77; H, 7.07. Found: C, 77.51; H, 7.08.

2,6-Diethynylanthracene (16). Add 15 (297 mg, 0.801 mmol), methanol 60 ml, THF 15 ml, KOH (181 mg, 0.801 mmol) to a 100 ml eggplant flask and stir at room temperature for 2 hours. The solvent is distilled off under reduced pressure using a rotary evaporator, 5% hydrochloric acid and chloroform are added, and the organic layer is washed once with each of a saturated aqueous sodium hydrogen carbonate solution and saturated brine. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was recrystallized from hexane to obtain yellow crystals 16 (146 mg, 0.646 mmol yield 81%).
¹ H NMR (CDCl ₃ , 400 MHz): δ = 3.22 (s, 2H), 7.49 (dd, J = 8.8, 1.2 Hz, 2H), 7.95 (d, J
= 8.8 Hz, 2H), 8.19 (s, 2H), 8.35 (s, 2H). MS (MALDI): m / z: 226.34 (calcd [M] = 226.08). Elemental analysis: Calcd. (%) For C ₁₈ H ₁₀ : C, 95.55; H, 4.45. Found: C, 95.28; H, 4.64.

1,6-Bis [p- (3,5-bis {3,4,5-tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzyloxy} benzamido) phenylethynyl] pyrene (1): 50 ml Schlenk Degas by adding 14 (500 mg, 0.198 mmol), 1,6-diethynylpyrene (19.8 mg, 7.90 × 10 ⁻² mmol), 30 ml of THF and 5 ml of distilled Et ₂ NH to the tube. CuI (1.50 mg, 7.90 × 10 ⁻³ mmol) and Pd (PPh ₃ ) ₄ (9.13 mg, 7.90 × 10 ⁻³ mmol) are added to the mixture, and the mixture is heated and stirred at 60 ° C. for 20 hours. Thereafter, the solvent is distilled off to some extent by a rotary evaporator, 5% hydrochloric acid and chloroform are added, and the organic layer is washed once with each of a saturated sodium hydrogen carbonate aqueous solution and a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified using flash silica column chromatography and GPC to give yellow waxy 1 (250 mg, 4.95 × 10 ⁻² mmol; 63% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 108H), 0.93 (d, J = 6.4 Hz, 36H), 1.02-1.40 (m, 144H), 1.46-1.71 (m, 48H), 1.78-1.87 (m, 12H), 3.92-4.03 (m, 24H), 4.95 (s, 8H), 5.00 (s, 8H), 5.04 (s, 16H), 6.74 (s, 8H), 6.77-6.79 ( m, 10H), 6.88 (d, J = 8.8 Hz, 16H), 7.06 (d, J = 2.0 Hz, 4H), 7.26-7.33 (m, 24H), 7.74 (s, 8H), 7.88 (s, 2H ), 8.17-8.24 (m, 6H), 8.70 (d, J = 8.8 Hz, 2H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.61, 19.67, 19.74, 22.63, 22.73, 24.36, 24.80, 24.81, 27.97, 29.88, 32.79, 36.21, 36.30, 37.27, 37.37, 37.44, 37.47, 39.34, 66.29 , 66.38, 70.55, 71.17, 74.83, 88.48, 95.32, 105.42, 106.20, 107.38, 114.11, 114.43, 118.50, 119.35, 119.77, 124.24, 125.15, 126.26, 128.13, 128.85, 129.15, 129.81, 131.11, 131.58, 131.11 , 131.97, 132.64, 137.02, 138.11, 138.42, 153.19, 158.92, 160.08, 165.37.
Elemental analysis: Calcd. (%) For C ₃₃₈ H ₄₈₄ N ₂ O ₃₀ : C, 80.30; H, 9.65; N, 0.55. Found: C, 80.10; H, 9.70; N, 0.59.

2,6-Bis [p- (3,5-bis {3,4,5-tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzyloxy} benzamido) phenylethynyl] anthracene (2): 50 ml Schlenk Degas by adding 14 (500 mg, 0.198 mmol), 2,6-diethynylanthracene (17.9 mg, 7.90 × 10 ⁻² mmol), 30 ml of THF, 5 ml of distilled Et ₂ NH to the tube. CuI (1.50 mg, 7.90 × 10 ⁻³ mmol) and Pd (PPh ₃ ) ₄ (9.13 mg, 7.90 × 10 ⁻³ mmol) are added to the mixture, and the mixture is heated and stirred at 60 ° C. for 20 hours. Thereafter, the solvent is distilled off to some extent by a rotary evaporator, 5% hydrochloric acid and chloroform are added, and the organic layer is washed once with each of a saturated sodium hydrogen carbonate aqueous solution and a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified using flash silica column chromatography and GPC to obtain yellow waxy 2 (150 mg, 2.98 × 10 ⁻² mmol; 38% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 108H), 0.94 (d, J = 6.0 Hz, 36H), 1.03-1.40 (m, 144H), 1.47-1.71 (m, 48H), 1.79-1.86 (m, 12H), 3.94-4.04 (m, 24H), 4.95 (s, 8H), 4.99 (s, 8H), 5.04 (s, 16H), 6.73 (s, 8H), 6.76-6.79 ( m, 10H), 6.88 (d, J = 8.8 Hz, 16H), 7.05 (d, J = 2.0 Hz, 4H), 7.26-7.33 (m, 24H), 7.55 (d, J = 9.6 Hz, 2H), 7.60 (d, J = 8.4 Hz, 4H), 7.69 (d, J = 8.8 Hz, 4H), 7.86 (s, 2H), 7.98 (d, J = 9.2 Hz, 2H), 8.21 (s, 2H), 8.37 (s, 2H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.60, 19.66, 19.73, 22.62, 22.71, 24.35, 24.79, 24.80, 27.96, 29.87, 32.77, 36.19, 36.28, 37.25, 37.36, 37.43, 37.45, 39.33, 66.27 , 66.37, 70.53, 71.16, 89.90, 90.45, 105.37, 106.16, 107.37, 114.09, 114.41, 119.11, 119.64, 120.49, 126.26, 128.02, 128.35, 128.84, 129.13, 129.79, 130.23, 131.06, 131.54, 131.687.02 132 , 138.02, 138.40, 153.17, 158.90, 160.06, 165.31.
Elemental analysis: Calcd. (%) For C ₃₃₆ H ₄₈₄ N ₂ O ₃₀ : C, 80.21; H, 9.70; N, 0.56.Found: C, 80.05; H, 9.71; N, 0.56.

1,5-Bis [p- (3,5-bis {3,4,5-tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzyloxy} benzamido) phenylethynyl] naphthalene (3): 50 ml Schlenk The tube is deaerated by adding 14 (500 mg, 0.198 mmol), 1,5-diethynylnaphthalene (16.6 mg, 9.41 × 10-2 mmol), 30 ml of THF, and 5 ml of distilled Et ₂ NH. CuI (1.79 mg, 9.41 × 10 ⁻³ mmol) and Pd (PPh ₃ ) ₄ (10.9 mg, 9.41 × 10 ⁻³ mmol) are added to the mixture, and the mixture is heated and stirred at 60 ° C. for 20 hours. Thereafter, the solvent is distilled off to some extent by a rotary evaporator, 5% hydrochloric acid and chloroform are added, and the organic layer is washed once with each of a saturated sodium hydrogen carbonate aqueous solution and a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified using flash silica column chromatography and GPC to obtain colorless waxy 3 (230 mg, 4.62 × 10 ⁻² mmol; yield 49%).
¹ H NMR (CDCl ₃ , 400 MHz): 0.84-0.87 (m, 108H), 0.94 (d, J = 6.8 Hz, 36H), 1.03-1.36 (m, 144H), 1.48-1.67 (m, 48H), 1.81-1.84 (m, 12H), 3.91-4.03 (m, 24H), 4.95 (s, 8H), 4.99 (s, 8H), 5.04 (s, 16H), 6.73 (s, 8H), 6.77-6.79 ( m, 10H), 6.88 (d, J = 8.8 Hz, 16H), 7.06 (d, J = 1.6 Hz, 4H), 7.26-7.33 (m, 24H), 7.58 (t, J = 8.0 Hz, 2H), 7.65 (d, J = 8.8 Hz, 4H), 7.72 (d, J = 8.8 Hz, 4H), 7.81 (d, J = 6.8 Hz, 2H), 7.90 (s, 2H), 8.45 (d, J = 9.2 Hz, 2H).
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.60, 19.66, 19.73, 22.62, 22.71, 24.35, 24.79, 24.80, 27.96, 29.86, 32.77, 36.19, 36.28, 37.25, 37.32, 37.36, 37.42, 37.45, 39.33 , 66.27, 66.36, 70.53, 71.16, 74.81, 87.23, 94.43, 105.36, 106.17, 107.38, 114.09, 114.41, 119.16, 119.67, 121.42, 126.15, 126.96, 128.83, 129.13, 129.78, 130.24, 130.86, 131,09 , 137.00, 138.10, 138.40, 153.17, 158.90, 160.07, 165.32.
Elemental analysis: Calcd. (%) For C ₃₃₂ H ₄₈₂ N ₂ O ₃₀ : C, 80.05; H, 9.75; N, 0.56.Found: C, 79.81; H, 9.78; N, 0.59.

9,10-Bis [p- (3,5-bis {3,4,5-tris [4- (3,7,11-trimethyldodecyloxy) benzyloxy] benzyloxy} benzamido) phenylethynyl] anthracene (4): 50 ml Schlenk Degas by adding 14 (750 mg, 0.296 mmol), 9,10-diethynylanthracene (33.5 mg, 0.148 mmol), THF 30 ml, distilled Et ₂ NH 5 ml to the tube. CuI (2.82 mg, 1.48 × 10 ⁻² mmol) and Pd (PPh ₃ ) ₄ (17.1 mg, 1.48 × 10 ⁻² mmol) are added to the mixture, and the mixture is heated and stirred at 60 ° C. for 20 hours. Thereafter, the solvent is distilled off to some extent by a rotary evaporator, 5% hydrochloric acid and chloroform are added, and the organic layer is washed once with each of a saturated sodium hydrogen carbonate aqueous solution and a saturated saline solution. Next, magnesium sulfate is added, dried and filtered, and then the solvent is distilled off under reduced pressure using a rotary evaporator. The residue was purified using flash silica column chromatography and GPC to obtain red waxy 4 (490 mg, 9.73 × 10 ⁻² mmol; 66% yield).
¹ H NMR (CDCl ₃ , 400 MHz): 0.83-0.87 (m, 108H), 0.94 (d, J = 6.4 Hz, 36H), 1.02-1.36 (m, 144H), 1.46-1.78 (m, 48H), 1.80-1.87 (m, 12H), 3.93-4.03 (m, 24H), 4.96 (s, 8H), 5.00 (s, 8H), 5.04 (s, 16H), 6.74 (s, 8H), 6.77-6.79 ( m, 10H), 6.88 (d, J = 8.4 Hz, 16H), 7.07 (d, J = 2.0 Hz, 4H), 7.26-7.33 (m, 24H), 7.64-7.66 (m, 4H), 7.78 (s , 8H), 7.95 (s, 2H), 8.68-8.71 (m, 4H),.
¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.60, 19.66, 19.73, 22.62, 22.72, 24.35, 24.79, 27.96, 29.87, 32.77, 36.19, 36.28, 37.25, 37.36, 37.43, 37.45, 39.34, 66.27, 66.37 , 70.55, 71.17, 74.82, 86.52, 102.24, 105.41, 106.20, 107.39, 114.10, 114.41, 118.40, 119.11, 119.33, 119.78, 126.80, 127.27, 128.84, 129.14, 129.80, 130.24, 131.56, 131.56, 132.03, 132.62 , 138.29, 138.42, 153.18, 158.91, 160.09, 165.35.
Elemental analysis: Calcd. (%) For C ₃₃₆ H ₄₈₄ N ₂ O ₃₀ : C, 80.21; H, 9.70; N, 0.56.Found: C, 79.98; H, 9.74; N, 0.58.

References for synthesis are as follows.

[1] CJ Bennett, ST Caldwell, DB McPhail, PC Morrice, GG Duthie, RC Hartley, Bioorg. Med. Chem. 2004, 12, 2079-2098.
[2] S. Leroy-Lhez, F. Fages, Eur. J. Org. Chem. 2005, 2684-2688.
[3] JG Rodriguez, JL Tejedor, J. Org. Chem. 2002, 67, 7631.
[4] MS Khan, MRA Al-Mandhary, MK Al-Suti, FR Al-Battashi, S. Al-Saadi, B. Ahrens, JK Bjernemose, MF Mahon, PR Raithby, M. Younus, N. Chawdhury, A. Kohler, EA Marseglia, E. Tedesco, N. Feeder, SJ Teat, Dalton Trans., 2004, 2377-2385.

In addition, FIG. 9, FIG. 10, FIG. 11, and FIG. 12 are ¹ H-NMR raw data of the following compounds 1, 2, 3, and 4, respectively.

[Hydrogen bond formation in liquid crystal phase]

FIG. 13 and FIG. 14 are the raw data of the IR spectrum before and after applying shear of Compound 1, respectively. The measurement was performed at room temperature, and the sample was a liquid crystal phase. FIG. 15 shows the raw data of the IR spectrum in the isotropic phase of Compound 1. The measurement was performed at 200 ° C. Similar results were obtained for compounds 2, 3, and 4.

In the liquid crystal phase (room temperature) before and after applying shear, peaks derived from C = O and NH stretching vibrations are observed around 1650 and 3280 cm ^-1, respectively, but in the isotropic phase (200 ° C), they originate from C = O stretching vibrations. peaks are observed in 1685 cm ^-1 (also can be observed what appears a peak derived from NH stretching vibration per 3430 cm ^-1). From the above results, it is understood that hydrogen bonds are not formed in the isotropic phase, and hydrogen bonds are formed in the liquid crystal phase before and after applying shear.

[Usage]

The compound of this embodiment can be applied to various uses. Examples include coating materials, security, wear sensors, sensing devices, ink, paint, UV-readable paper, fingerprint sensors, footprint sensors, personal authentication, coating materials, paints, artificial skin, artificial luminescent skin, artificial luminescence Hair, various light emitting elements, display devices, artificial light emitting skin, light emitting body, light emitting fabric, artificial skin, parts of various robots (work robot, entertainment robot, healing robot, etc.), various audio devices (including speakers), television, video , Body of home appliances such as personal computers, pressure indicators, pressure sensors, temperature sensors, dyes, blending into micro and nano fibers by electrospinning process. It can also be applied to confirm the presence or absence of an accident if applied to the guardrail.

[Summary]

As described above, according to the present embodiment, for example, a liquid crystal phase transition is exhibited by application of shear at room temperature, the emission color changes, and the emission color can be restored by heating to 80 ° C. Functional liquid crystal materials and the like are provided. In addition, the present embodiment can provide a useful approach in producing a functional material using a liquid crystal that undergoes phase transition in response to shear.

In particular, according to the present embodiment, for example, a functional liquid crystal material that exhibits a reversible change in emission color in a bulk state by an external stimulus such as shear and heat will be developed. Since the emission color can be restored without going through a melting step at a high temperature, the practicality is remarkably improved as compared with the previously reported compounds, and it is possible to prevent the compounds from decomposing. Further, since it can be dispersed in an organic solvent, it can be used as a coating agent having stimulus responsiveness.

[Interpretation of rights, etc.]

The present invention has been described above with reference to specific embodiments. However, it is obvious that those skilled in the art can make modifications or substitutions of the embodiments without departing from the gist of the present invention. That is, the present invention has been disclosed in the form of exemplification, and the contents described in the present specification should not be interpreted in a limited manner. In order to determine the gist of the present invention, the claims section described at the beginning should be considered.

It will also be appreciated that illustrative embodiments of the invention achieve the above objects, but that many modifications and other examples can be made by those skilled in the art. The elements or components of each embodiment described in the claims, specification, drawings, and description may be employed in combination with one or more other elements. The claims are intended to cover such modifications and other embodiments, which are within the spirit and scope of the present invention.

It is a figure which shows the liquid-crystal material from which luminescent color changes in response to irritation | stimulation. It is a figure which shows the liquid crystalline pyrene derivative which shows a reversible luminescent color change, and its application example. It is a figure which shows the change of the luminescent color of each compound. FIG. 2 is a view showing a polarization microscope observation of compound 1 before and after applying shear. It is a figure which shows the concept of excimer light emission. It is a figure which shows the assembly state of the molecule | numerator in a liquid crystal phase. It is a figure which shows the coating agent using the liquid crystalline compound of this embodiment. It is a conceptual diagram about the side chain of the compound applicable to this embodiment. 2 is a ¹ H-NMR raw data of Compound 1. 2 is a ¹ H-NMR raw data of Compound 2. 2 is a ¹ H-NMR raw data of Compound 3. 2 is a ¹ H-NMR raw data of Compound 4. 2 is a raw data of IR spectrum of Compound 1 before applying shear. 3 is a raw data of IR spectrum after applying a shearing force of Compound 1. 2 is a raw data of an IR spectrum in the isotropic phase of Compound 1. It is a figure which shows an example of the material from which luminescent color changes. It is a figure which shows an example of the material from which luminescent color changes. It is a figure which shows an example of the material from which luminescent color changes. It is a figure which shows an example of the material from which luminescent color changes. It is a figure which shows an example of the material from which luminescent color changes. It is a figure which shows an example of the material from which luminescent color changes. It is a figure which shows an example of the material from which luminescent color changes.

Claims (4)

A core that is a light emitting site;
A dendron skeleton bonded to the core ;
A branched alkyl group bonded to the outer edge of the dendron skeleton , and
In response to an external stimulus, it shows a luminescent color change by direct phase transition between the two phases in the liquid crystal state,
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. Either a dye or a derivative thereof,
The dendron skeleton is either a poly (aryl ether) type or an aromatic polymer,
The branched alkyl group is an alkyl group represented by the following chemical formula or 3,7,11-trimethyldodecane .
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen. ) A core that is a light emitting site;
A dendron skeleton bonded to the core ;
A branched alkyl group bonded to the outer edge of the dendron skeleton , and
In response to an external stimulus, it shows a luminescent color change by direct phase transition between the two phases in the liquid crystal state,
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. Either a dye or a derivative thereof,
The dendron skeleton is poly (aryl
ether) type or aromatic polymer,
The branched alkyl group is one of an alkyl group represented by the following chemical formula and 3,7,11-trimethyldodecane .
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen. ) A core that is a light emitting site;
A dendron skeleton bonded to the core ;
A branched alkyl group bonded to the outer edge of the dendron skeleton , and
In response to an external stimulus, it shows a luminescent color change by direct phase transition between the two phases in the liquid crystal state,
The core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylenevinylene, oligophenyleneethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine. Either a dye or a derivative thereof,
The dendron skeleton is poly (aryl
ether) type or aromatic polymer,
The branched alkyl group is an alkyl group represented by the following chemical formula or 3,7,11-trimethyldodecane .
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen. ) It comprises a core that is a light emitting site, a dendron skeleton bonded to the core, and a branched alkyl group that is bonded to an outer edge of the dendron skeleton, and between two phases in a liquid crystal state according to an external stimulus. Emission color change is shown by direct phase transition, and the core is pyrene, anthracene, naphthalene, perylene, coronene, triphenylene, tetracene, pentacene, carbazole, fluorenone, phenanthrene, azulene, oligophenylene vinylene, oligophenylene It is any one of ethynylene, porphyrin, phthalocyanine, rhodamine, coumarin, fluorescein, cyanine dyes, or derivatives thereof, and the dendron skeleton is either poly (aryl ether) type or aromatic polymer And the branched alkyl group has the following formula: A step of the liquid crystal material to form a solution as a solute or an alkyl group or 3,7,11-trimethyl-dodecane formula,
Applying the solution onto a substrate to form a liquid crystal material film.
(R may be hydrogen or an alkyl chain, and may have a different number of carbons depending on the location, except that R is all hydrogen.)