JP2003292494A - Dendrimer having temperature-dependent aggregation form and light emitter comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new dendrimer molecule, and to provide a light emitter comprising the molecule. <P>SOLUTION: This compound represented by formula I [R<SP>1</SP>and R<SP>2</SP>are each H or methyl; M is the monovalent ion of Au, Ag or Cu; (n) is an integer of 2 to 4]. For example, a compound of formula II (R is n-C<SB>18</SB>H<SB>37</SB>) is exemplified. The molecule aggregate is changed into an aggregation state dependent on temperature, and emits light having a wavelength characteristic to the aggregation state. Further, the aggregation state of the molecule aggregate is reversibly changed into various aggregation states by the change of temperature. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dendrimer molecule having a metal complex portion in the center of its composition and a light-emitting body composed of this molecule. The present invention relates to a dendrimer molecule having a specific emission wavelength and an illuminant composed of this molecule.

[0002]

2. Description of the Related Art A dendrimer having a benzene ring as a building block can absorb ultraviolet light by the benzene ring. If a luminescent site such as a dye is introduced into the center of the dendrimer, the absorbed energy It is already known that the light is transmitted to the central part and exhibits luminescence originating from the dye. That is, the dendrimer can function as a light collecting antenna. For example, in a dendrimer that has a conjugated unit that emits blue light composed of a polyphenylene ethynylene unit in the center and a poly (benzyl ether) type dendron (a branched unit) is introduced in the center, the dendrimer-derived luminescence is generated. Instead of being observed, only the emission from the central conjugate unit is observed, demonstrating the antenna function. (T. Sato, D.-L. Jiang, T. Aida J. Am. C
hem. Soc., 1999, 121, 10658-10659.) In addition, liquid crystal display devices used for so-called liquid crystal displays have various problems. For example, it is not used as a light emitting material for colorization, and a separate color filter or the like is required. From that principle, it is generally necessary to sandwich it between a hard substrate such as a glass plate, and it is difficult to make a thin and flexible display device. There is a defect as a recordable display material in that the display content disappears without being recorded when the external electric field is turned off.

[0003]

In the process of studying dendrimer molecules, the present inventors have found that they form a luminescent helical fiber (J. Am. Chem. Soc., 2
001, 123, 5608), in the present invention, by further modifying the dendrimer molecule, the molecular assembly takes an assembly state depending on the temperature depending on the temperature, and emits light at a wavelength peculiar to the assembly state. Found. Furthermore, it was found that various assembly states of this molecular assembly can be reversibly changed by changing the temperature.
Due to such characteristic properties, it has been found that the aggregate of dendrimer molecules can be usefully used as a light emitting material or a display material.

[0004]

Means for Solving the Problems and Embodiments of the Invention That is, the present invention includes the following general formula (Formula 1).

[Chemical 1] Is a compound represented by. In this formula (Formula 1), R ¹ and R ² may be the same or different and represent a hydrogen atom or a methyl group, and R is

[Chemical 2]

[Chemical 3] Or

[Chemical 4] , Preferably Chemical Formula 2 or Chemical Formula 3, more preferably Chemical Formula 2, M represents a monovalent ion of Au, Ag or Cu, and n represents an integer of 2 to 4, preferably 3.

In the formulas (formula 2 and formula 3), R ′ may be the same or different, and the following formula (formula 5)

[Chemical 5] It is represented by. In the formula (Formula 5), R ³ , R ⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom or an alkyl group or an alkoxy group, preferably a hydrogen atom or an alkoxy group, and R ³ , At least one of R ⁴ and R ⁵ is an alkyl group or an alkoxy group having 6 or more carbon atoms, preferably an alkoxy group. Each of R ³ , R ⁴ and R ⁵ is preferably a straight chain and may have a short chain (having about 3 or less carbon atoms) side chain.

Further, at least one of R ³ and R ⁵ is an alkyl group or alkoxy group having 6 or more carbon atoms,
It is preferably an alkoxy group, and R ⁴ is R ³
It is preferable that at least one of R ⁵ and R ⁵ is an alkyl group or alkoxy group having a smaller number of carbon atoms than an alkyl group or an alkoxy group having 6 or more carbon atoms, or a hydrogen atom, preferably an alkoxy group or a hydrogen atom. Furthermore, at least one of R ³ and R ⁵ has a carbon number of 16
A straight-chain alkoxy group of R 20 and R ³ and R ⁵
When is not the alkoxy group, it is preferably a hydrogen atom, and further, R ⁴ is preferably a hydrogen atom.

When the compound is irradiated with light that optically excites it, the dendrimer part absorbs the light, carries the light energy to the metal complex part, and emits light. That is, the present invention is a luminescent material comprising the above compound.

The emission wavelength depends on the aggregated state of the compound. That is, when this compound is kept at a certain temperature for a certain period of time, it has an aggregation state peculiar to that temperature and has an emission wavelength peculiar to that aggregation state. Therefore, by heating this compound to an appropriate temperature, the emission wavelength is changed. It will be possible to change. From this point of view, it becomes possible to use this compound as a light emitting body having a unique property. This compound has a large number of multi-molecules as an aggregate to have such an effect, and does not have such an effect when dispersed in a solvent or the like. When this compound is subjected to differential thermal analysis, it usually has two heat absorption peaks at a temperature of about several tens of degrees. The temperature range sandwiched between these two temperatures is called the liquid crystal region.

It is considered that when the compound of the present invention is kept at a temperature higher than the upper end temperature of the liquid crystal region for a certain period of time, the compound becomes an isotropic liquid, and when it is cooled in such a state, it is derived from a liquid crystal state. It is considered that a stacked state different from the liquid crystal state is formed, and when this compound is irradiated with excitation light such as ultraviolet rays, it emits light at a wavelength peculiar to this stacked state. However, when this compound is placed in the liquid crystal region for an appropriate time, it will be in a liquid crystal state, and if it is cooled in this state and irradiated with excitation light such as ultraviolet rays, it will emit light at a wavelength peculiar to this liquid crystal state. Conceivable. Therefore, if the compound is to emit light at a wavelength peculiar to the laminated state, the compound is heated once above the upper temperature of the liquid crystal region and then passed through the liquid crystal region as soon as possible. It may be cooled to a temperature below the lower end of the region. That is, the compound may be rapidly cooled so as not to be in a liquid crystal state. On the other hand, if the compound is to emit light at a wavelength peculiar to the liquid crystal state, the compound may be once heated to the liquid crystal region.

Further, the present invention comprises the above-mentioned light emitting body, a heat source capable of changing the temperature of the light emitting body in a temperature range including the liquid crystal region thereof, and a light source for irradiating the excitation light required for the light emitting body to emit light. It is a light emitting device. This illuminant can be formed into an appropriate shape depending on its purpose. For example,
It may be a pure product as it is, may be molded into an appropriate shape, or may be applied onto an appropriate medium. The heat source is not particularly limited as long as it can heat such a luminous body. The light source is not particularly limited as long as it can irradiate the excitation light corresponding to the absorption wavelength of the compound forming the light emitting body. Further, the heat source may be capable of heating the light emitter so that the temperature can be changed for each part of the light emitter. With such a device, it is possible to change the temperature of the character portion or the graphic portion and the other portion in the light emitting body, and it becomes possible for the character portion or the graphic portion to have an emission wavelength different from that of the other portions. Therefore, it becomes possible to visually identify the character portion and the graphic portion.
Further, once such visually identifiable characters and figures are formed, if heated again to the above temperature range,
It is also possible to form other characters or figures, or to make them have the same emission wavelength as other parts (that is, to erase visually identifiable characters or figures).

[0011]

By using the liquid crystal light emitting material of the present invention, a device capable of recording and displaying can be constructed with a single material. The operating temperature of this luminescent material is close to room temperature, so it is easy to handle, can be adsorbed on paper, has good film-forming properties, and emits phosphorescence at extremely low temperatures (77K). Is shown (yellowish green, yellow, orange, red).

The light emitting material of the present invention can be applied as follows.・ Recording information such as characters that are difficult to see under visible light and characters that do not need to be seen. (A type of secret document, a recording material that may be useful for privacy protection) -As a temperature sensor that uses the fact that the luminescent color changes when the temperature rises above 60 ° C. (A sensor that does not need to be visible or is difficult to see under direct visible light.) ・ Paper that can be recorded on both sides for the purpose of realizing the above characteristics on the surface. -A sticky note that can record both visible and annoying information. -In addition, the display medium or the display device according to the present invention can be used in various forms as a display body that a part or all of the display medium or display device occupies.
For example, a small card (a part of) may be used for the purpose of recording information or becoming a temperature sensor. -In addition, it can be used as a decorative material that is sensitive to temperature. In a situation where UV light can be illuminated, it is possible to use an easy-to-use object such as a dryer to switch the light emission, which can be an effective production method. Specifically, it could be used for stage production. In addition, since it has a good film forming property, it is considered that it can be compounded not only with paper but also with any flexible material. Therefore, not only the card but also various applications such as a sheet, a poster, and a signboard can be applied.

[0013]

EXAMPLES The present invention will be illustrated below with reference to Examples.
It is not intended to limit the light.Production example 1 In this production example, the following formula used in the following examples

[Chemical 6] Dendrimer represented by (wherein, R is abbreviated. [C18] that represents the _{n-C 18 H 37.)} ( "Cu [C18]
L2pz ". ) Was synthesized. This synthetic route is shown in FIGS. (1) Synthesis of [R] L1ester In a 1 L two-necked eggplant flask, 120 mL of n-octadodecyl bromide (manufactured by Tokyo Kasei), 25.0 g of methyl 3,5-dihydroxybenzoate (manufactured by Tokyo Kasei) and potassium carbonate 123. 6 g was added, and 200 mL of DMF distilled after purging with argon was added. Stir overnight at 70 ° C,
After the solid was collected by filtration, it was separated with chloroform / water to separate the chloroform layer. After separating the filtrate with chloroform / water, the chloroform layer was separated, combined with the previous chloroform layer, and dried. The obtained solid was purified by silica gel column chromatography. [Eluent is chloroform] Yield 82.5 g, 82%.

(2) Synthesis of [C18] L1OH [C18] L1es was placed in a 500 mL two-necked eggplant flask.
9.90 g of ter was added, and 300 mL of THF was added. LAH606 after heating to 45 ℃ and completely dissolving
mg was gradually added and stirred overnight. After stopping the reaction with a concentrated aqueous solution of magnesium sulfate, the mixture was filtered while hot and the filtrate was dried. The obtained solid was purified by silica gel column chromatography. [Eluent is chloroform] Yield 7.84 g, 83%. (3) Synthesis of [C18] L1Cl [R] L1OH was added to a 500 mL two-necked eggplant flask.
7.84 g was added and the atmosphere was replaced with nitrogen. CH ₂ Cl ₂ 20
After adding 0 mL and completely dissolving, a few drops (0.1 mL or less) of DMF was added, and 1.3 mL of SOCl ₂ was added to 1 mL.
It was added dropwise over 5 minutes. After stirring at room temperature for 3 hours, the reaction solution was dried. It was redissolved in chloroform and washed 3 times with water. This was dried over magnesium sulfate and then dried again, and the obtained solid was purified by silica gel column chromatography. [Eluent is chloroform] Yield 8.02 g, yield 99%.

(4) Synthesis of [C18] L2ester [C18] L1Cl was placed in a 500 mL two-necked eggplant flask.
8.01 g, tetrabutylammonium iodide 213
mg, methyl 3,5-dihydroxybenzoate 970 mg
And 4.78 g of potassium carbonate were added, and the atmosphere was replaced with nitrogen. Acetone (200 mL) was added, and the mixture was heated under reflux for 2 days. After the reaction solution was dried, it was redissolved in chloroform, filtered,
The filtrate was dried. The obtained solid was purified by silica gel column chromatography. [Eluent is chloroform] Yield 7.50 g, 92%. (5) Synthesis of [C18] L2OH [C18] L2es was placed in a 500 mL two-necked eggplant flask.
7.50 g of ter was added, and 80 mL of THF was added.
302 mg of LAH was gradually added at room temperature and stirred overnight. After stopping the reaction with a concentrated aqueous solution of magnesium sulfate, the mixture was filtered and the filtrate was evaporated to dryness. The obtained solid was purified by silica gel column chromatography. [Eluent was chloroform] Yield 4.59 g, yield 62.4%.

(6) Synthesis of [C18] L2Cl In a 500 mL two-necked eggplant flask, [R] L2OH
Add 4.59 g and replace with nitrogen. CH_TwoCl_Two60m
L, and after complete dissolution, a few drops of DMF, and
Add 1.5 mL of 2,6-ditert-butylpyridine.
Oh, and SOCL _TwoDrop 0.3 mL over 15 minutes
did. After stirring at room temperature for 3 hours, the reaction solution was dried. Black
It was redissolved in Loform and washed twice with water. this
After drying over magnesium sulphate and drying again,
The solids were purified by silica gel column chromatography.
Made [Eluent is chloroform] Yield 4.53g, yield
Rate 97%. (7) Synthesis of [C18] L2acac In a 300 mL two-neck eggplant flask, add [C18] L2Cl
 1.96 g, tetrabutylammonium iodide 51.
Add 2 mg and 576 mg of potassium carbonate and replace with nitrogen.
It was After adding 100 mL of acetone, acetylacetone
Add 0.45 mL and heat to reflux for 60 hours. Reaction solution
To dryness, re-dissolve in chloroform, filter,
The liquid was dried. The resulting waxy solid is applied to silica gel.
Pre-purified by ram chromatography. (Eluent
Chloroform] The obtained crude product is excluded from preparative size.
Purified by chromatography. Yield 571 mg,
Yield 28%.

(8) Synthesis of [C18] L2pz [C18] L2aca was placed in a 50 mL two-necked eggplant flask.
c 1.96 g was added, 15 mL of ethanol was added, the mixture was heated under reflux, and 28 μL of hydrazine monohydrate was added. The mixture was heated under reflux at room temperature overnight and cooled to 0 ° C. The pale yellow precipitate was collected by filtration and washed with a small amount of cold ethanol (0 ° C). The obtained solid was dissolved in 5 ml of chloroform and ethanol 6 was added.
Reprecipitated with 0 ml. This was repeated twice, and the obtained solid was subjected to preparative silica gel thin layer chromatography (manufactured by Nippon Analytical Industry Co., Ltd., LC-908 recycle preparative HPLC (with variable wavelength UV-visible spectroscopic detector), eluents were all chloroform, column. Set is 2 Polystyle
1 (registered trademark) packed column is used (inner diameter 20 mm × length 600 mm; JAIGEL-1H / exclusion limit molecular weight 10)
00, JAIGEL-2H / exclusion limit molecular weight 500
Purified in 0))). Yield 421 mg, 74% yield. (9) Synthesis of Cu [C18] L2pz [C18] L2pz was placed in a 30 mL two-necked eggplant flask.
_{235mg, [Cu (CH 3 CN} ) 4] [PF 6] 5
8.5 mg was added and the atmosphere was replaced with argon. Add 9 mL of THF and add triethylamine (NEt ₃ manufactured by Yoneyama Yakuhin Kogyo).
35 μL was added dropwise. Note that [Cu (CH ₃ CN) ₄ ]
[PF ₆ ] is Kubas, GJ Inorganic Synthesis, 197.
It was synthesized by the method described in 9, 19, 90; 1990, 28, 68. After stirring this at room temperature overnight, the reaction solution was dried. After redissolving in ₂ mL of CH ₂ Cl ₂ , 20 mL of cold methanol (-78 ° C) was added dropwise, and the precipitate was collected by filtration. The pale yellow solid obtained was dissolved in 5 mL of benzene and freeze-dried. Yield 204.7 mg, 83% yield.

Regarding the obtained Cu [C18] L2pz
The results of elemental analysis are shown below. Total from above chemical formula 6
It agrees well with the calculated value. Molecular formula: C₂₉₄H₅₀₇Cu_ThreeN₆O₁₈ Determination of carbon, hydrogen and nitrogen (sample 1.2301 mg) Measured value C 75.02%, H 10.94%, N 1.78% (Calculated value C 76.682%, H 11.10%, N 1.83%)

Further, for the obtained Cu [C18] L2pz, a mass spectrometer (MALDI-TOF-MS, Bru) was used.
Diskeranol was used for all Protein TOF matrices manufactured by ker. ), ¹ H nuclear magnetic resonance spectrum (JEOL J
EOL GSX-270 type spectrometer, all measurements were carried out in CDCl ₃ , and the signal of CHCl ₃ was used as a reference (δ 7.24 ppm). ), Differential scanning calorific value (Met
ler DSC30 and Metler TCIIJ TA processor are used. Scan speed is 10 Kmin ^-1 . ) Was measured. The respective results are shown in FIGS.

The attribution of MALDI-TOF-MS in FIG. 3 is shown below: m / z = 1472.0 [C18] L2pz +; 1535.2 [C1
8] L2pz + Cu ⁺ = monomer; 1605.1 monomer + Cu ⁺ (1886.5
the monomer ⁺ Cu +, seems dithranol ⁺ Cu + is bound. ); 3009.0 2 ([C18] L2pz) + Cu ⁺ ; 3071.9
2 ([C18] L2pz + Cu ⁺ ) = dimer; 3134.8 dimer + Cu ⁺ ； 4
607.8 3 ([C18] L2pz + Cu ⁺ ) = trimer; 4670.3 trimer
+ Cu ⁺ (4959.7 trimer + Cu ⁺ , dithranol (mw = 22
6.23) + Cu ⁺ seems to be connected. ); 6204.8 4
([C18] L2pz + Cu ⁺ ) + Cu ⁺

In FIG.¹The attribution of 1 H NMR is shown below.
The proton integral value in the vector is 3/3 of the following value.
It is indicated by 1. ): Δ / ppm = 6.49 12H, ArH; 6.40
3H, ArH; 6.34 12H, ArH; 4.87 12H, ArCH₂O; 3.88 2
4H, ArOCH₂C; 3.67 6H, ArCH₂pz ； 3.49 Residual methano
Peak; impurity peak around 3.2; 2.19 18H, pzCH₃; 1.7
1 24H, ArOCH₂CH₂; 1.22 360H, CCH₂C; 0.85 36H, CCH
₃ From the measurement results of the differential scanning calorimetry shown in FIG.
Has two endothermic peaks at about 40 ° C and about 60 ° C. High
The temperature peak is a broad peak over about 55 to 70 ° C.
Is. Therefore, the compound of Chemical formula 6 has a temperature of about 40 to 70 ° C.
It is considered that a liquid crystal state is obtained in the region.

[0022]Example 1 In this example, the light emission spectrum of the dendrimer synthesized in Production Example 1 was used.
The vector was measured. The measurement system used is shown in Fig.6.
The conditions are shown below. Measurement conditions: fluorescence spectrum mode, excitation side bandwidth 1.
5 nm, fluorescence side bandwidth 5 nm, response 1se
c, Sensitivity Medium, Excitation wavelength 280.0 nm, Run
Inspection speed 500 nm / min, data acquisition interval 0.
5 nm Cu [C18] L obtained in Production Example 1 on a 1 cm square quartz plate
Insert 2 pz about 1 mg. Once heated and melted at 80 ℃
After that, allow to cool to room temperature. Seal the gap between each side with adhesive
(Sample cell). This sample cell is a fluorescence spectrum device
(JASCO JASCO FP-777Win type)
Peltier temperature control device (JASCO ECT2
71 type) to measure the emission spectrum while controlling the temperature.
went.

First, the sample cell is heated to 80 ° C.,
From there, the temperature was lowered in steps of 10 ° C., and the emission from the sample was measured with excitation light of 280 nm. At that time, process A in which the temperature is kept at 40 ° C. for 30 minutes, and the temperature is kept at 40 ° C.
There was a difference in the luminescent color from the process B of lowering the temperature to ℃. The emission behavior of process A is shown in FIG. From this spectrum, in process A, the peak of luminescence after incubation at 40 ° C for 30 minutes is 64.
It can be seen that the color changed from 0 nm (red) to 610 nm (orange) and remained the same even when the temperature was lowered to room temperature.
The state in which the temperature is lowered to room temperature is called cell A. The emission behavior of process B is shown in FIG. From this spectrum, it can be seen that in Process B, the wavelength was 640 nm without any change. The state where the temperature is lowered to room temperature is referred to as cell B. On the other hand, when the cell A was heated to 80 ° C., red light emission of 640 nm was restored (FIG. 9). Furthermore, when the cell B is heated to 40 ° C., the emission color changes to 610 nm (orange),
When heated to 0 ° C. or higher, the color changed again to 640 nm (red) (FIG. 10).

In Examples 2 and 3 below, based on the test results of Example 1, further application of the luminescent material of the present invention was investigated. For confirmation of the light emission, a handy UV lamp SLUV-4 manufactured by Inei Seieidou was used and observed while applying excitation light on the 254 nm side. The arrangement of the measuring device is shown in FIG. Place a black sheet on the table, place the sample luminescent paper on it, irradiate it with a UV lamp (254 nm), and emit the emitted light with a digital camera (Nikon COOLPiX950
(E950) or Nikon COOLPiX5000
(E5000)). The distance between the luminescent paper and the UV lamp was about 10 cm, and the distance between the luminescent paper and the digital camera was about 30 cm. Observations were done in a bright room, while photography was done in a dark room.

[0025]Example 2 Distill 5 mg of Cu [C18] L2pz obtained in Production Example 1
Dissolve in 10 ml of methylene chloride prepared. Excitation at 280 nm
Filter paper (diameter 7 cm) is used as a paper that does not emit fluorescence against light.
Soak in the solution, dry, and repeat to put the complex on the paper
Stick Finally, dry well so that no solvent remains. here
The paper made in 1. will be called luminous paper A. This luminous paper
A is put in an electric furnace and kept at 40 ° C. Keep it warm for at least 15 minutes
It Then, if it is left to cool at room temperature,
Dichromatic emission was observed. The luminescent paper in this state is called luminescent paper B.
Say. Also, place the luminous paper A in an electric furnace at 80 ° C for a few minutes.
Keep it warm. Then, let it cool at room temperature, and let it cool to room temperature.
Red emission was observed. Replace the luminescent paper in this state with the luminescent paper.
Called C.

A part of the luminous paper B is covered with S-shaped rubber,
The uncoated part is heated with a dryer and allowed to cool at room temperature. Only the coated part emits orange light and the non-coated part emits red light. As a result, the S-shape can be read.
This is shown in FIG. When this was left to stand at room temperature, the characters were similarly observable for at least 2 months. The luminescent paper in this state is called luminescent paper D.
When the luminescent paper D was cooled to 77 K with liquid nitrogen, the red luminescent part became yellow luminescent. The luminescent paper D is placed in an electric furnace to keep it warm. At that time, if the temperature is kept at 40 ° C., it returns to the luminescent paper B. If the temperature is kept at 80 ° C., it becomes the luminous paper C.
Since this process can be repeated, it can be said that such a luminescent paper is a rewritable device.

[0027]Example 3 Distill 5 mg of Cu [C18] L2pz obtained in Production Example 1
Dissolve in 10 ml of methylene chloride prepared. Excitation at 280 nm
Filter paper (1.5 cm x 6) that does not emit fluorescence to light
(cm size) to the solution, dry it, and repeat
Stick your body on the paper. At the end, good so that no solvent remains
To dry. The paper made here is called luminous paper E. Luminous paper
E is put in an electric furnace and kept at 40 ° C. for 15 minutes or more. That
Then, if it is left to cool at room temperature, it emits an orange light at room temperature.
Is memorized. This state is called luminescent paper F. Thermal transfer pre
Input head (Hitachi D-2500 type chromatographic data processing
At least the printer section of the processing device and the head for thermal transfer
It is 70 ° C or higher. ) To type letters on the luminescent paper F.
To Actually, the luminescent paper F is used instead of the thermal paper,
Write a string. This state is called luminous paper G. Luminous paper
As shown in FIG. 13, G has an orange background with a red color.
Is written. Also, this luminescent paper G has a front
I was able to write on both sides without showing through. on the other hand
Insulate the entire luminescent paper G at 40 ° C for 15 minutes or more in an electric furnace.
To do. After that, when it is left to cool at room temperature, it returns to the luminescent paper F.
It was

[Brief description of drawings]

FIG. 1 is a dendrimer (Chemical Formula 6, Cu
It is a figure which shows the synthetic pathway (the 1) of [C18] L2pz).

2 is a dendrimer (Chemical Formula 6, Cu
It is a figure which shows the synthetic route (the 2) of [C18] L2pz).

FIG. 3 is a dendrimer (Chemical formula 6, Cu obtained in Production Example 1).
It is a figure which shows MALDI-TOF-MS of [C18] L2pz).

FIG. 4 is a dendrimer (chemical formula 6, Cu obtained in Production Example 1).
Is a chart showing ¹ H nuclear magnetic resonance spectrum of [C18] L2pz).

FIG. 5: Dendrimer (Chemical formula 6, Cu obtained in Production Example 1)
It is a figure which shows the differential scanning calorimetry profile of [C18] L2pz).

FIG. 6 is a schematic diagram of a fluorescence spectrum apparatus whose emission was measured in Example 1.

FIG. 7 is an emission spectrum of a dendrimer (Chemical Formula 6) measured in Example 1 while controlling the temperature. 30 at 40 ° C
It was cooled from 80 ° C. to 20 ° C. while being held for minutes.

FIG. 8 is an emission spectrum of a dendrimer (Chemical Formula 6) measured in Example 1 while controlling the temperature. Instead of holding at 40 ° C, it was cooled from 80 ° C to 20 ° C.

FIG. 9 is an emission spectrum of a dendrimer (Chemical formula 6) measured in Example 1 while controlling the temperature. What was cooled to room temperature as shown in FIG. 7 was heated to 80 ° C.

10 is an emission spectrum of a dendrimer (Chemical Formula 6) measured in Example 1 while controlling the temperature. FIG. What was cooled as shown in FIG. 8 was heated to 80 ° C.

FIG. 11 is a diagram showing an arrangement of a luminescence measuring device for a luminescent material according to the present invention.

FIG. 12: Dendrimer (Chemical formula 6, Cu obtained in Production Example 1)
[C18] L2pz) is applied to a filter paper, covered with an S-shaped portion, heated, and irradiated with ultraviolet rays to photograph the emitted light. Since the parts other than the S-shape are heated to 80 ° C and the S-shape is not heated, the emission wavelength is different,
You can visually recognize the S-shape.

FIG. 13: Dendrimer (Chemical Formula 6, Cu obtained in Production Example 1)
[C18] L2pz) is applied to a filter paper and printed on by a thermal transfer printer. Since the printed portion is heated to 70 ° C. or higher and the printed portion is not heated, the emission wavelength is different and the printed portion can be visually recognized.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H048 AA01 AA03 AB92 VA30 VA32                       VA56 VB10

Claims (7)

[Claims] 1. The following general formula (Formula 1): (In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom or a methyl group, and R is [Chemical 3] Or [Chemical 4] (In the formula, R ′ may be the same or different, and each of the following formulas (Formula 5) (In the formula, R ³ , R ⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom, an alkyl group or an alkoxy group, and at least one of R ³ , R ⁴ and R ⁵ has a carbon number. Is an alkyl group or an alkoxy group having 6 or more.). ), M is Au, Ag
Alternatively, it represents a monovalent ion of Cu, and n represents an integer of 2 to 4. ) The compound represented by. 2. The compound according to claim 1, wherein R is represented by Chemical formula 2 or Chemical formula 3. 3. At least one of R ³ and R ⁵ is an alkyl group or an alkoxy group having 6 or more carbon atoms, and R ⁴ has at least one of R ³ and R ⁵ having 6 or more carbon atoms. The compound according to claim 1 or 2, which is an alkyl group or alkoxy group having a smaller number of carbon atoms than the alkyl group or alkoxy group which is, or a hydrogen atom. 4. At least one of R ³ and R ⁵ is a linear alkoxy group having 16 to 20 carbon atoms, and R
The compound according to claim 1 or 2, wherein ³ and R ⁵ are a hydrogen atom when they are not the alkoxy group, and R ⁴ is a hydrogen atom. 5. A luminescent material comprising the compound according to any one of claims 1 to 4. 6. The light-emitting body according to claim 5, a heat source capable of changing the temperature of the light-emitting body in a temperature range including a liquid crystal region thereof, and a light source for irradiating excitation light required for the light-emitting body to emit light. A light emitting device. 7. The light emitting device according to claim 6, wherein the heat source can heat the light emitter so that the temperature can be changed for each part of the light emitter.