JP4517154B2 - Polyphenylene dendrimer - Google Patents

Description

  The present invention relates to a novel polyphenylene dendrimer and a method for producing the same.

  The dendrimer compound has a unique chemical structure in which a central core, a dendritic structure composed of a branching unit (dendron) extending from the core, and a surface functional group arranged in the outermost layer develop three-dimensionally. For example, many studies have been made in the fields of electronic material science, interface science, material science, and the like. As an application example of the dendrimer compound, various techniques such as use for electronic materials (Patent Document 1), use for liquid crystal (Patent Document 2), use for fluorescent resin sheet (Patent Document 3), etc. have been proposed. .

  Further, as a technique related to a polyphenylene compound, a technique using a condensed polycyclic aromatic compound as a semiconductor (Patent Document 4), a technique using a tribenzotriphenylenovalene derivative as an organic light emitting element (Patent Document 5), and the like are known. ing.

JP-A-11-171812 JP 2000-264965 A JP-A-11-323324 JP-A-2005-79163 JP 2002-216963 A

  The subject of this invention is providing a novel polyphenylene dendrimer compound and its manufacturing method.

  As a result of diligent research to solve the above problems, the present inventors synthesized a dendrimer molecule having stilbene in the dendrimer core and polyphenylene in the dendron, and completed a novel polyphenylene dendrimer.

Although not limited thereto, the present invention includes the following inventions.
(1) Polyphenylene dendrimer having the following formula:

[In the formula, one X is introduced at the para-position of the benzene ring of stilbene, or two are introduced at the meta-position,
X is represented by the following formula:

[In the formula, two Rs may be the same or different and are independently of each other a linear, branched or cyclic C1-C20 alkyl group, C1-C20 alkenyl group, C1-C20 An alkynyl group, a C1-C20 alkoxy group; an amino group (—NH2) group; a carboxylic acid (—COOH) group; a C1-C10 alkylamino group; a C1-C10 acylamino group, wherein these groups are —COOH _{, -NH 2, -SH, -OH,} -CH = CH2, may be substituted by -Ph (phenyl)];
Here, the stilbene moiety can have a trans or cis configuration.
(2) Polyphenylene dendrimer having the following formula:

[Wherein R is as described in (1)].
(3) A method for producing the dendrimer according to (2), comprising cyclizing the dendrimer according to (1).

  The above-described problems have been solved by the present invention. Moreover, the dendrimer of the present invention can be used as a photochemical material.

  The present invention, in one embodiment, is a polyphenylene dendrimer having the following formula I:

[In the formula, one X is introduced at the para-position of the benzene ring of stilbene, or two are introduced at the meta-position,
X is represented by the following formula:

[In the formula, two Rs may be the same or different and are independently of each other a linear, branched or cyclic C1-C20 alkyl group, C1-C20 alkenyl group, C1-C20 An alkynyl group, a C1-C20 alkoxy group; an amino group (—NH2) group; a carboxylic acid (—COOH) group; a C1-C10 alkylamino group; a C1-C10 acylamino group, wherein these groups are —COOH _{, -NH 2, -SH, -OH,} -CH = CH2, optionally substituted by -Ph];
Here, the stilbene moiety can have a trans or cis configuration.

  In the present invention, stilbene is used as the core of the dendrimer. In general, stilbene molecules are known to undergo isomerization between trans and cis isomers at the C = C double bond by UV irradiation, and the trans isomer is known to emit fluorescence. ing. Furthermore, in the present invention, polyphenylene is used as the dendron of the dendrimer. The dendron in the present invention has a relatively rigid structure. In the polyphenylene dendrimer of the present invention having such a core and a dendron, the stilbene moiety that is the core is photoisomerized between the cis form and the trans form by irradiation with ultraviolet rays. In the present specification and claims appended hereto, even if only a trans isomer or a cis isomer may be represented in the structural formula as a stilbene moiety, it is particularly clearly indicated. It should be noted that unless stated otherwise, the cis form or trans form is not excluded, but is described as including the cis form or trans form.

Furthermore, the polyphenylene dendron of the present invention can adjust the solubility in a solvent by the alkyl chain R. For example, by employing a long alkyl chain as R, it is possible to increase the solubility of the dendrimer molecule in a solvent. Specifically, as R, a linear, branched or cyclic C1-C20 alkyl group, C1-C20 alkenyl group, C1-C20 alkynyl group, C1-C20 alkoxy group can be used. R is more preferably a linear, branched or cyclic C5-C15 alkyl group, a C5-C15 alkenyl group, a C5-C15 alkynyl group, a C5-C15 alkoxy group, and more preferably a linear, branched or cyclic group. Cyclic, C8-C15 alkyl group, C8-C15 alkenyl group, C8-C15 alkynyl group, C8-C15 alkoxy group, most preferably linear, branched or cyclic C10-C14 alkyl group, C10-C14 An alkenyl group is a C10-C14 alkynyl group, a C10-C14 alkoxy group. Furthermore, R may be an amino group (—NH 2) group; a carboxylic acid (—COOH) group; a C 1 -C 10 alkylamino group; a C 1 -C 10 acylamino group. In addition, R is one or more of _{-COOH, -NH 2, -SH, -OH} , -CH = CH2, may be substituted by -Ph.

  Furthermore, the polyphenylene dendrimer of the present invention can be formed into a film. Therefore, the dendrimer of the present invention can be used as, for example, a fluorescent film. When a film comprising the polyphenylene dendrimer of the present invention is irradiated with ultraviolet light, a photoisomerization reaction proceeds, and the ultraviolet / visible absorption and fluorescence spectrum of the film change. Therefore, the polyphenylene dendrimer of the present invention can be suitably used as a photochromic material.

  As a method for forming the polyphenylene dendrimer of the present invention into a film, a known method can be used. For example, the polyphenylene dendrimer of the present invention is dissolved in a solvent, the solution is dropped on a glass plate, and the solvent is evaporated. Can be obtained. The solvent used for film formation is not particularly limited as long as it can dissolve the polyphenylene dendrimer of the present invention, and preferred examples include hexane, chloroform, diethyl ether, THF, benzene, dichloromethane, and ethyl acetate. Particularly preferred are hexane and chloroform. Here, the film comprising the polyphenylene dendrimer of the present invention may contain a compound other than the polyphenylene dendrimer, and various additives can be appropriately added depending on the application. For example, various luminescent dyes such as porphyrin compounds and aromatic polycyclic hydrocarbons such as pyrene and anthracene are particularly suitable because they can be expected to be used as luminescent materials when combined with the dendrimer of the present invention. In one embodiment, the dendrimer of the present invention can be filmed by the following procedure. That is, when the polyphenylene dendrimer of the present invention is dissolved in hexane and chloroform and dropped onto glass at room temperature, and then the solvent is evaporated, the polyphenylene dendrimer film can be obtained.

  In addition, the dendrimer of the present invention can be used by mixing in a polymer compound. The polymer in which the dendrimer of the present invention is dispersed is not particularly limited as long as it is a polymer compound that uniformly dissolves the dendrimer. However, when used as an optical material, a transparent polymer without scattering is preferable. Specific examples include at least one selected from the group consisting of methacrylic resin, acrylic resin, polycarbonate resin, urea resin, polyimide resin, epoxy resin, silicone resin, polyamide resin, polyurethane resin, and copolymers and mixtures thereof. be able to.

In addition, since the polyphenylene dendrimer of the present invention exhibits a characteristic photochemical behavior, it can be considered to be used as an organic EL, a semiconductor material, and a fluorescent material.
The present invention, in one embodiment, is also a polyphenylene dendrimer having the following formula:

[Wherein R is as described above].
Moreover, this invention is the manufacturing method of the said polyphenylene dendrimer in one aspect | mode. Specifically, the method for producing the polyphenylene dendrimer of the present invention includes cyclization of the dendrimer represented by the formula I.

  In the present invention, a known oxidant can be used as the oxidant in the cyclization reaction, and suitable oxidants include aluminum chloride, iron (III) chloride, copper trifluoromethanesulfonate (II), Examples include copper (II) chloride potassium permanganate, dichlorodicyano-p-benzoquinone, thallium (III) acetate, and manganese dioxide. The amount of the oxidizing agent in the cyclization reaction is also not particularly limited, but is preferably 10 to 1000 mol, more preferably 100 to 800 mol, and still more preferably 400 to 500 mol per mol of the raw dendrimer. Also, the reaction temperature and pH are not particularly limited. For example, the reaction can be performed at room temperature, and the reaction can be performed in an acid-neutral state.

  The following examples further illustrate the present invention. However, the description of the following examples is merely illustrative for explaining the present invention, and does not limit the scope of the present invention.

[Example 1] Synthesis of alkyl-substituted dendron (1) Synthesis of 1-bromo-4-dodecanoylbenzene Add AlCl ₃ (13.0 g, 0.0978 mol) to bromobenzene (24.9 g, 0.158 mol), at room temperature under air Then lauroyl chloride (17.4 g, 0.0796 mol) was added dropwise. After 1 hour, the reaction solution was poured into ice water (200 ml) and extracted with dichloromethane. The organic layer was washed with dilute hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated. Recrystallization from ethanol and vacuum drying gave 1-bromo-4-dodecanoylbenzene (0.0762 mol, yield 96%).
1H NMR (200 MHz, CDCl3, 298 K) d 0.88 (t, J = 6.4 Hz, 3H), 1.32-1.25 (m, 18H), 1.72 (t, J = 7.2 Hz, 2H), 7.60 (d, J = 8.6 Hz, 2H), 7.85 (d, J = 8.6 Hz, 2H)

(2) Synthesis of 1-bromo-4-dodecylbenzene KOH (12.4 g, 0.188 mol) and hydrazine monohydrate in a solution of 1-bromo-4-dodecanoylbenzene (18.6 g, 0.0548 mol) in diethylene glycol (120 ml) (8.20 g, 0.164 mol) was added, and the mixture was stirred at 210 ° C. for 3 hours under nitrogen. The reaction solution was poured into 200 ml of ice water and extracted with dichloromethane. The organic layer was washed with water and saturated aqueous NaHCO 3, dried over anhydrous MgSO 4 and concentrated. This was purified by silica gel chromatography using a developing solvent hexane / AcOEt (97/3) to obtain 1-bromo-4-dodecylbenzene (9.26 g, yield 67%).
1H NMR (200 MHz, CDCl3, 298 K) d 0.88 (t, J = 6.4, 3H), 1.40-1.20 (m, 18H), 1.57-1.51 (br, 2H), 2.54 (t, J = 7.6 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H)

(3) Synthesis of 1,2-bis (4-dodecylphenyl) ethane-1,2-dione In a solution of 1-bromo-4-dodecylbenzene (2.52 g, 0.00998 mol) in distilled tetrahydrofuran (10 ml) under nitrogen, Sec-Butyllithium (10 ml, 0.0099 mol) was added at -78 ° C. The above reaction solution was added to a solution of 1,4-dimethylpiperazine-2,3-dione (0.936 g, 0.00497 mol) in distilled tetrahydrofuran (10 ml) at 0 ° C. under nitrogen. After stirring for 3 hours, the organic layer was washed with dilute hydrochloric acid and saturated aqueous sodium hydrogen carbonate, dried over anhydrous MgSO4, and concentrated. This was purified by silica gel chromatography using a developing solvent hexane / ethyl acetate (95/5) to obtain 1,2-bis (4-dodecylphenyl) ethane-1,2-dione (yield 56%).
1H NMR (200 MHz, CDCl3, 298 K) d 0.88 (t, J = 6.4 Hz, 6H), 1.40-1.20 (m, 36H), 1.62-1.57 (br, 4H), 2.67 (t, J = 7.6 Hz , 4H), 7.31 (d, J = 8.4 Hz, 4H), 7.89 (d, J = 8.4 Hz, 4H)

(4) Synthesis of alkyl-substituted dendron 1,2-bis (4-dodecylphenyl) ethane-1,2-dione (1.00 g, 1.83 mmol), 1,3-diphenylacetone (0.354 g, 1.66) in ethanol under nitrogen mmol) was dissolved and refluxed. KOH (1.83 mmol) previously dissolved in a small amount of ethanol was added to the above reaction solution, reacted for 15 minutes, extracted with dichloromethane, and the organic layer was dried over magnesium sulfate and concentrated. The product was isolated by silica gel column chromatography using a developing solvent dichloromethane / hexane (1/2) to obtain an alkyl-substituted dendron (0.533 g, 0.739 mmol, yield 45%).
1H NMR (200 MHz, CDCl3, 298 K) d 0.89 (t, J = 6.3 Hz, 6H), 1.40-1.20 (m, 36H), 1.61-1.54 (br, 4H), 2.56 (t, J = 7.6 Hz , 4H), 6.81 (d, J = 8.2 Hz, 4H), 6.97 (d, J = 8.6 Hz, 4H), 7.27-7.22 (m, 10 H)

[Example 2] Synthesis of stilbene core (1) Synthesis of 1,3-dibromo-5-bromomethylbenzene 3,5-dibromotoluene (4.15 g, 0.0166 mol), NBS (2.95 g, 0.0166 mol), AIBN ( 10 mg) was dissolved in CCl ₄ and refluxed for 2.5 hours. After the succinic acid was filtered off, the filtrate was concentrated and recrystallized with hexane to obtain 1,3-dibromo-5-bromomethylbenzene (1.94 g, 5.90 mmol).
1H NMR (200 MHz, CDCl3, 298 K) d 4.37 (s, 2H), 7.47 (s, 2H), 7.60 (s, 1H)

(2) Synthesis of diethyl (3,5-dibromobenzyl) phosphate Phosphate triethyl (0.993 g, 5.98 mmol) was added to 1,3-dibromo-5-bromomethylbenzene (1.94 g, 5.90 mmol), and nitrogen was added. The reaction was performed at 180 ° C. for 5 hours. Drying gave diethyl (3,5-dibromobenzyl) phosphate. Diethyl (3,5-dibromobenzyl) phosphate was used in the next reaction without purification.

(3) Synthesis of 3,3,5,5-tetrabromostilbene Nitrogen substitution, diethyl (3,5-dibromobenzyl) phosphate in a solution of tetrahydrofuran and sodium hydride (288 mg, 7.08 mmol) while cooling with ice And stirred for a while. 3,5-dibromobenzaldehyde (2.28 g, 5.90 mmol) was added thereto, and the mixture was allowed to return to room temperature and reacted for 2 hours. Pour into water and extract with CH ₂ Cl ₂ , concentrate the organic layer, isolate by silica gel column chromatography with 100% hexane as developing solvent, recrystallize with chloroform and colorless needle crystals 3,3,5,5-tetra Bromostilbene (0.355 g, 12% yield) was obtained.
1H NMR (400 MHz, DMSO, 289 K) d 7.44 (s, 2H, Olefin-H), 7.79 (t, J = 1.6 Hz, 2H), 7.87 (d, J = 1.6 Hz, 4H).

(4) Synthesis of 3,3,5,5-tetrakis [(triisopropylsilanyl) ethynyl] stilbene Toluene, triethylamine and 3,3,5,5-tetrabromostilbene (0.0965 g, 0.195 mmol), [Ph3P] PdCl2 (4 mg, 0.006 mmol), copper iodide (2 mg, 0.011 mmol), and triphenylphosphine (3 mg, 0.011 mmol) were added and heated to 50 ° C. Triisopropylsilylacetylene (200 mg, 1.10 mmol) was added and stirred for a while, then raised to 70 ° C. and allowed to react overnight. It was poured into water, extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The crude product was purified by silica gel column chromatography with 100% hexane and then isolated with 100% GPC in hexane to obtain 3,3,5,5-tetrakis [(triisopropylsilanyl) ethynyl] stilbene. In place of the TIPS group, a TBDMS group (t-butyldimethylsilyl group) or a TBDPS group (t-butyldiphenylsilyl group) can be used.
1H NMR (200 MHz, CDCl3, 298 K) d 1.09-1.14 (br, 84H), 7.04 (s, 2H, Olefin-H), 7.45 (t, J = 1.4 Hz, 2H), 7.54 (d, J = (1.2 Hz, 4H)

(5) Synthesis of 4,4-bis [(triisopropylsilanyl) ethynyl] stilbene Toluene, triethylamine, 4,4-diiodostilbene (0.100 mg, 0.233 mmol), [Ph3P] PdCl2 (5 mg), iodide Copper (3 mg) and triphenylphosphine (4 mg) were added and heated to 50 ° C. Triisopropylsilylacetylene (512 mg, 2.81 mmol) was added and stirred for a while, then heated to 80 ° C. and reacted overnight. It was poured into water, extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. It was isolated by silica gel column chromatography using 100% developing solvent hexane to obtain 4,4-bis [(triisopropylsilanyl) ethynyl] stilbene. In the above reaction, the reaction can be allowed to proceed using 4,4-dibromostilbene and potassium iodide instead of 4,4-diiodostilbene.
1H NMR (200 MHz, CDCl3, 298 K) d 1.00-1.10 (m, 42H), 7.08 (s, 2H, Olefin-H), 7.45 (s, 8H)

[Example 3] Synthesis of polyphenylene dendrimer (1) Synthesis of alkyl-substituted polyphenylene dendrimer (in which dendron is substituted at the meta position of stilbene: also referred to as trans-meta-G1 in this specification) Example 2 (4) 3,3,5,5-tetrakis [(triisopropylsilanyl) ethynyl] stilbene (217 mg, 0.241 mmol) obtained by the method described in 1. was dissolved in tetrahydrofuran, and tetrabutylammonium fluoride was dissolved at room temperature under nitrogen. The mixture was stirred for 5 minutes. Water was added to stop the reaction, and tetrahydrofuran was distilled off, followed by extraction with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated. A small amount of methanol was added to the light brown residue to obtain an undissolved light brown compound (59.4 mg). NMR confirmed that this mixture contained deprotected stilbene. No further generation was performed and the next reaction proceeded.

(Diels-Alder reaction)
The core stilbene obtained by the above method and the alkyl-substituted dendron (614 mg, 0.852 mmol) obtained by the method described in Example 1 (4) are dissolved in diphenyl ether and reacted at 120 ° C. for 26 hours under nitrogen. It was. Extracted with dichloromethane and extracted with dichloromethane, and the organic layer was concentrated and purified by silica gel column chromatography using chloroform / hexane as a developing solvent, and then isolated with chloroform GPC to obtain an alkyl-substituted polyphenylene dendrimer (128 mg, 0.0425 mmol, yield). Rate 18%).
1H NMR (600 MHz, CDCl3, 298 K) d 0.90 (t, J = 6.6 Hz, 24H), 1.15-1.20 (m, 16H), 1.20-1.38 (m, 128H), 1.38-1.46 (m, 16H) , 2.36 (t, J = 6.6 Hz, 8H), 2.40 (t, J = 6.6 Hz, 8H), 6.28 (s, 2H, Olefin-H), 6.60-6.64 (m, 16H), 6.68-6.72 (m , 16H), 6.76-6.77 (m, 8H), 6.80-6.83 (m, 4H), 6.86-6.87 (m, 12H), 6.94 (s, 2H), 7.12-7.18 (m, 20H), 7.24-7.26 (m, 4H)

(2) Synthesis of alkyl-substituted polyphenylene dendrimer (in which dendron is substituted at the para-position of stilbene: also referred to herein as trans-para-G1) 4 obtained by the method described in Example 2 (5) , 4-Bis [(triisopropylsilanyl) ethynyl] stilbene (40.5 mg, 0.158 mmol) was dissolved in tetrahydrofuran and reacted in the same manner as in Example 3 (1) to obtain an alkyl-substituted polyphenylene dendrimer (269 mg). , 0.167 mmol).
1H NMR (600 MHz, CDCl3, 298 K) d 0.90 (t, J = 7.2 Hz, 12H), 1.12-1.16 (m, 8H), 1.20-1.33 (m, 64H), 1.39-1.48 (m, 8H) , 2.37 (t, J = 7.8 Hz, 4H), 2.41 (t, J = 7.8 Hz, 4H), 6.64-6.67 (m, 8H), 6.71-6.73 (m, 8H), 6.87-6.88 (m, 4H ), 6.94-6.97 (m, 8H), 7.12-7.18 (m, 14H), 7.26-7.28 (m, 4H), 7.58 (s, 2H, Olefin-H)

[Example 4] Synthesis of cyclized polyphenylene dendrimer (1) Synthesis of cyclized polyphenylene dendrimer (in which dendron is substituted at the meta position of stilbene: also referred to as trans-meta- [G1] PAH in this specification) A solution of copper (II) trifluoromethanesulfonate (2.13 g) and aluminum chloride (0.788 g) in carbon disulfide (100 ml) was stirred for a while under nitrogen and obtained by the method described in Example 3 (1). Polyphenylene dendrimer (44.4 mg) was added and reacted at room temperature for 4 days. Methanol (50 ml) was added and the precipitate was filtered. The solid on the filter paper was washed with aqueous ammonia, dilute hydrochloric acid and methanol to obtain a black brown solid (34.4 mg). Thereafter, the mixture was sonicated in a mixed solvent of THF / n-butylamine (4/1), and separated into a solvent-insoluble component and a soluble component by a centrifugal separator.

(2) Synthesis of cyclized polyphenylene dendrimer (in which dendron is substituted at the para-position of stilbene: also referred to herein as trans-para- [G1] PAH) Copper (II) trifluoromethanesulfonate (3.18 g) And a solution of aluminum dichloride (1.23 g) in carbon disulfide (100 ml) was stirred for a while under nitrogen, and polyphenylene dendrimer (37.3 mg) obtained by the method described in Example 3 (2) was added to room temperature. For 4 days. Methanol (50 ml) was added and the precipitate was filtered. The solid on the filter paper was washed with aqueous ammonia, dilute hydrochloric acid and methanol to obtain a black brown solid (35.6 mg). Thereafter, the mixture was sonicated in a mixed solvent of THF / n-butylamine (4/1), and separated into a solvent-insoluble component and a soluble component by a centrifugal separator.

[Example 5] Measurement of various physical properties (1) Measurement method
Hexane (for Kanto Chemical, for fluorescence analysis), benzene (for Wako Pure Chemical, for spectral analysis), and chloroform (for Kanto Chemical, for fluorescence analysis) were used as solvents for measurement of fluorescence . The absorption spectrum was measured using a Shimadzu UV-1600 type visible ultraviolet spectrophotometer. Moreover, Hitachi F-4500 type fluorimeter was used for fluorescence and fluorescence excitation spectrum measurement.

Calculation of Fluorescence Quantum Yield Fluorescence quantum yield was calculated by a relative method according to the following formula using an ethanol solution of anthracene as a standard substance.

Benzene was used as a solvent for measuring changes in ultraviolet and visible absorption spectra associated with photoisomerization . The light source was a JASCO FP333-type fluorimeter 150 W xenon lamp, which was irradiated with a bandwidth of 10 nm. Absorption spectra of pure trans form and cis form were measured in advance, and the change in absorbance at a specific wavelength of the trans form or cis form upon light irradiation was calculated as the change in the respective percent concentration. The percent concentration of trans isomer and cis isomer when the change in absorbance became constant was taken as the light steady state ratio.

(2) Measurement of physical properties of polyphenylene dendrimer The photochemical behavior of trans-meta-G1 obtained in Example 3 (1) and trans-para-G1 obtained in Example 3 (2) was measured.

  According to the method described above, the fluorescence excitation spectrum of these compounds in an organic solvent (chloroform, benzene, hexane) was measured. As a result of measuring fluorescence derived from stilbene core, the fluorescence quantum yield of trans-meta-G1 was 0.50 when the solvent was chloroform, 0.70 when benzene, and 0.69 when hexane. there were. On the other hand, the fluorescence quantum yield of trans-para-G1 is 0.88 when the solvent is chloroform, 0.83 when benzene, and 0.90 when hexane, regardless of the polarity of the solvent. The fluorescence quantum yield was shown. This means that trans-meta-G1 has a fluorescence quantum yield of about 10 times that of stilbene and trans-para-G1 has a fluorescence quantum yield of about 20 times that of stilbene. This indicates that energy transfer occurs from the dendron site to the stilbene site with high efficiency.

  Furthermore, when the ultraviolet and visible collection spectrum was measured by the above method, the trans-meta-G1 obtained in Example 3 (1) and the trans-para-G1 obtained in Example 3 (2) were obtained. It was confirmed that isomerization occurs between the trans and cis forms when irradiated with ultraviolet light. Specifically, when trans-meta-G1 was irradiated with ultraviolet rays, the absorbance at the long wavelength part peculiar to trans stilbene decreased in the UV spectrum, and the spectrum derived from the trans isomer was also observed in the fluorescence spectrum. The photo-steady-state ratio in meta-G1 isomerization was calculated to be trans / cis = 12/88.

  On the other hand, with respect to para-G1, when trans-para-G1 was irradiated with ultraviolet rays, the absorbance of the long wavelength part peculiar to trans stilbene decreased in the UV spectrum, and the spectrum derived from the trans isomer was also observed in the fluorescence spectrum. As a result of calculating the steady state ratio of para-G1 isomerization, trans-cis / cis-form was 85/15 in para-G1.

(3) Physical property measurement of cyclized polyphenylene dendrimer The cyclized polyphenylene dendrimer obtained in Example 4 (Dendron is substituted at the meta position of stilbene (trans-meta- [G1] PAH) and substituted at the para position The optical properties of the product (trans-para- [G1] PAH) were measured. trans-meta- [G1] PAH and trans-para- [G1] PAH are added to a mixed solvent of THF / n-butylamine (4/1), sonicated, and insoluble in solvent using a centrifuge. The component was separated into a soluble component and a soluble component, and an ultraviolet / visible absorption spectrum and a fluorescence spectrum were measured for each of the insoluble component and the soluble component. The results are shown in FIGS. The spectrum of FIGS. 1 to 4 suggests that the aromatic polycyclic hydrocarbon spreads in a sheet form.

FIG. 1 is a graph showing absorption (Absorbance: Abs), fluorescence (FL), and fluorescence excitation (FLE) spectra of insoluble components (Precipitant) of the cyclized polyphenylene dendrimer obtained in Example 4 (1). In the graph, the horizontal axis represents wavelength, and the vertical axis represents absorption and fluorescence intensity. FIG. 2 is a graph showing absorption (Abs), fluorescence (FL), and fluorescence excitation (FLE) spectra of a soluble component (supernatant) of the cyclized polyphenylene dendrimer obtained in Example 4 (1). FIG. 3 is a graph showing absorption (Abs), fluorescence (FL), and fluorescence excitation (FLE) spectra of insoluble components of the cyclized polyphenylene dendrimer obtained in Example 4 (2). FIG. 4 is a graph showing absorption (Abs), fluorescence (FL), and fluorescence excitation (FLE) spectra of insoluble components of the cyclized polyphenylene dendrimer obtained in Example 4 (2).

Claims (3)

Polyphenylene dendrimer having the formula:
[In the formula, one X is introduced at the para position of the benzene ring of stilbene or two are introduced at the meta position, and X is represented by the following formula:
[In the formula, two Rs may be the same or different and are independently of each other a linear, branched or cyclic C1-C20 alkyl group, C1-C20 alkenyl group, C1-C20. An alkynyl group, a C1-C20 alkoxy group; an amino group (—NH ₂ ) group; a carboxylic acid (—COOH) group; a C1-C10 alkylamino group; a C1-C10 acylamino group, wherein these groups are — _{COOH, -NH 2, -SH, -OH} , -CH = CH 2, may be substituted by -Ph]
Wherein the stilbene moiety can take the trans or cis configuration]. A polyphenylene dendrimer having the following formula , obtained by cyclization of the polyphenylene dendrimer of claim 1 with an oxidizing agent :
[Wherein R is as defined in claim 1]. A method for producing a dendrimer according to claim 2, comprising cyclizing the dendrimer according to claim 1 with an oxidizing agent .