JP5540302B2 - Organic inorganic composite - Google Patents
Organic inorganic composite Download PDFInfo
- Publication number
- JP5540302B2 JP5540302B2 JP2008060381A JP2008060381A JP5540302B2 JP 5540302 B2 JP5540302 B2 JP 5540302B2 JP 2008060381 A JP2008060381 A JP 2008060381A JP 2008060381 A JP2008060381 A JP 2008060381A JP 5540302 B2 JP5540302 B2 JP 5540302B2
- Authority
- JP
- Japan
- Prior art keywords
- organic
- layered
- coumarin
- doc
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims description 14
- 239000000126 substance Substances 0.000 claims description 41
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 51
- 229960000956 coumarin Drugs 0.000 description 26
- 235000001671 coumarin Nutrition 0.000 description 26
- 239000000975 dye Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- -1 molded body Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- DDRNURGGQREYNQ-UHFFFAOYSA-N CC1=C2C(=C(C(OC2=CC=C1)=O)N1CCCCC1)C(F)(F)F Chemical compound CC1=C2C(=C(C(OC2=CC=C1)=O)N1CCCCC1)C(F)(F)F DDRNURGGQREYNQ-UHFFFAOYSA-N 0.000 description 1
- VFIFCUVHZDIEKO-UHFFFAOYSA-N NC(=O)OCC.C(C)O[Si](CCCOC1=CC=C2C(=CC(OC2=C1)=O)C)(OCC)OCC Chemical compound NC(=O)OCC.C(C)O[Si](CCCOC1=CC=C2C(=CC(OC2=C1)=O)C)(OCC)OCC VFIFCUVHZDIEKO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明は、層状ケイ酸塩と有機物とからなる有機無機複合体に関する。 The present invention relates to an organic-inorganic composite comprising a layered silicate and an organic substance.
本発明の有機無機複合体は、異なる有機分子をナノ空間に共存させる手段として従前より行われた構造を有するものである。
このような構造を用いずに、複数の有機物（色素等）を層間に挿入しようとするとき、先ず１つ目の有機物を層間に挿入し、得られた複合体をホスト複合体とし２つ目の色素を層間に挿入しようとすると、多くの場合、以下の３つのいずれかの結果に至り、異種有機物（色素等）の共存は難しい。
・１つ目の色素が２つ目の色素と交換して系外に放出されるデインターカレーションが起こる。
・１つ目の色素の再配列が起こり、各々の色素が別の層に取り込まれた層別と呼ばれる状態になる。
・２つ目の色素が取り込まれない。
The organic-inorganic composite of the present invention has a structure that has been conventionally used as a means for allowing different organic molecules to coexist in the nanospace.
When trying to insert a plurality of organic substances (dyes, etc.) between layers without using such a structure, first the first organic substance is inserted between the layers, and the resulting complex is used as the host complex. In many cases, it is difficult to coexist with different kinds of organic substances (pigment etc.).
Deintercalation occurs where the first dye is exchanged with the second dye and released out of the system.
A rearrangement of the first dye occurs, resulting in a state called stratification where each dye is incorporated into another layer.
-The second dye is not taken up.
本発明はこのような実情に鑑み、異種の有機物を互いに緩衝することなく保持させた有機無機複合体を提供することを目的とする。 In view of such a situation, an object of the present invention is to provide an organic-inorganic composite in which different organic substances are held without buffering each other.
発明１の有機無機複合体は、層状無機物に有機物を共有結合又は配位結合した結合複合体の層間に第二の有機物を挿入し、前記層状無機物に結合する有機物を所定波長での発光を生じる色素とし、前記第二の有機物が、前記発光波長域内に吸収域を有する色素であり、前記層状無機物が層状ケイ酸塩、層状燐酸ジルコニウム、層状チタン酸塩、層状ニオブ酸塩又は層状シロキサンの群から選択されるいずれかであり、前記有機物及び前記第二有機物がいずれも有機色素であることを特徴とする。
The organic-inorganic composite according to the first aspect of the present invention inserts a second organic substance between layers of a bonded composite in which an organic substance is covalently bonded or coordinated to the layered inorganic substance, and the organic substance bonded to the layered inorganic substance emits light at a predetermined wavelength. A dye, wherein the second organic substance is a dye having an absorption region in the emission wavelength range, and the layered inorganic substance is a group of layered silicate, layered zirconium phosphate, layered titanate, layered niobate or layered siloxane The organic substance and the second organic substance are both organic dyes.
発明２は、発明１の有機無機複合体において、前記層状ケイ酸塩は、式１に示される化学組成を有することを特徴とする。
（式１）
Ｌｉｍ（Ｍｇ３−ｍＬｉｍ）Ｓｉ４Ｏ１０（ＯＨ）２……（１）
（０．２＜ｍ＜０．３）
発明３は、発明１又は２に記載の有機無機複合体において、前記層状無機物に結合する有機物が、クマリン、キノリン、ローダミンＢ、メチルビオロゲンの群から選択されるいずれかの有機色素であることを特徴とする。
Invention 2 is characterized in that in the organic-inorganic composite of Invention 1, the layered silicate has a chemical composition represented by Formula 1.
(Formula 1)
Li m (Mg 3-m Li m) Si 4 O 10 (OH) 2 ...... (1)
(0.2 <m <0.3)
A third aspect of the present invention is an organic-inorganic composite according to Invention 1 or 2, organic compounds that bind to the layered inorganic substance, coumarin, quinoline, and rhodamine B, is any organic dye selected from the group of methyl viologen It is characterized by.
二種の有機物は、一方が層状無機物に共有結合又は配位結合にて強固に保持され、他方が層間にインターカレントされて保持され、それぞれが別々の保持構造で保持されているので、両者が緩衝することなく安定して保持することができるようになった。
また、層状ケイ酸塩を用いることで、粉体、成形体、膜等にする事ができ、実用上の諸要求に対応した形状としても上記のような効果を発揮させることができ、大変便利である。
また、蛍光発色団であるクマリン等の色素を有機物とし、その発光波長の域内に吸収波長を有する色素を第二の有機物とした場合に、有機物間のエネルギー移動が起こるので、エネルギー変換素子等への応用も期待できる。
特にクマリンは、その発光波長が３５０−６００ｎｍと広い波長範囲に及ぶので、クマリンと第二の有機物であるＤＯＣの間の異種色素間距離を制御する事も可能であり、またエネルギー移動効率は異種色素間距離に依存するため、エネルギー移動効率の制御も可能である。
当該共存系の構築は、クマリンと無機材料が共有結合又は配位結合したホスト複合体へゲスト色素を挿入するだけという、発明者独自の発案により非常に容易に達成でき、広く応用できると思われる。
One of the two organic substances is firmly held by a covalent bond or a coordinate bond to the layered inorganic substance, the other is held in an intercurrent manner between the layers, and each is held by a separate holding structure. It became possible to hold stably without buffering.
In addition, by using layered silicate, it can be made into powder, molded body, film, etc., and the above effects can be exhibited even in the shape corresponding to various practical requirements, so it is very convenient It is.
In addition, when a dye such as coumarin, which is a fluorescent chromophore, is used as an organic substance, and a dye having an absorption wavelength within the emission wavelength range is used as a second organic substance, energy transfer occurs between the organic substances. The application of can also be expected.
In particular, since the emission wavelength of coumarin covers a wide wavelength range of 350-600 nm, it is possible to control the distance between the different dyes between the coumarin and the second organic substance DOC, and the energy transfer efficiency is different. Since it depends on the distance between the dyes, it is possible to control the energy transfer efficiency.
The construction of the coexistence system can be achieved very easily by the inventor's original idea that only a guest dye is inserted into a host complex in which coumarin and an inorganic material are covalently bonded or coordinated. .
本発明の有機無機複合体は、層状無機物に有機物を共有結合又は配位結合した結合複合体の層間に第二の有機物を挿入したことを特徴とするものである。
前記層状無機物としては、以下の実施例に示す下記式（１）に示す層状ケイ酸塩が有利なものであるが、本発明はこれに限らず、次表に示す層状燐酸ジルコニウム、層状チタン酸塩、層状ニオブ酸塩、層状シロキサンのような層状無機物が使用可能である。
（式１）
Ｌｉｍ（Ｍｇ３−ｍＬｉｍ）Ｓｉ４Ｏ１０（ＯＨ）２……（１）
（０．２＜ｍ＜０．３）
The organic-inorganic composite of the present invention is characterized in that the second organic substance is inserted between the layers of the bonded composite in which the organic substance is covalently or coordinately bonded to the layered inorganic substance.
As the layered inorganic substance, a layered silicate represented by the following formula (1) shown in the following examples is advantageous, but the present invention is not limited to this, and the layered zirconium phosphate and layered titanate shown in the following table are preferred. Layered inorganic materials such as salts, layered niobates and layered siloxanes can be used.
(Formula 1 )
L i m (Mg 3-m Li m) Si 4 O 10 (OH) 2 ...... (1)
(0.2 <m <0.3)
また、結合複合体を構成するために前記層状無機物に共有結合される有機物としては、その機能からクマリンが有用であるが、これに限らず、以下の表１に示すような有機物が使用可能である。
さらに、前記結合複合体の層間に挿入される第二の有機物としては、以下のようなものが有効である
クマリンを共有結合している場合は、波長３５０−４５０ｎｍに吸収域を有する以下のような色素。３，３’−ジエチルオキシカルボシアニン（ＤＯＣ）等の本技術に使える化合物の例を以下に述べます。
・シアニン色素のうち、３５０−４５０ｎｍに吸収が有るもの（３，３’−ジエチルオキシカルボシアニン、ジメチル−エチルシアカルボシアニン等）
・クマリン誘導体のうち、３５０−４５０ｎｍに吸収が有るもの（ベンゾチアゾイル−７−ジエチルアミノクマリン、メチル−トリフルオロメチルピペリジノ−クマリン、テトラハイドロ−８−トリフルオロメチルキノリジノ−［９，９ａ，１−ｇｈ］クマリン等）
・その他の色素で、３５０−４５０ｎｍに吸収が有るもの（フルオレセイン、ジメチルアミノスチリル−ベンゾチアゾリルエチル、ジメチルアミノスチリル−ピリジルメチル）
・その他の化合物で、３５０−４５０ｎｍに吸収が有るもの（ルテニウムビピリン錯体等）
層状ケイ酸塩の層間に構築されたクマリン／シアニン共存系。クマリンは層状ケイ酸塩に共有結合しており、組成式は次の式２で与えられる。
（式２）
（Ｃ２１Ｈ２１Ｎ２Ｏ４）ｊ（Ｃ１４Ｈ１４ＮＯ４）ｋＬｉｍ（Ｍｇ３−ｍＬｉｍ）Ｓｉ４Ｏ１０（ＯＨ）２…（２）
（０．０１ ＜ ｊ ＜ １０， ０．００１＜ｋ＜０．０１，０．２＜ｍ＜０．３）
形状は、粉体、バルク、膜状等目的に応じて、成形される。この飽和吸収剤は、およそ３００−５００ｎｍで発される蛍光等の光を吸収する。
特許文献１に示す飽和吸収剤と同様の効果が文献より広い波長域（３００−５００ｎｍ）で発揮できると期待できる。
Further, as the second organic substance inserted between the layers of the binding complex, the following are effective. When coumarin is covalently bonded, it has an absorption region at a wavelength of 350 to 450 nm as follows. Pigment. Examples of compounds that can be used in this technology such as 3,3'-diethyloxycarbocyanine (DOC) are described below.
-Among cyanine dyes, those having absorption at 350-450 nm (3,3'-diethyloxycarbocyanine, dimethyl-ethylsiacarbocyanine, etc.)
Of the coumarin derivatives, those having absorption at 350-450 nm (benzothiazoyl-7-diethylaminocoumarin, methyl-trifluoromethylpiperidino-coumarin, tetrahydro-8-trifluoromethylquinolidino- [9, 9a, 1-gh] coumarin etc.)
Other dyes that absorb at 350-450 nm (fluorescein, dimethylaminostyryl-benzothiazolylethyl, dimethylaminostyryl-pyridylmethyl)
・ Other compounds with absorption at 350-450 nm (ruthenium bipyrin complex, etc.)
A coumarin / cyanine coexistence system built between layered silicate layers. Coumarin is covalently bonded to the layered silicate, and the composition formula is given by the following formula 2.
(Formula 2)
(C 21 H 21 N 2 O 4) j (C 14 H 14 NO 4) k Li m (Mg 3-m Li m) Si 4 O 10 (OH) 2 ... (2)
(0.01 <j <10, 0.001 <k <0.01, 0.2 <m <0.3)
The shape is formed according to the purpose such as powder, bulk, or film. This saturated absorbent absorbs light such as fluorescence emitted at approximately 300-500 nm.
It can be expected that the same effect as the saturated absorbent shown in Patent Document 1 can be exhibited in a wider wavelength range (300-500 nm) than the literature.
その他の有機物を共有結合している場合は、下表２のような有機物を層間に挿入するのが望ましい。
・合成；図１及び表３参照。
共有結合型の層状ケイ酸塩／クマリン複合体（ホスト複合体）は、７−（３−トリエトキシシリルプロピル）−Ｏ−（４−メチルクマリン）ウレタン、シリカゾル、Ｍｇ（ＯＨ）２及びＬｉＦを、以下の反応条件で、反応させて合成した。
その反応方法は、特許文献２又は非特許文献６に記載の方法により行った。
反応条件１；１５０℃以下の温度で１〜３日間保持
反応条件２；１〜５日間還流
層状ケイ酸塩／クマリン複合体（以下、ホスト複合体）４ｇを２００ｍｌのＨ２Ｏに分散。
別に用意したＤＯＣの２ｕＭ水溶液２００ｍｌを上記ホスト複合体の分散液に加えた後、１週間撹拌し、ＤＯＣをホスト複合体の層間へ挿入し、図２に示す試料No.１のクマリン／ＤＯＣ共存系を創製した。
・構造の確認；吸収スペクトル、Ｘ線回折等。
・蛍光発光波長域；図３の様に、共存系は広い波長域で発光を示す。
Synthesis; see Figure 1 and Table 3.
The covalently bonded layered silicate / coumarin complex (host complex) comprises 7- (3-triethoxysilylpropyl) -O- (4-methylcoumarin) urethane, silica sol, Mg (OH) 2 and LiF. The reaction was carried out under the following reaction conditions.
The reaction method was performed by the method described in Patent Document 2 or Non-Patent Document 6.
Reaction condition 1; held for 1 to 3 days at a temperature of 150 ° C. or less Reaction condition 2; 4 g of refluxing layered silicate / coumarin complex (hereinafter referred to as host complex) was dispersed in 200 ml of H 2 O.
Separately, 200 ml of a 2 uM aqueous solution of DOC was added to the above-mentioned dispersion of the host complex, and the mixture was stirred for one week. The DOC was inserted between the layers of the host complex, and sample No. 1 coumarin / DOC coexisted in FIG. The system was created.
-Confirmation of structure; absorption spectrum, X-ray diffraction, etc.
Fluorescence emission wavelength range: As shown in FIG. 3, the coexistence system emits light in a wide wavelength range.
・合成；実施例１と同様に、ホスト複合体４ｇを２００ｍｌのＨ２Ｏに分散。別に用意したＤＯＣの２０ｕＭ水溶液２００ｍｌをホスト複合体の分散液に加えた後、１週間撹拌し、ＤＯＣをホスト複合体の層間へ挿入し、試料No.２のクマリン／ＤＯＣ共存系を創製した。
比較試料；ホスト複合体の代わりに、合成スメクタイトＳＷＮ（コープケミカル（株）製）を用いて、ＤＯＣのみが二次元場に固定された系を準備。
・蛍光発光波長域；試料No.１と同様、広い波長域で発光を示す。
・エネルギー移動；３２０ｎｍで励起しても、５２０ｎｍ付近に発光（図４）。
比較試料；３２０ｎｍで励起すると図４の点線の様に発光はみられない。
ＤＯＣは５２０ｎｍで発光するが、３２０ｎｍの光は吸収しないため、３２０ｎｍで励起しても通常発光しない。３２０ｎｍの光は先ずクマリンに吸収され、その後、励起されたクマリンからＤＯＣへのエネルギー移動反応が起こるため、クマリン／ＤＯＣ共存系では３２０ｎｍで励起してもＤＯＣの発光が起こると考えられる。
Synthesis: In the same manner as in Example 1, 4 g of the host complex was dispersed in 200 ml of H 2 O. Separately, 200 ml of a 20 uM aqueous solution of DOC was added to the dispersion of the host complex, and the mixture was stirred for 1 week, and the DOC was inserted between the layers of the host complex to create a coumarin / DOC coexistence system of sample No. 2.
Comparative sample: A system in which only DOC is fixed in a two-dimensional field using synthetic smectite SWN (manufactured by Corp Chemical Co., Ltd.) instead of the host complex is prepared.
-Fluorescence emission wavelength range: Like the sample No. 1, it emits light in a wide wavelength range.
Energy transfer: Even when excited at 320 nm, light is emitted at around 520 nm (FIG. 4).
Comparative sample: When excited at 320 nm, no light emission is seen as shown by the dotted line in FIG.
DOC emits light at 520 nm, but does not absorb 320 nm light, so it does not normally emit light even when excited at 320 nm. The 320 nm light is first absorbed by the coumarin, and then an energy transfer reaction from the excited coumarin to the DOC occurs. Therefore, in the coumarin / DOC coexisting system, it is considered that DOC emission occurs even when excited at 320 nm.
・合成；実施例１と同様に、ホスト複合体４ｇを２００ｍｌのＨ２Ｏに分散。別に用意したＤＯＣの２００ｕＭ水溶液２００ｍｌをホスト複合体の分散液に加えた後、１週間撹拌し、ＤＯＣをホスト複合体の層間へ挿入し、試料No.３のクマリン／ＤＯＣ共存系を創製した。
・蛍光発光波長域；クマリン／ＤＯＣ共存系−１と同様、広い波長域で発光を示す。
・エネルギー移動；クマリン／ＤＯＣ共存系−２と同様、３２０ｎｍで励起しても、５２０ｎｍ付近に発光がみられる。
・エネルギー移動効率；図５に試料No.１〜３を３２０ｎｍで励起した時の蛍光発光スペクトルを示す。試料No.１から３へＤＯＣ量が増大する程エネルギー移動効率が高くなる。同じ順で、クマリンとＤＯＣの異種色素間距離が短くなっている。この範囲（２〜１００ｎｍ）では異種色素間距離は、ＤＯＣ量（１ｇ当り１ｅ−５〜１ｅ−１ｍｍｏｌ）に良く依存し、さらに、異種色素間距離とエネルギー移動効率の関係は理論式にのっているため、ＤＯＣ量を調節するだけでエネルギー移動効率を制御できる。
Synthesis: In the same manner as in Example 1, 4 g of the host complex was dispersed in 200 ml of H 2 O. Separately, 200 ml of a DOC 200 uM aqueous solution was added to the dispersion of the host complex and stirred for 1 week, and the DOC was inserted between the layers of the host complex to create a coumarin / DOC coexistence system of Sample No. 3.
-Fluorescence emission wavelength range: As in the coumarin / DOC coexistence system-1, it emits light in a wide wavelength range.
Energy transfer: As with the coumarin / DOC coexistence system-2, even when excited at 320 nm, light emission is observed at around 520 nm.
Energy transfer efficiency: FIG. 5 shows a fluorescence emission spectrum when sample Nos. 1 to 3 are excited at 320 nm. As the amount of DOC increases from sample No. 1 to 3, the energy transfer efficiency increases. In the same order, the distance between the different pigments of coumarin and DOC is shortened. In this range (2 to 100 nm), the distance between the different dyes depends well on the amount of DOC (1e-5 to 1e-1 mmol per gram), and the relationship between the distance between the different dyes and the energy transfer efficiency follows the theoretical formula. Therefore, the energy transfer efficiency can be controlled only by adjusting the DOC amount.
・合成；実施例１と同様に、ホスト複合体０．４ｇを２０ｍｌのＨ２Ｏに分散。別に用意したＤＯＣの２００ｕＭ水溶液２００ｍｌをホスト複合体の分散液に加えた後、１週間撹拌し、ＤＯＣをホスト複合体の層間へ挿入し、試料No.４を、同様にＤＯＣ２００ｕＭ水溶液２０００ｍｌを用いて試料No.５を、それぞれ創製した。ＤＯＣの比率を上げる事により、異種色素間距離が非常に短い（０．５〜３ｎｍ）系を得た。
消光；色素間距離が非常に短い場合は、励起された色素のエネルギーは濃度消光等により失われ、図６に示す様に蛍光は発されない。
光学系に必要な蛍光吸収剤等に用いる事ができると考えられる。
Quenching; When the distance between dyes is very short, the energy of the excited dye is lost due to concentration quenching or the like, and no fluorescence is emitted as shown in FIG.
It can be considered that it can be used as a fluorescent absorber necessary for an optical system.
Claims (3)
前記層状無機物に結合する有機物を所定波長での発光を生じる色素とし、前記第二の有機物が、前記発光波長域内に吸収域を有する色素であり、
前記層状無機物が層状ケイ酸塩、層状燐酸ジルコニウム、層状チタン酸塩、層状ニオブ酸塩又は層状シロキサンの群から選択されるいずれかであり、
前記有機物及び前記第二有機物がいずれも有機色素であることを特徴とする有機無機複合体。 A second organic substance is inserted between layers of a bonded complex in which the organic substance is covalently or coordinately bonded to the layered inorganic substance;
The organic substance bonded to the layered inorganic substance is a dye that emits light at a predetermined wavelength, and the second organic substance is a dye having an absorption region in the emission wavelength range,
The layered inorganic material is any one selected from the group of layered silicate, layered zirconium phosphate, layered titanate, layered niobate or layered siloxane,
The organic-inorganic composite, wherein both the organic substance and the second organic substance are organic pigments.
（式１）
Ｌｉｍ（Ｍｇ３−ｍＬｉｍ）Ｓｉ４Ｏ１０（ＯＨ）２……（１）
（０．２＜ｍ＜０．３） The organic-inorganic composite according to claim 1, wherein the layered silicate has a chemical composition represented by Formula 1.
(Formula 1)
Li m (Mg 3-m Li m) Si 4 O 10 (OH) 2 ...... (1)
(0.2 <m <0.3)
In the organic-inorganic composite according to claim 1 or 2, organic compounds that bind to the layered inorganic material, and wherein coumarin, quinoline, rhodamine B, that is any organic dye selected from the group of methyl viologen Organic-inorganic composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008060381A JP5540302B2 (en) | 2008-03-11 | 2008-03-11 | Organic inorganic composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008060381A JP5540302B2 (en) | 2008-03-11 | 2008-03-11 | Organic inorganic composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009215106A JP2009215106A (en) | 2009-09-24 |
| JP5540302B2 true JP5540302B2 (en) | 2014-07-02 |
Family
ID=41187372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008060381A Expired - Fee Related JP5540302B2 (en) | 2008-03-11 | 2008-03-11 | Organic inorganic composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5540302B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5321543B2 (en) * | 2010-07-01 | 2013-10-23 | 東洋インキＳｃホールディングス株式会社 | Resin composition for solar cell encapsulant |
| JP5577895B2 (en) * | 2010-07-01 | 2014-08-27 | 東洋インキＳｃホールディングス株式会社 | Phosphor composition |
| JP7016493B2 (en) * | 2016-09-09 | 2022-02-07 | 国立研究開発法人物質・材料研究機構 | Organic-inorganic complex and its manufacturing method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256251A (en) * | 1999-03-09 | 2000-09-19 | New Japan Chem Co Ltd | Rare-earth metal-carrying nano-size (host-guest) complex |
| JP4613302B2 (en) * | 2001-03-19 | 2011-01-19 | 独立行政法人物質・材料研究機構 | Covalently bonded layered silicate / dye complex and method for producing the same |
| JP2004002491A (en) * | 2002-04-08 | 2004-01-08 | National Institute For Materials Science | Fluorescent layered inorganic-organic composite synthesized by including a laser dye in an inorganic layered compound and a method for producing the same |
| JP4507581B2 (en) * | 2003-12-11 | 2010-07-21 | 株式会社豊田中央研究所 | Method for producing dye-containing mesoporous material |
| JP5110497B2 (en) * | 2006-02-21 | 2012-12-26 | 独立行政法人物質・材料研究機構 | Layered silicate composite and method for producing the same |
-
2008
- 2008-03-11 JP JP2008060381A patent/JP5540302B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009215106A (en) | 2009-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Carbon dots‐in‐matrix boosting intriguing luminescence properties and applications | |
| Cha et al. | Formation and encapsulation of all-inorganic lead halide perovskites at room temperature in metal–organic frameworks | |
| Takagi et al. | Size-matching effect on inorganic nanosheets: Control of distance, alignment, and orientation of molecular adsorption as a bottom-up methodology for nanomaterials | |
| Zhou et al. | Conquering aggregation-induced solid-state luminescence quenching of carbon dots through a carbon dots-triggered silica gelation process | |
| Daliran et al. | CsCu2I3 nanoparticles incorporated within a mesoporous metal–organic porphyrin framework as a catalyst for one-pot click cycloaddition and oxidation/knoevenagel tandem reaction | |
| Lotsch et al. | Photonic clays: a new family of functional 1D photonic crystals | |
| Lee et al. | Luminescent metal–organic framework-functionalized graphene oxide nanocomposites and the reversible detection of high explosives | |
| Xu et al. | Metal–organic frameworks with aggregation‐induced emission | |
| Chandra et al. | Multi-core-shell composite SnO2NPs@ ZIF-8: potential antiviral agent and effective photocatalyst for waste-water treatment | |
| Yuan et al. | Long afterglow MOFs: a frontier study on synthesis and applications | |
| Tsukamoto et al. | Supramolecular surface photochemistry: Cascade energy transfer between encapsulated dyes aligned on a clay nanosheet surface | |
| Sasai et al. | Preparation and characterization of rhodamine 6G/alkyltrimethylammonium/laponite hybrid solid materials with higher emission quantum yield | |
| TWI589229B (en) | Mycotoxin adsorbent | |
| Li et al. | Mesoporous silica functionalized with an AIE luminogen for drug delivery | |
| Romolini et al. | Tunable luminescence from stable silver nanoclusters confined in microporous zeolites | |
| JP5540302B2 (en) | Organic inorganic composite | |
| Li et al. | Preparation and characterization of 5, 10, 15, 20-tetrakis (4-carboxyphenyl) porphyrin grafted on organosilane-pillared montmorillonite by covalent bonding | |
| Olla et al. | The void side of silica: Surveying optical properties and applications of mesoporous silica | |
| Jana et al. | Facile synthesis and optical study of organic-inorganic lead bromide perovskite-clay (kaolinite, montmorillonite, and halloysite) composites | |
| Karabel Ocal et al. | Natural wax-stabilized perovskite nanocrystals as pen-on-paper inks and doughs | |
| Miyamoto et al. | Intercalation of a cationic cyanine dye into the layer silicate magadiite | |
| Xiang et al. | 2D Nanomaterial-Directed Molecular Aggregation and Energy Transfer between Edge-Bound Donor–Acceptor Pairs | |
| Wang et al. | Study on the fluorescence properties of fluorescein dye incorporated into SBA-15 | |
| Irie et al. | Reticular construction of a two-dimensional Ag 12 cluster-assembled material for rapid and selective luminescent sensing of antibiotics in aqueous media | |
| Balkus Jr et al. | Photoluminescent and redox active periodic mesoporous organosilicas based on 2, 7-diazapyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110224 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130108 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130304 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130903 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130926 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140401 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140409 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5540302 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |