JP5757615B2 - Organic / metal hybrid polymer comprising a metal having a coordination number of 4 and a bisphenanthroline derivative, a ligand thereof, and a production method thereof - Google Patents
Organic / metal hybrid polymer comprising a metal having a coordination number of 4 and a bisphenanthroline derivative, a ligand thereof, and a production method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims description 68
- 239000002184 metal Substances 0.000 title claims description 68
- 229920000642 polymer Polymers 0.000 title claims description 55
- 239000003446 ligand Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010949 copper Substances 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 125000006850 spacer group Chemical group 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- -1 phenylacetyl group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 3
- 230000009918 complex formation Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 150000005041 phenanthrolines Chemical class 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical class N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- QSPYZQVJFFAIEE-UHFFFAOYSA-L copper diperchlorate hydrate Chemical compound O.[Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O QSPYZQVJFFAIEE-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KAYXDWIILRESPY-UHFFFAOYSA-N 2-[7-(1,3,2-dioxaborinan-2-yl)-9,9-dioctylfluoren-2-yl]-1,3,2-dioxaborinane Chemical compound C1=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B4OCCCO4)=CC=C3C2=CC=C1B1OCCCO1 KAYXDWIILRESPY-UHFFFAOYSA-N 0.000 description 1
- GWKGPQCKIBRXGW-UHFFFAOYSA-N 5-bromo-1,10-phenanthroline Chemical compound C1=CC=C2C(Br)=CC3=CC=CN=C3C2=N1 GWKGPQCKIBRXGW-UHFFFAOYSA-N 0.000 description 1
- RXACYPFGPNTUNV-UHFFFAOYSA-N 9,9-dioctylfluorene Chemical compound C1=CC=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 RXACYPFGPNTUNV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明は新規な有機／金属ハイブリッドポリマーに関し、更に詳細には配位数が４の金属を使用した有機／金属ハイブリッドポリマー、更にはその配位子及び製造方法に関する。 The present invention relates to a novel organic / metal hybrid polymer, and more particularly to an organic / metal hybrid polymer using a metal having a coordination number of 4, and further to a ligand and a production method thereof.
有機／金属ハイブリッドポリマーは、有機部位（有機モジュール）と金属種がナノスケールでハイブリッド化（複合化）したポリマーであり、従来の有機ポリマーにない電子・光・磁気・触媒機能の発現が期待されている。本願発明者らはある種の有機／金属ハイブリッドポリマーにおいては、電圧の印加によるその金属イオンの酸化／還元によって特定の色で発色／脱色するという優れたエレクトロクロミック特性を有することを見出し、これに基づき、このような特性を有する各種の有機／金属ハイブリッドポリマー、その配位子として使用されるビスターピリジン誘導体、及びその表示素子などへの各種応用について特許出願等を行ってきた（特許文献１〜１０）。 An organic / metal hybrid polymer is a polymer in which organic sites (organic modules) and metal species are hybridized (composited) on a nanoscale, and is expected to exhibit electronic, optical, magnetic, and catalytic functions not found in conventional organic polymers. ing. The inventors of the present invention have found that certain organic / metal hybrid polymers have excellent electrochromic properties of developing / decoloring with a specific color by oxidation / reduction of the metal ions by application of voltage. Based on various organic / metal hybrid polymers having such characteristics, bisterpyridine derivatives used as ligands thereof, and various applications to display devices, etc., patent applications have been made (Patent Documents 1 to 3). 10).
しかし、これまでに提案された何れの有機／金属ハイブリッドポリマーも、その配位子が両端に夫々３配位座を有することで、配位数が６の金属との間でキレートを形成するという構造を有していたため、配位数が６以外の金属を使用した有機／金属ハイブリッドポリマーは実現されていなかった。 However, any of the organic / metal hybrid polymers proposed so far is said to form a chelate with a metal having a coordination number of 6 because the ligand has tricoordinates at both ends. Since it has a structure, an organic / metal hybrid polymer using a metal having a coordination number other than 6 has not been realized.
本発明の課題は配位数が４の金属を使用した有機／金属ハイブリッドポリマーを実現し、これによって有機／金属ハイブリッドポリマーの多様性を更に拡張することにある。 An object of the present invention is to realize an organic / metal hybrid polymer using a metal having a coordination number of 4, thereby further expanding the diversity of the organic / metal hybrid polymer.
本発明の一側面によれば、以下の構造式で表される配位数４の金属及びビスフェナントロリン誘導体を含む有機／金属ハイブリッドポリマーが与えられる。
ただし、Ｍは配位数が４の金属、Ｘはカウンターアニオン、Ａはスペーサーである。
ここにおいて、前記Ｒ１とＲ２は、水素、メチル基、t-ブチル基、フェニル基、チエニル基、ビチエニル基及びターチエニル基から成る群から選択され、前記Ｒ３とＲ４は、水素、フェニル基及びフェニルアセチル基から成る群から選択されてよい。
また、前記配位数が４の金属イオンは、白金（Ｐｔ）、銅（Ｃｕ）、ニッケル（Ｎｉ）、銀（Ａｇ）及びパラジウム（Ｐｄ）から成る群から選択されてよい。
また、前記スペーサーＡは以下に記載の何れかの構造式で表されるものであってよい。
また、前記カウンターアニオンは、過塩素酸イオン、トリフラートイオン、四フッ化ホウ素イオン、塩化物イオン及び六フッ化リン酸イオンから成る群から選択されてよい。
また、これらの有機／金属ハイブリッドポリマーはエレクトロクロミック特性を有してよい。
また、これらの有機／金属ハイブリッドポリマーは蛍光性を有してよい。
本発明の他の側面によれば、以下の構造式で表されるビスフェナントロリン誘導体から成る配位子が与えられる。
ただし、Ａはスペーサーである。
ここで、前記Ｒ１とＲ２は、水素、メチル基、t-ブチル基、フェニル基、チエニル基、ビチエニル基及びターチエニル基から成る群から選択され、前記Ｒ３とＲ４は、水素、フェニル基及びフェニルアセチル基から成る群から選択されてよい。
また、前記スペーサーＡは以下に記載の何れかの構造式で表されるものであってよい。
本発明の更に他の側面によれば、フェナントロリン誘導体を臭素化し、ボロン酸を有するスペーサーとクロスカップリングさせることにより上記何れかの配位子を製造する方法が与えられる。
本発明の更に他の側面によれば、上記何れかの配位子を配位数が４の金属のイオンと錯形成させることにより上記何れかの有機／金属ハイブリッドポリマーを製造する方法が与えられる。
ここで、前記錯形成はアセトニトリルとハロゲン系溶剤の混合液中で行われてよい。
また、前記ハロゲン化溶剤はジクロロメタン、テトラクロロエタン及びクロロホルムから成る群から選択されてよい。
According to one aspect of the present invention, an organic / metal hybrid polymer including a metal having a coordination number of 4 represented by the following structural formula and a bisphenanthroline derivative is provided.
However, M is a metal having a coordination number of 4, X is a counter anion, and A is a spacer.
Wherein R 1 and R 2 are selected from the group consisting of hydrogen, methyl group, t-butyl group, phenyl group, thienyl group, bitienyl group, and tertenyl group, and R 3 and R 4 are hydrogen, phenyl, May be selected from the group consisting of a group and a phenylacetyl group.
The metal ion having a coordination number of 4 may be selected from the group consisting of platinum (Pt), copper (Cu), nickel (Ni), silver (Ag), and palladium (Pd).
The spacer A may be represented by any structural formula described below.
The counter anion may be selected from the group consisting of perchlorate ions, triflate ions, boron tetrafluoride ions, chloride ions, and hexafluorophosphate ions.
These organic / metal hybrid polymers may also have electrochromic properties.
Moreover, these organic / metal hybrid polymers may have fluorescence.
According to another aspect of the present invention, a ligand comprising a bisphenanthroline derivative represented by the following structural formula is provided.
However, A is a spacer.
Here, R 1 and R 2 are selected from the group consisting of hydrogen, methyl group, t-butyl group, phenyl group, thienyl group, bithienyl group, and tertenyl group, and R 3 and R 4 are hydrogen, phenyl, May be selected from the group consisting of a group and a phenylacetyl group.
The spacer A may be represented by any structural formula described below.
According to yet another aspect of the present invention, there is provided a method for producing any of the above ligands by brominating a phenanthroline derivative and cross-coupling with a boronic acid-containing spacer.
According to still another aspect of the present invention, there is provided a method for producing any one of the above organic / metal hybrid polymers by complexing any one of the above ligands with a metal ion having a coordination number of 4. .
Here, the complex formation may be performed in a mixed solution of acetonitrile and a halogen-based solvent.
The halogenated solvent may be selected from the group consisting of dichloromethane, tetrachloroethane, and chloroform.
上述のように、本発明では白金（Ｐｔ）、銅（Ｃｕ）、ニッケル（Ｎｉ）、銀（Ａｇ）、パラジウム（Ｐｄ）等の配位数が４の金属を使った金属／有機ハイブリッドポリマーを実現することができたので、従来の配位数が６の金属を使用したものでは見られない新たな物性を有する有機／金属ハイブリッドポリマーを提供することができる。 As described above, in the present invention, a metal / organic hybrid polymer using a metal having a coordination number of 4 such as platinum (Pt), copper (Cu), nickel (Ni), silver (Ag), palladium (Pd), etc. Since it was realizable, the organic / metal hybrid polymer which has a new physical property which cannot be seen in the thing using the metal whose coordination number is 6 conventionally can be provided.
従来の有機／金属ハイブリッドポリマーの有機物側の原料である配位子は、スペーサー部位を挟んで両端にターピリジン誘導体を有する構造を取っていた。それに対して本発明ではターピリジン誘導体の代わりに、２つの配位座を有するビス（フェナントロリン）誘導体を使用する。この構造により、一つの配位子上の２つのフェナントロリン誘導体のうちの一方と別の配位子上の２つのフェナントロリン誘導体のうちの一方との間に配位数が４の金属イオンが入るという形態で、金属−配位子の繰り返しが形成されることにより、新規な構造の有機／金属ハイブリッドポリマーが得られる。 The ligand, which is a raw material on the organic material side of a conventional organic / metal hybrid polymer, has a structure having terpyridine derivatives at both ends with a spacer portion in between. In contrast, in the present invention, a bis (phenanthroline) derivative having two coordination positions is used instead of a terpyridine derivative. According to this structure, a metal ion having a coordination number of 4 enters between one of two phenanthroline derivatives on one ligand and one of two phenanthroline derivatives on another ligand. In form, metal-ligand repeats are formed, resulting in an organic / metal hybrid polymer with a novel structure.
このような配位子の一般的な構造は以下の通りである。 The general structure of such a ligand is as follows:
フェナントロリン誘導体を臭素化し、ボロン酸を有するスペーサー部位Ａとクロスカップリングさせることで、目的とするビス（フェナントロリン）誘導体、すなわち上述の構造を持った配位子を合成することができる。 By brominating a phenanthroline derivative and cross-coupling with a spacer site A having a boronic acid, a target bis (phenanthroline) derivative, that is, a ligand having the above-described structure can be synthesized.
なお、フェナントロリン誘導体の置換基Ｒ１とＲ２は、水素、メチル基、t-ブチル基、フェニル基、チエニル基、ビチエニル基、ターチエニル基が挙げられる。置換基Ｒ３とＲ４は、水素、フェニル基、フェニルアセチル基が挙げられる。これらの置換基の構造式を以下に示す。 Examples of the substituents R 1 and R 2 of the phenanthroline derivative include hydrogen, a methyl group, a t-butyl group, a phenyl group, a thienyl group, a bithienyl group, and a tertenyl group. Examples of the substituents R 3 and R 4 include hydrogen, a phenyl group, and a phenylacetyl group. The structural formulas of these substituents are shown below.
また、スペーサー部位Ａとしては、フェニル基、ビフェニル基、ターフェニル基、チエニル基、ビチエニル基、ターチエニル基が代表例として挙げられる。また、ビス（フェナントロリン）誘導体の溶解性を高めるために、アルキル基（炭素数１から１６）やアルコキシ基（炭素数１から１６）で修飾したスペーサーを用いることも望ましい。さらに、ジオキソアルキル基（炭素数２から１６）でフェニル基間が連結されたスペーサーを用いることもできる。このようなスペーサー部位Ａの構造式を以下に示す。 Examples of the spacer site A include a phenyl group, a biphenyl group, a terphenyl group, a thienyl group, a bithienyl group, and a tertienyl group. In order to increase the solubility of the bis (phenanthroline) derivative, it is also desirable to use a spacer modified with an alkyl group (1 to 16 carbon atoms) or an alkoxy group (1 to 16 carbon atoms). Furthermore, a spacer in which phenyl groups are connected by a dioxoalkyl group (having 2 to 16 carbon atoms) can also be used. The structural formula of such a spacer site A is shown below.
このようにして得られた配位子を配位数が４の金属イオンを含む金属塩及び溶媒などとともに錯体形成することにより、以下に一般的な構造を示す有機／金属ハイブリッドポリマーを得ることができる。 An organic / metal hybrid polymer having the following general structure can be obtained by complexing the thus obtained ligand with a metal salt containing a metal ion having a coordination number of 4 and a solvent. it can.
ここで、Ｍは白金（Ｐｔ）、銅（Ｃｕ）、ニッケル（Ｎｉ）、銀（Ａｇ）、パラジウム（Ｐｄ）等の配位数が４の金属イオン、Ｘはカウンターアニオンを示す。カウンターアニオンとしては過塩素酸イオン、トリフラートイオン、四フッ化ホウ素イオン、塩化物イオン、六フッ化リン酸イオンが挙げられる。
このようにして合成された金属／有機ハイブリッドポリマーは、使用される金属Ｍ等によってエレクトロクロミック特性や蛍光性などの種々の特徴を有する。
Here, M is a metal ion having a coordination number of 4 such as platinum (Pt), copper (Cu), nickel (Ni), silver (Ag), palladium (Pd), and X is a counter anion. Counter anions include perchlorate ions, triflate ions, boron tetrafluoride ions, chloride ions, and hexafluorophosphate ions.
The metal / organic hybrid polymer synthesized in this way has various characteristics such as electrochromic properties and fluorescence depending on the metal M used.
以下では、配位数が４の金属としてＣｕを使用した本発明の一実施例を説明する。 In the following, an embodiment of the present invention using Cu as a metal having a coordination number of 4 will be described.
先ず、配位子を図１に示すようにして合成した。 First, a ligand was synthesized as shown in FIG.
フェナントロリンを発煙硫酸の存在下で臭素と１３５℃で２３時間反応させることにより、５−ブロモフェナントロリン（5-bromophenanthroline）を合成した。収率は１５％であった。これをジクロロビス(トリフェニルホスフィン)パラジウム（ＰｄＣｌ２（ＰＰｈ３）２）、炭酸カリウム、ＤＭＳＯの存在下で９，９−ジオクチルフルオレン２，７−ジボン酸ビス（１，３−プロパンジオール）エステル（9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol)ester）と１００℃２４時間クロスカップリング反応させることにより、以下の構造式で表される配位子を得た（収率３５％)。 5-Bromophenanthroline was synthesized by reacting phenanthroline with bromine in the presence of fuming sulfuric acid at 135 ° C. for 23 hours. The yield was 15%. In the presence of dichlorobis (triphenylphosphine) palladium (PdCl 2 (PPh 3 ) 2 ), potassium carbonate, DMSO, 9,9-dioctylfluorene 2,7-divonic acid bis (1,3-propanediol) ester ( A ligand represented by the following structural formula was obtained by cross-coupling reaction with 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3-propanediol) ester) at 100 ° C. for 24 hours ( Yield 35%).
このようにして得られた配位子を、図２に示すように、直ちにジクロロメタン（ＤＣＭ）及びアセトニトリルに溶解した等モルの過塩素酸銅水和物と窒素雰囲気中で室温で２４時間反応させることで、以下の構造式で示される有機／金属ハイブリッドポリマーを得た。 The ligand thus obtained is immediately reacted with equimolar copper perchlorate hydrate dissolved in dichloromethane (DCM) and acetonitrile at room temperature for 24 hours in a nitrogen atmosphere as shown in FIG. Thus, an organic / metal hybrid polymer represented by the following structural formula was obtained.
こうして得られた金属／有機ハイブリッドポリマーは緑色の固体で、アセトニトリルにはやや溶けにくく、ジメチルスルホキシド（ＤＭＳＯ）には高い溶解度を示した。 The metal / organic hybrid polymer thus obtained was a green solid, slightly soluble in acetonitrile, and showed high solubility in dimethyl sulfoxide (DMSO).
本実施例のＣｕ（ＩＩ）ベースの有機／金属ハイブリッドポリマーの形成過程を紫外・可視分光分析によってモニターした。その結果を図３に示す。図３に示すように、過塩素酸銅水和物溶液を配位子溶液に加えていくと、錯形成に基づくスペクトル変化が確認された。配位子に対して等量の銅塩を加えるまでスペクトルは変化するが、それ以上銅塩を加えてもスペクトルは変化しなくなった。この結果から、配位子であるビス（フェナントロリン）誘導体と銅イオンは１対１で錯形成していることが確認された。 The formation process of the Cu (II) -based organic / metal hybrid polymer of this example was monitored by ultraviolet / visible spectroscopy. The result is shown in FIG. As shown in FIG. 3, when a copper perchlorate hydrate solution was added to the ligand solution, a spectral change based on complex formation was confirmed. The spectrum changed until an equal amount of copper salt was added to the ligand, but the spectrum did not change even when copper salt was further added. From this result, it was confirmed that the bis (phenanthroline) derivative, which is a ligand, and the copper ion were complexed on a one-to-one basis.
このようにして合成された有機／金属ハイブリッドポリマーのＡＦＭ像を図４に示す。画面の右上から左下にかけてほぼ平行な多数の線が見えるが、これらの線のそれぞれが合成された有機／金属ハイブリッドポリマーのチェーンである。 An AFM image of the organic / metal hybrid polymer synthesized in this manner is shown in FIG. From the upper right to the lower left of the screen, many parallel lines are visible, each of which is a synthesized organic / metal hybrid polymer chain.
なお、この有機／金属ハイブリッドポリマー合成の際の溶媒としてはＤＣＭとアセトニトリルに限定されるわけではなく、例えばＤＣＭの代わりにテトラクロロエタン（Ｃ２Ｈ２Ｃｌ４）やクロロホルムなどのハロゲン系溶剤を使用することもできる。 Note that the solvent for synthesizing the organic / metal hybrid polymer is not limited to DCM and acetonitrile. For example, a halogen solvent such as tetrachloroethane (C 2 H 2 Cl 4 ) or chloroform is used instead of DCM. You can also
また、有機／金属ハイブリッドポリマーの合成の際、Ｐｔ、Ｎｉ、Ａｇ、ＰｄなどのＣｕ以外の配位数が４の金属イオンを使用することにより、Ｃｕ以外の金属ベースの本発明の有機／金属ハイブリッドポリマーを得ることもできる。
有機／金属ハイブリッドポリマーは、含まれる金属イオンの種類に応じた電気化学特性を示す。例として、銅イオンとビス（フェナントロリン）誘導体からなる有機／金属ハイブリッドポリマーのサイクリックボルタモグラムを図５に示す。この測定条件は以下の通りであった。作用電極：グラッシーカーボン電極、対極：Ｐｔワイヤー電極、参照電極：Ａｇ／Ａｇ＋、電解質溶液：０．１ＭＴＢＡＰ、溶媒：アセトニトリル、ハイブリッドポリマーを作用電極にキャストして測定した。ポリマー中の銅イオンの酸化還元（Ｃｕ（Ｉ）／Ｃｕ（ＩＩ））に対応する酸化還元波が約１．０Ｖ（ｖｓ．Ａｇ／Ａｇ＋）に観測された。
Further, when synthesizing an organic / metal hybrid polymer, a metal ion having a coordination number other than Cu, such as Pt, Ni, Ag, Pd, or the like, is used, so that the organic / metal of the present invention based on a metal other than Cu is used. Hybrid polymers can also be obtained.
The organic / metal hybrid polymer exhibits electrochemical characteristics depending on the type of metal ions contained. As an example, FIG. 5 shows a cyclic voltammogram of an organic / metal hybrid polymer composed of a copper ion and a bis (phenanthroline) derivative. The measurement conditions were as follows. Working electrode: glassy carbon electrode, counter electrode: Pt wire electrode, reference electrode: Ag / Ag +, electrolyte solution: 0.1 MTBAP, solvent: acetonitrile, and hybrid polymer cast on working electrode and measured. A redox wave corresponding to redox (Cu (I) / Cu (II)) of copper ions in the polymer was observed at about 1.0 V (vs. Ag / Ag + ).
非特許文献１〜１０で詳細に説明され、また当業者周知の通り、従来の配位数が６の金属を使用した有機／金属ハイブリッドポリマーは電圧を印加してハイブリッドポリマーを構成する金属イオンを還元・酸化することによって着色・脱色するというエレクトロクロミック特性を有している。本発明においても、上述のようにして合成したＣｕ（ＩＩ）ベースの有機／金属ハイブリッドポリマーは、以下に示すように、従来と同様なエレクトロクロミック特性を有していることが確認された。 As described in detail in Non-Patent Documents 1 to 10 and as is well known to those skilled in the art, a conventional organic / metal hybrid polymer using a metal having a coordination number of 6 is a metal ion constituting a hybrid polymer by applying a voltage. It has electrochromic properties of coloring and decoloring by reduction and oxidation. Also in the present invention, it was confirmed that the Cu (II) -based organic / metal hybrid polymer synthesized as described above has the same electrochromic characteristics as the conventional one, as shown below.
合成されたＣｕ（ＩＩ）ベースの有機／金属ハイブリッドポリマーで薄膜を作成し、これに電圧を印加してＣｕを還元していくと、図６（ａ）に示すように、３０分ほどかけて徐々に可視光線域の吸光度、特に４００ｎｍ〜５００ｎｍを中心として、更に６００ｎｍまでの吸光度が増大した。視覚的には、薄膜は当初ほぼ無色に見えたものが、次第に黄色に着色した。この変化は可逆的であった。すなわち、図６（ｂ）に示すように、逆方向の電圧を薄膜に印加することにより、有機／金属ハイブリッドポリマーは酸化され、約１時間かけて元の低濃度かつほぼ無色の状態に復帰した。 When a thin film is prepared with the synthesized Cu / II-based organic / metal hybrid polymer and Cu is reduced by applying a voltage thereto, as shown in FIG. 6A, it takes about 30 minutes. The absorbance in the visible light region gradually increased, particularly the absorbance up to 600 nm centered around 400 nm to 500 nm. Visually, the thin film initially appeared almost colorless, but gradually became yellow. This change was reversible. That is, as shown in FIG. 6B, by applying a reverse voltage to the thin film, the organic / metal hybrid polymer was oxidized and returned to its original low concentration and almost colorless state over about 1 hour. .
このような薄膜の濃度変化の写真を図７に示す。図７（ａ）はまだ電圧を印加する前の状態の写真である。また、図７（ｂ）は図６（ａ）で電圧を印加してから十分時間が経過した後の状態、図７（ｃ）は図６（ｂ）で逆方向の電圧を印加して十分時間が経過した後の状態の写真である。図７はモノクローム写真なので、図７（ｂ）が他のものよりも若干濃度が高く見えるだけであるが、実際には図７（ｂ）を撮影したときには薄膜が黄色に着色しているのが明瞭に観測された。 A photograph of such a thin film concentration change is shown in FIG. FIG. 7A is a photograph of the state before the voltage is applied. FIG. 7B shows a state after a sufficient time has elapsed after applying the voltage in FIG. 6A, and FIG. 7C shows a state in which a reverse voltage is applied in FIG. 6B. It is a photograph of the state after time has passed. Since FIG. 7 is a monochrome photograph, FIG. 7B only looks slightly higher in density than the others, but in reality, when the photograph of FIG. 7B is taken, the thin film is colored yellow. Observed clearly.
更に、Ｃｕ（ＩＩ）ベースの有機／金属ハイブリッドポリマーと同様にして合成したＰｔ（ＩＶ）ベースの有機／金属ハイブリッドポリマーも同様にエレクトロクロミック特性を示すことが確認された。 Furthermore, it was confirmed that a Pt (IV) -based organic / metal hybrid polymer synthesized in the same manner as the Cu (II) -based organic / metal hybrid polymer also exhibits electrochromic properties.
また、Ｐｔ（ＩＶ）ベースの有機／金属ハイブリッドポリマーでは、紫外線で励起することによって蛍光を発することが確認された。 Moreover, it was confirmed that the Pt (IV) -based organic / metal hybrid polymer emits fluorescence when excited with ultraviolet rays.
以上詳細に説明したように、本発明により従来技術では得られなかった新しいタイプの有機／金属ハイブリッドポリマーを提供することができるようになったため、有機／金属ハイブリッドポリマーの応答を検討する際に従来とは異なる性質を有する有機／金属ハイブリッドポリマーが新たな選択肢として加わることは大いに有益である。 As described above in detail, the present invention has made it possible to provide a new type of organic / metal hybrid polymer that could not be obtained by the prior art. It is highly beneficial to add organic / metal hybrid polymers with different properties as a new option.
Claims (10)
ただし、ｎ≦５０００であり、
Ｍは配位数が４の金属であり、
Ｘはカウンターアニオンであり、
Ｒ １ とＲ ２ は、水素、メチル基、t-ブチル基、フェニル基、チエニル基、ビチエニル基及びターチエニル基から成る群から選択され、
Ｒ ３ とＲ ４ は、水素、フェニル基及びフェニルアセチル基から成る群から選択され、
Ａは以下に記載の何れかの構造式で表されるスペーサーである。
However, n ≦ 5000,
M is a metal with a coordination number of 4,
X is a counter anion,
R 1 and R 2 are selected from the group consisting of hydrogen, methyl group, t-butyl group, phenyl group, thienyl group, bitienyl group and tertenyl group;
R 3 and R 4 are selected from the group consisting of hydrogen, phenyl group and phenylacetyl group;
A is a spacer represented by any structural formula described below.
ただし、ＲHowever, R １1 とＲAnd R ２2 は、水素、メチル基、t-ブチル基、フェニル基、チエニル基、ビチエニル基及びターチエニル基から成る群から選択され、Is selected from the group consisting of hydrogen, a methyl group, a t-butyl group, a phenyl group, a thienyl group, a bithienyl group and a tertenyl group;
前記Ｒ R ３3 とＲAnd R ４4 は、水素、フェニル基及びフェニルアセチル基から成る群から選択され、Is selected from the group consisting of hydrogen, a phenyl group and a phenylacetyl group;
Ａは以下に記載の何れかの構造式で表されるスペーサーである。 A is a spacer represented by any structural formula described below.
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