JP3977649B2 - Phenylazomethine dendron complex - Google Patents
Phenylazomethine dendron complex Download PDFInfo
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- JP3977649B2 JP3977649B2 JP2002020786A JP2002020786A JP3977649B2 JP 3977649 B2 JP3977649 B2 JP 3977649B2 JP 2002020786 A JP2002020786 A JP 2002020786A JP 2002020786 A JP2002020786 A JP 2002020786A JP 3977649 B2 JP3977649 B2 JP 3977649B2
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- dendron
- group
- phenylazomethine
- complex
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Links
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012776 electronic material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000009918 complex formation Effects 0.000 description 4
- 239000012973 diazabicyclooctane Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- -1 biphenyloxy group Chemical group 0.000 description 3
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011365 complex material Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000006616 biphenylamine group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【0001】
【発明の属する技術分野】
この出願の発明は、フェニルアゾメチンデンドロン錯体に関するものである。さらに詳しくは、この出願の発明は、発光材料、電子材料、触媒あるいはそれらの製造用等として有用な、電子勾配を有するフェニルアゾメチンデンドロンの金属塩錯体に関するものである。
【0002】
【従来の技術とその課題】
近年、ディスプレイやノート型パソコンの高性能化に伴い、高分子錯体材料を用いた、従来にない高輝度発光材料やナノ電子材料の開発と実用化が望まれている。
【0003】
従来の発光・電子材料は、主に金属・無機物質から構成されているが、最近では、より高い発光輝度や発光波長のコントロールが可能な、ナノサイズレベルで構造制御された電子デバイズの構築に適した高分子錯体材料が注目を集めている。
【0004】
このような高分子錯体においては、高分子鎖内に電子勾配を持たせることで金属の配位を高度にコントロールすることが機能の発現に極めて重要となるが、金属の配位数、配位位置を明確に制御することはこれまで困難であった。
【0005】
一方、ポリフェニルアゾメチンは高い耐熱性と金属塩に対し高い配位性をもつアゾメチン部位を多数有し、この特徴のある構造に由来する機能の発現が注目されている。しかしながら、これらは溶解性が極めて低く、高分子材料としての利用は限定されているのが実情である。
【0006】
このような問題を解決するためには、ポリフェニルアゾメチンを溶解させ、電子勾配を高分子内に構築する方法としては、分岐型構造(デンドロン)の導入が考えられる。
【0007】
しかしながら、これまでのところ、フェニルアゾメチンデンドロンの構造を形成し、その中に電子勾配を構築することや金属配位をコントロールすることは実現されていない。
【0008】
そこで、この出願の発明は、以上の通りの事情に鑑みなされたものであり、従来の発光・電子材料に代わる高機能高分子錯体への展開が期待される、新しいフェニルアゾメチンデンドロンの金属塩錯体を提供することを課題としている。
【0009】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、第1には、フェニルアゾメチン骨格を有する樹状分子構造を有し、次の一般式
【0010】
【化9】
(式中のAは、次式
【0011】
【化10】
【0012】
の構造で表わされ、R1は、置換基を有していてもよい芳香族基を示し、lはR1への結合数を示し;Bは、前記Aに対してl個の
アゾメチン結合を形成する次式
【0013】
【化11】
【0014】
の構造で表わされ、R2は、同一または別異に、置換基を有していてもよい芳香族基を示し;nは、前記Bの構造によって樹状構造が形成される場合の世代数を表し;Rは樹状構造デンドロンの未端基であって、前記Bにアゾメチン結合する次式
【0015】
【化12】
【0016】
の構造で表わされ、R3は、同一または別異に、置換基を有していてもよい芳香族基を示し;mは、未端基Rの数であって、n=0時はm=1であり、n≧1の時m=2n1であることを示す)で表わされるフェニルアゾメチンデンドロンに塩化スズが配位していることを特徴とするフェニルアゾメチンデンドロン錯体を提供する。
【0018】
以上のとおりのこの出願の発明は、前記の課題を解決すべく、発明者による鋭意研究の結果、フェニルアゾメチンデンドロンのコアユニットあるいは分岐末端ユニットに電子供与性あるいは電子吸引性の官能基を導入することで電子勾配の構造に基づいた多段階的錯形成が可能であって、さらに、錯体はその機能を発光材料や電子材料、触媒等へと応用可能であるとの知見に基づいている。
【0019】
この出願の発明のフェニルアゾメチンデンドロン錯体では、コアあるいは分岐末端の芳香族基に様々な置換基を導入することで電子勾配の発現に基づいた金属塩の多段階錯形成が可能であるため、高分子内の金属イオンの数と位置をコントロールすることができ、従来の高分子錯体とは異なって、光・電子機能等の発現と制御が可能となる。
【0020】
【発明の実施の形態】
この出願の発明は以上のとおりの特徴をもつものであるが、以下にその実施の形態について説明する。
【0021】
まず、この出願の発明においては、フェニルアゾメチンデンドロンの符号R1、R2およびR3で示される、置換基を有していてもよい芳香族基は、フェニル基またはその類縁の構造を有していてよく、たとえばフェニル基、ビフェニル基、ビフェニルアルキレン基、フェニルアルキル基、ビフェニルオキシ基、ビフェニルアミノ基、ビフェニルカルボニル基等の骨格構造を有し、置換基として、塩素原子、臭素原子、フッ素原子等のハロゲン原子、メチル基、エチル基等のアルキル基、クロルメチル基、トリフルオロメチル基等のハロゲンアルキル基、メトキシ基、エトキシ基等のアルコキシ基、メトキシエチル基等のアルコキシアルキル基、アルキルチオ基、チオールアルキル基、カルボニル基、シアノ基、アミノ基、ニトロ基等の各種の置換基を1ないし2以上、また適宜に複数種のものとして有していてもよい。
【0022】
なかでも、メトキシ基、アミノ基のような電子供与位の高い官能基あるいはシアノ基やカルボニル基のような電子受容性の高い官能基が望ましい。
【0023】
デンドロマーの世代数(n)については、0または1以上であるが、たとえば3〜5世代のものが発光材料への応用等の観点からは好ましいものとして例示される。また、結合数を表すlは、1以上の数である。
【0024】
金属塩との錯体は、各種の金属の塩によって構成されてよく、なかでも金属としては、発光材料や電子材料への応用の観点からは、Sn、Ga、Ti、In、Ge、Ta、Zr、Hf、Sb、Si、B、Mn、Fe、V、Mo、W、Pb、Zn、Cd、Cu、Ni、Y、Sc、Eu、Er、La等が好ましいものとして例示され、また、塩を構成するアニオンとしては、各種のものであってよいが、ハロゲン、硫酸、スルホン酸等のアニオンがたとえば好ましいものとして例示される。
【0025】
一般式として前記のとおりに表わされるデンドロンについては公知の方法をはじめとして各種の方法で合成することができる。たとえば、四塩化チタンや、パラトルエンスルホン酸などの酸存在下で、ジアミノベンゾフェノンの脱水反応によってデンドリマーの世代数(n)を増やしていくことができる。
【0026】
たとえば、ハロゲン化炭化水素、アセトントリル、DMF、DMSO等の極性溶媒を用い、30〜200℃程度の温度において反応させることができる。大気中あるいは不活性雰囲気下で反応させてよい。
【0027】
また、この出願の発明の錯体の合成については、前記各種の方法により合成されたフェニルアゾメチンデンドロンに、金属化合物を混合して、配位錯体を生成させることで可能とされる。
【0028】
この場合、配位数については、デンドロンのアゾメチン結合の総数の範囲内において、所定モル数の金属化合物の混合によって調整が可能とされる。また、この配位に際して特徴的なことは、金属イオンが、デンドロンの樹状分子構造において中心から外側へと段階的に、添加する金属塩のモル数に対応して規則正しく錯位集積されるという特異的な挙動が見られることである。このような挙動は分子の中の電子勾配に基づくものと考えられる。そして、この電子勾配は、中心や外側の部分構造(置換基)を変えることで簡単に変化させることができる。
【0029】
デンドロンの配位については、溶媒を用いることができる。なかでも、ハロゲン化炭化水素、ニトリル類、アミド類などの極性溶媒が好ましく、たとえば塩化メチレン、クロロベンゼン、アセトニトリル、DMF、DMSO等が例示される。配位のための混合は、温度としては、たとえば−10℃〜30℃程度でよく、雰囲気は大気中、もしくはAr、N2等の不活性雰囲気とすることができる。
【0030】
そこで以下に実施例を示し、さらに詳しく説明する。
【0031】
もちろん、以下の例によって発明が限定されることはない。
【0032】
【実施例】
<実施例1> 電子勾配を有するフェニルアゾメチンデンドロンの合成
次の反応式に従って、フェニルアゾメチンデンドロンを合成した。
【0033】
【化13】
【0034】
▲1▼ ベンゾフェノン(25.7g,141mmol)、4,4′−ジアミノベンゾフェノン(3.00g,14.1mmol)、DABCO(9.51g,84.8mmol)をクロロベンゼン(90mL)に溶かし、その溶液に四塩化チタン(4.02g,21.2mmol)を滴下した。125℃で24時間反応させた後、ろ過し、ろ液を濃縮した。シリカゲルクロマトグラフィーを用いて、デンドロンG2(n=0)を単離した(3.63g,6.71mmol,48%)。
【0035】
▲2▼ デンドロンG2(4.85g,8.97mmol)、4,4′−ジアミノベンゾフェノン(380mg,1.79mmol)、DABCO(1.21g10.8mmol)をクロロベンゼン(40mL)に溶かし、その溶液に四塩化チタン(510mg,2.69mmol)を滴下した。125℃で24時間反応させた後、ろ過し、ろ液を濃縮した。シリカゲルクロマトグラフィーを用いて、デンドロンG3(n=1)を単離した(1.43g,1.14mmol,64%)。
【0036】
▲3▼ デンドロンG3(9.52g,7.57mmol)、4,4′−ジアミノベンゾフェノン(268mg,1.26mmol)、DABCO(849mg,7.57mmol)をクロロベンゼン(120mL)に溶かし、その溶液に四塩化チタン(358mg,1.89mmol)を滴下した。125℃で44時間反応させた後、ろ過し、ろ液を濃縮した。シリカゲルクロマトグラフィーを用いて、デンドロンG4(n=2)を単離した(668mg,0.248mmol,20%)。
【0037】
▲4▼ デンドロンG4(50mg,0.02mmol)、p−アニジン(23mg,0.2mmol)、DABCO(849mg,7.57mmol)をクロロベンゼン(40mL)に溶かし、その溶液に四塩化チタン(36mg,0.2mmol)を滴下した。125℃で2時間反応させた後、ろ過し、ろ液を濃縮した。シリカゲルクロマトグラフィーを用いて、コアにメトキシ基を導入したデンドロンG4を単離した(42mg,81%)。
【0038】
得られた目的物を、赤外吸収スペクトル、質量分析、及び元素分析により固定した。結果を表1および表2に示した。
【0039】
【表1】
【0040】
【表2】
【0041】
<実施例2> フェニルアゾメチンデンドロンと塩化スズの錯形成
MeO−デンドロンG4の塩化メチレン/アセトニトリル(1:1)溶液に塩化スズのアセトニトリル溶液を滴下していき、その紫外可視吸収スペクトルの変化を観測することにより、錯形成挙動を検討した。塩化スズが配位したイミン基に基づく400nm付近の吸収が増加し、デンドロンへのスズ塩の配位が確認できた。このスペクトル変化において、等吸収点の位置が4段階で変化し、その等量数から塩化スズの錯形成がデンドロンの電子勾配に従って、次にしめしたように、第1層から2、3、4層へと階段的に進行していることが判明した。
【0042】
【化14】
【0043】
15当量の塩化スズが配位したデンドロン錯体は、表3のように、原子吸光スペクトル、赤外吸収スペクトル、およびマススペクトルにより同定した。
【0044】
【表3】
【0045】
<実施例3> フェニルアゾメチンデンドロンによる金表面の修飾と電気応答性
コアにアルキルチオール基を導入したデンドロンは、金表面において厚さ約1.4nmの均一な単分子膜をLB法により形成した。得られた膜を塩化スズの塩化メチレン/アセトニトリル溶液に浸し、錯形成を完了した。
【0046】
以上詳しく説明した通り、この出願の発明によって、発光材料、電子材料等への展開が期待される、新しいフェニルアゾメチンデンドロンの金属塩錯体が提供される。[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a phenylazomethine dendron complex . More specifically, the invention of this application relates to a metal salt complex of phenylazomethine dendron having an electron gradient, which is useful as a light emitting material, an electronic material, a catalyst, or production thereof .
[0002]
[Prior art and its problems]
In recent years, with the improvement in performance of displays and notebook computers, the development and practical application of unprecedented high-luminance light-emitting materials and nanoelectronic materials using polymer complex materials are desired.
[0003]
Conventional light-emitting and electronic materials are mainly composed of metals and inorganic substances. Recently, however, it has been developed to construct nano-sized structure-controlled electronic devices that can control higher light emission brightness and light emission wavelength. Suitable polymer complex materials are attracting attention.
[0004]
In such a polymer complex, it is extremely important to control the metal coordination by giving an electron gradient in the polymer chain, but the number of coordination and coordination of the metal are very important. It has been difficult to control the position clearly.
[0005]
On the other hand, polyphenylazomethine has many azomethine moieties having high heat resistance and high coordination properties to metal salts, and attention is paid to the expression of functions derived from this characteristic structure. However, these are extremely low in solubility, and the fact is that their use as polymer materials is limited.
[0006]
In order to solve such a problem, introduction of a branched structure (dendron) can be considered as a method for dissolving polyphenylazomethine and constructing an electron gradient in the polymer.
[0007]
However, so far, it has not been possible to form a phenylazomethine dendron structure, to build an electron gradient in it, or to control metal coordination.
[0008]
Accordingly, the invention of this application has been made in view of the circumstances as described above, and a new metal salt complex of phenylazomethine dendron , which is expected to be developed into a high-performance polymer complex that replaces conventional light emitting / electronic materials. It is an issue to provide.
[0009]
[Means for Solving the Problems]
The invention of this application, as to solve the above problems, the first has a dendritic partial molecular structure having a phenyl azomethine skeleton of the following general formula [0010]
[Chemical 9]
(A in the formula is the following formula :
[Chemical Formula 10]
[0012]
Wherein R 1 represents an aromatic group which may have a substituent , 1 represents the number of bonds to R 1 ; B represents 1 azomethine bond to A The following formula forms
Embedded image
[0014]
Wherein R 2 is the same or different and represents an aromatic group which may have a substituent; n represents a generation when a dendritic structure is formed by the structure of B; R represents an unterminated group of a dendritic dendron and has the following formula for azomethine bond to B:
Embedded image
[0016]
Wherein R 3 is the same or different and represents an optionally substituted aromatic group; m is the number of unterminated groups R, and when n = 0 a m = 1, provides phenyl azomethine dendron complexes of tin chloride full E sulfonyl azomethine dendron you express in shown) that is m = 2n1 when n ≧ 1 is characterized in that coordinated To do.
[0018]
The invention of this application as described above has introduced an electron donating or electron withdrawing functional group into the core unit or branched terminal unit of phenylazomethine dendron as a result of intensive studies by the inventors in order to solve the above problems. Therefore, multi-step complex formation based on the structure of the electron gradient is possible, and the complex is based on the knowledge that its function can be applied to a light emitting material, an electronic material, a catalyst and the like.
[0019]
In the phenylazomethine dendron complex of the invention of this application, it is possible to form a multi-stage complex of a metal salt based on the expression of an electron gradient by introducing various substituents into the aromatic group at the core or branch end. The number and position of metal ions in the molecule can be controlled, and unlike conventional polymer complexes, expression and control of optical / electronic functions and the like can be achieved.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The invention of this application has the features as described above, and an embodiment thereof will be described below.
[0021]
First, in the invention of this application, the aromatic group which may have a substituent represented by the symbols R 1 , R 2 and R 3 of phenylazomethine dendron has a phenyl group or a similar structure. For example, it has a skeletal structure such as a phenyl group, a biphenyl group, a biphenylalkylene group, a phenylalkyl group, a biphenyloxy group, a biphenylamino group, a biphenylcarbonyl group, and the substituent includes a chlorine atom, a bromine atom, and a fluorine atom. Halogen atoms such as methyl groups, alkyl groups such as ethyl groups, halogen alkyl groups such as chloromethyl groups and trifluoromethyl groups, alkoxy groups such as methoxy groups and ethoxy groups, alkoxyalkyl groups such as methoxyethyl groups, alkylthio groups, Various types such as thiol alkyl group, carbonyl group, cyano group, amino group, nitro group You may have 1 or 2 or more substituents as appropriate, and multiple types.
[0022]
Among these, a functional group having a high electron donating position such as a methoxy group or an amino group or a functional group having a high electron accepting property such as a cyano group or a carbonyl group is desirable.
[0023]
The generation number (n) of the dendromer is 0 or 1 or more. For example, the generation of 3 to 5 generations is preferable from the viewpoint of application to a light emitting material. Further, l representing the number of bonds is a number of 1 or more.
[0024]
A complex with a metal salt may be composed of various metal salts. Among them, as a metal, Sn, Ga, Ti, In, Ge, Ta, Zr are used from the viewpoint of application to a light emitting material and an electronic material. Hf, Sb, Si, B, Mn, Fe, V, Mo, W, Pb, Zn, Cd, Cu, Ni, Y, Sc, Eu, Er, La, etc. are exemplified as preferred ones, Various anions may be used as the constituent anion, and anions such as halogen, sulfuric acid and sulfonic acid are exemplified as preferable examples.
[0025]
The dendron represented as described above as a general formula can be synthesized by various methods including known methods. For example, the generation number (n) of dendrimers can be increased by the dehydration reaction of diaminobenzophenone in the presence of an acid such as titanium tetrachloride or p-toluenesulfonic acid.
[0026]
For example, the reaction can be performed at a temperature of about 30 to 200 ° C. using a polar solvent such as halogenated hydrocarbon, acetone tolyl, DMF, DMSO or the like. You may make it react in air | atmosphere or inert atmosphere.
[0027]
Further, the synthesis of the complex of the invention of this application can be achieved by mixing a metal compound with phenylazomethine dendron synthesized by the various methods described above to form a coordination complex.
[0028]
In this case, the coordination number can be adjusted by mixing a predetermined number of moles of metal compound within the range of the total number of azomethine bonds of dendron. Another characteristic of this coordination is that the metal ions are regularly complexed and accumulated according to the number of moles of the metal salt to be added stepwise from the center to the dendron dendritic molecular structure. The behavior is typical. Such behavior is thought to be based on the electron gradient in the molecule. This electron gradient can be easily changed by changing the center or outer partial structure (substituent).
[0029]
A solvent can be used for the coordination of the dendron. Of these, polar solvents such as halogenated hydrocarbons, nitriles, and amides are preferable, and examples include methylene chloride, chlorobenzene, acetonitrile, DMF, DMSO, and the like. Mixing for coordination may be performed at a temperature of about −10 ° C. to 30 ° C., for example, and the atmosphere may be air or an inert atmosphere such as Ar or N 2 .
[0030]
Therefore, an example will be shown below and will be described in more detail.
[0031]
Of course, the invention is not limited by the following examples.
[0032]
【Example】
<Example 1> Synthesis of phenylazomethine dendron having electron gradient Phenylazomethine dendron was synthesized according to the following reaction formula.
[0033]
Embedded image
[0034]
(1) Benzophenone (25.7 g, 141 mmol), 4,4′-diaminobenzophenone (3.00 g, 14.1 mmol), DABCO (9.51 g, 84.8 mmol) are dissolved in chlorobenzene (90 mL), and the solution is dissolved. Titanium tetrachloride (4.02 g, 21.2 mmol) was added dropwise. After reacting at 125 ° C. for 24 hours, the mixture was filtered and the filtrate was concentrated. Dendron G2 (n = 0) was isolated using silica gel chromatography (3.63 g, 6.71 mmol, 48%).
[0035]
{Circle around (2)} Dendron G2 (4.85 g, 8.97 mmol), 4,4′-diaminobenzophenone (380 mg, 1.79 mmol), DABCO (1.21 g 10.8 mmol) were dissolved in chlorobenzene (40 mL). Titanium chloride (510 mg, 2.69 mmol) was added dropwise. After reacting at 125 ° C. for 24 hours, the mixture was filtered and the filtrate was concentrated. Dendron G3 (n = 1) was isolated using silica gel chromatography (1.43 g, 1.14 mmol, 64%).
[0036]
(3) Dendron G3 (9.52 g, 7.57 mmol), 4,4′-diaminobenzophenone (268 mg, 1.26 mmol) and DABCO (849 mg, 7.57 mmol) were dissolved in chlorobenzene (120 mL), and Titanium chloride (358 mg, 1.89 mmol) was added dropwise. After reacting at 125 ° C. for 44 hours, the mixture was filtered and the filtrate was concentrated. Dendron G4 (n = 2) was isolated using silica gel chromatography (668 mg, 0.248 mmol, 20%).
[0037]
(4) Dendron G4 (50 mg, 0.02 mmol), p-anidin (23 mg, 0.2 mmol), DABCO (849 mg, 7.57 mmol) were dissolved in chlorobenzene (40 mL), and titanium tetrachloride (36 mg, 0 mg) was dissolved in the solution. .2 mmol) was added dropwise. After reacting at 125 ° C. for 2 hours, the mixture was filtered and the filtrate was concentrated. Dendron G4 having a methoxy group introduced into the core was isolated using silica gel chromatography (42 mg, 81%).
[0038]
The obtained object was fixed by infrared absorption spectrum, mass spectrometry, and elemental analysis. The results are shown in Tables 1 and 2.
[0039]
[Table 1]
[0040]
[Table 2]
[0041]
<Example 2> Phenylazomethine dendron and tin chloride complex formation MeO-dendron G4 in methylene chloride / acetonitrile (1: 1) was dropped into a solution of tin chloride in acetonitrile, and changes in its UV-visible absorption spectrum were observed. By doing so, the complex formation behavior was examined. Absorption near 400 nm based on the imine group coordinated with tin chloride increased, and the coordination of the tin salt to the dendron was confirmed. In this spectral change, the position of the isosbestic point changes in four steps, and from the equivalence number, the complexation of tin chloride follows the electron gradient of the dendron, and as shown next, 2, 3, 4 from the first layer. It turns out that it is progressing step by step.
[0042]
Embedded image
[0043]
The dendron complex coordinated with 15 equivalents of tin chloride was identified by atomic absorption spectrum, infrared absorption spectrum, and mass spectrum as shown in Table 3.
[0044]
[Table 3]
[0045]
<Example 3> Modification of gold surface with phenylazomethine dendron and dendron in which an alkylthiol group was introduced into the electrically responsive core formed a uniform monomolecular film having a thickness of about 1.4 nm on the gold surface by the LB method. The resulting membrane was immersed in a methylene chloride / acetonitrile solution of tin chloride to complete complex formation.
[0046]
As described above in detail, the invention of this application provides a new metal salt complex of phenylazomethine dendron , which is expected to be developed into light emitting materials, electronic materials, and the like.
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