1992 Fiscal Year Annual Research Report

新しいホトクロミック化合物の合成に適した分子設計手法の確立に関する研究

Research Project

Project/Area Number	04453094
Research Institution	Saitama University
Principal Investigator	時田澄男埼玉大学, 工学部, 教授 (20008866)
Co-Investigator(Kenkyū-buntansha)	前川仁埼玉大学, 工学部, 助教授 (30135660) 井門俊二埼玉大学, 工学部, 助教授 (40135752) 横山泰横浜国立大学, 工学部, 助教授 (60134897) 宮下晃埼玉大学, 工学部, 助教授 (90132729) 野平博之埼玉大学, 工学部, 教授 (50008819)
Keywords	ホトクロミック化合物 / 分子設計 / 分子軌道法 / 熱安定性 / スピロピラン / フルギド / ベンゾジキサンテン / 電子スペクトル
Research Abstract	本研究では、スピロピラン系、フルギド系、ベンゾジキサンテン系という、三種の異なるホトクロミック化合物について、それぞれ独立に研究してきた合成化学者達が、相互の有機的連携の下に分子設計手法の改良という一つのテーマに取り組み、種々の新しいホトクロミック化合物の開発を行うことができた。スピロピラン系では、「準安定系の熱安定化」をキーワードに種々の誘導体を合成し、その溶液における構造と固体における構造とが大きく異なることを初めて明らかにした。つぎに、スピロピラン誘導体をビニルモノマーと共重合し、ポリマーフィルム中における準安定系の熱安定性を評価した。また、ポリマーなどの媒体に依存せずに化学的安定性を向上させるために、スピロピラン誘導体を配位子に持つクロムカルボニル錯体を全く独自のアプローチとして合成し、その準安定系の熱安定性に関する考察を行った。さらに、関連化合物として、スピロベンゾセレナゾリノベンゾピランを側鎖とする逆ホトクロミックポリマーの合成についても研究し、準安定系の固定化に関して新しい知見を得た。フルギド系では、インドリルフルギド類のPPP分子軌道法計算を行い、実測データと比較することによりパラメーターの検討を行った。また、これら新規化合物の光反応の研究から、量子収率と構造の関係についてMNDO分子軌道法を援用して考察した。ベンゾジキサンテン系では、PPP法ならびにINDOIS法により窒素類縁体が長波長域に吸収を有することを予測し、近赤外領域に吸収を持つ新規ホノクロミック化合物を合成することができた。以上の一連の研究により、パーソナルコンピューターまたはワークステーションを用いる計算化学的手法を再吟味し、ホトクロミック化合物の熱安定性、吸収極大や量子収率の予測の効率化が実現できた。

Research Products

(22 results)

All Other

All Publications (22 results)

[Publications] 時田澄男ら5名第1著者:Y.Kubo: "“Synthesis of 1.3-Bis(indoaniline)-derived Calix〔4〕-arene as an Optical Senor for Calcium Ion"" J.Chem.Soc.,Chem.Commun.(1993)
[Publications] 時田澄男ら4名第1著者:S.Tokita: "“INDO/S Self-Consistent Reaction Field Study of Indoaniline Dyes"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 時田澄男ら4名第1著者:H.Kihara: "“An Interactive Software for Predicting Electronic Spectra of Organic Compounds by Personal Computers"" Proc.2nd Int.Symp.on Chem.of Functinal Dyes. (1993)
[Publications] 時田澄男ら4名第1著者:Y.Hattori: "“Hole Drift Mobility and Electronic State of Charge Transfer Materials"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 時田澄男ら2名第一著者:S.Tokita: "“Synthesis and Properties of Benzo〔1,2,3-kl:4,5,6-K',l'〕diacridines"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 時田澄男ら2名第1著者:S.Tokita: "“Synthesis of Several Analogues of Anthra〔1,9-bc:4,10-b',c'〕dichromene and Their Photochromic Properties"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 時田澄男ら7名第1著者:Y.Kobayashi: "“Structural Chemistry of Photochromic Benzodixanthene and Its Sulfur Analogue"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 時田澄男ら6名第1著者:K.Kitahara: "“Synthesis of Soluble 2,3-Naphthalocyanines Having Ester Groups"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 時田澄男ら5名第1著者:時田澄男: "“ベンゾ〔1,2,3-kl;4,5,6-K'l'〕ジキサンテンの非対称型類縁体ならびにそれらのエンドペルオキシドの合成とホトクロミック特性"," 日本化学会誌. 1097-1101 (1992)
[Publications] 時田澄男ら5名第1著者:S.A.Tucker: "“Polycyclic Aromatic Nitrogen Heterocycles.Part 4.Effect of Solvent Polarity,Solvent Acidity,Nitromethane and 1,2,4-Trimethoxy benzene on the Fluores,Emission Behavior of Mono-and Diazaarenes"," Applied Spectroscopy. 46. 1630-1635 (1992)
[Publications] 時田澄男ら5名第1著者:K.Kitahara: "“Synthesis of Octasubstituted Metal Phthalocyanines"," Phosphorus,Sulfur,Silicon and Related Elements. 67. 373-376 (1992)
[Publications] 時田澄男ら3名第1著者:S.Tokita: "“Molecular Structure and Electronic Spectrum of Organic Colorants(2):Molecular Orbital Approach to Indoaniline Dyes"," J.Photopolymer Sci.and Technol. 5. 533-544 (1992)
[Publications] 時田澄男ら5名第1著者:S.A.Tucker: "“Spectroscopic Properties of Polycyclic Aromatic Compounds:Examination of Nitromethane as a Selective Fluorescence Quenching Agent for Alternant Polycyclic Aromatic Nitrogen Hetero-Atom Derivatives"," Applied Spectroscopy. 229-235 (1992)
[Publications] 野平博之ら3名第1著者:S.Nakano: "“Metastable Solution Structures of Spirobenzoselenazo-Linobenzopyranes and Their Negative Photochromic Propertiea"," Chem.Lett.13-16 (1992)
[Publications] 野平博之ら 4名第1著者:A.Miyashita: "“Susceptible Photochromic Polymers.Synthesis and Photochemical Properties of Poly(methyl methacrylate)Anchoring Spirobenzothiopirans as Side Chain" J.Material Chemistry. (1993)
[Publications] 宮下晃ら 5名第1著者:A.Miyashita: "“Synthesis and Negative Photochromic Properties of Spirobwnzoselenazolinobenzopyranes"," Chemistry Express. (1993)
[Publications] 横山泰ら 3名第1著者:Y.Yokoyama: "“Non-destructive Readout Method for Photon-mode Optical Memory.Photochromism of Protonated 5-Dimethyl-aminoindolyl fulgide"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)
[Publications] 横山泰ら 8名第1著者:J.Takeda: "“Intermolecular interaction of Photochromic Furylfulgide Dispersed in a Polymer Film"" Chem.Phys.Lett.198. 609-614 (1992)
[Publications] 横山泰ら 2名第1著者:横山泰: "“光記録材料としてのホトクロミックなフルギド類"," 日本化学会誌. 998-1005 (1992)
[Publications] 横山泰ら 2名第1著者:横山泰: "“フルギドのフォトクロミズム"" 染料と薬品. 37. 143-154 (1992)
[Publications] 横山泰ら 3名第1著者:Y.Yokoyama: "“A Non-destructive Readout Method of Photochromic Optical Memory Utilizing Acid-base Equilibrium"," 14th IUPAC Symposium on Photochemistry. 284-285 (1992)
[Publications] 前川仁,井門俊二ら3名第1著者:R.J.Dong: "“A Motion Path Generation in an Environment Consists of Movable and Fixed Objects"" Proc.9th International CAD/CAM,Robotics and Fact of the Future Conference. (1993)

1992 Fiscal Year Annual Research Report

新しいホトクロミック化合物の合成に適した分子設計手法の確立に関する研究

Principal Investigator

時田 澄男 埼玉大学, 工学部, 教授 (20008866)

Research Products

[Publications] 時田 澄男ら5名 第1著者:Y.Kubo: "“Synthesis of 1.3-Bis(indoaniline)-derived Calix〔4〕-arene as an Optical Senor for Calcium Ion"" J.Chem.Soc.,Chem.Commun.(1993)

[Publications] 時田 澄男ら4名 第1著者:S.Tokita: "“INDO/S Self-Consistent Reaction Field Study of Indoaniline Dyes"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田 澄男ら4名 第1著者:H.Kihara: "“An Interactive Software for Predicting Electronic Spectra of Organic Compounds by Personal Computers"" Proc.2nd Int.Symp.on Chem.of Functinal Dyes. (1993)

[Publications] 時田 澄男ら4名 第1著者:Y.Hattori: "“Hole Drift Mobility and Electronic State of Charge Transfer Materials"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田 澄男ら2名 第一著者:S.Tokita: "“Synthesis and Properties of Benzo〔1,2,3-kl:4,5,6-K',l'〕diacridines"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田 澄男ら2名 第1著者:S.Tokita: "“Synthesis of Several Analogues of Anthra〔1,9-bc:4,10-b',c'〕dichromene and Their Photochromic Properties"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田 澄男ら7名 第1著者:Y.Kobayashi: "“Structural Chemistry of Photochromic Benzodixanthene and Its Sulfur Analogue"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田 澄男ら6名 第1著者:K.Kitahara: "“Synthesis of Soluble 2,3-Naphthalocyanines Having Ester Groups"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田 澄男ら5名 第1著者:時田 澄男: "“ベンゾ〔1,2,3-kl;4,5,6-K'l'〕ジキサンテンの非対称型類縁体ならびにそれらのエンドペルオキシドの合成とホトクロミック特性"," 日本化学会誌. 1097-1101 (1992)

[Publications] 時田 澄男ら5名 第1著者:S.A.Tucker: "“Polycyclic Aromatic Nitrogen Heterocycles.Part 4.Effect of Solvent Polarity,Solvent Acidity,Nitromethane and 1,2,4-Trimethoxy benzene on the Fluores,Emission Behavior of Mono-and Diazaarenes"," Applied Spectroscopy. 46. 1630-1635 (1992)

[Publications] 時田 澄男ら5名 第1著者:K.Kitahara: "“Synthesis of Octasubstituted Metal Phthalocyanines"," Phosphorus,Sulfur,Silicon and Related Elements. 67. 373-376 (1992)

[Publications] 時田 澄男ら3名 第1著者:S.Tokita: "“Molecular Structure and Electronic Spectrum of Organic Colorants(2):Molecular Orbital Approach to Indoaniline Dyes"," J.Photopolymer Sci.and Technol. 5. 533-544 (1992)

[Publications] 時田 澄男ら5名 第1著者:S.A.Tucker: "“Spectroscopic Properties of Polycyclic Aromatic Compounds:Examination of Nitromethane as a Selective Fluorescence Quenching Agent for Alternant Polycyclic Aromatic Nitrogen Hetero-Atom Derivatives"," Applied Spectroscopy. 229-235 (1992)

[Publications] 野平 博之ら3名 第1著者:S.Nakano: "“Metastable Solution Structures of Spirobenzoselenazo-Linobenzopyranes and Their Negative Photochromic Propertiea"," Chem.Lett.13-16 (1992)

[Publications] 野平 博之ら 4名 第1著者:A.Miyashita: "“Susceptible Photochromic Polymers.Synthesis and Photochemical Properties of Poly(methyl methacrylate)Anchoring Spirobenzothiopirans as Side Chain" J.Material Chemistry. (1993)

[Publications] 宮下 晃ら 5名 第1著者:A.Miyashita: "“Synthesis and Negative Photochromic Properties of Spirobwnzoselenazolinobenzopyranes"," Chemistry Express. (1993)

[Publications] 横山 泰ら 3名 第1著者:Y.Yokoyama: "“Non-destructive Readout Method for Photon-mode Optical Memory.Photochromism of Protonated 5-Dimethyl-aminoindolyl fulgide"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 横山 泰ら 8名 第1著者:J.Takeda: "“Intermolecular interaction of Photochromic Furylfulgide Dispersed in a Polymer Film"" Chem.Phys.Lett.198. 609-614 (1992)

[Publications] 横山 泰ら 2名 第1著者:横山 泰: "“光記録材料としてのホトクロミックなフルギド類"," 日本化学会誌. 998-1005 (1992)

[Publications] 横山 泰ら 2名 第1著者:横山 泰: "“フルギドのフォトクロミズム"" 染料と薬品. 37. 143-154 (1992)

[Publications] 横山 泰ら 3名 第1著者:Y.Yokoyama: "“A Non-destructive Readout Method of Photochromic Optical Memory Utilizing Acid-base Equilibrium"," 14th IUPAC Symposium on Photochemistry. 284-285 (1992)

[Publications] 前川 仁,井門 俊二ら3名 第1著者:R.J.Dong: "“A Motion Path Generation in an Environment Consists of Movable and Fixed Objects"" Proc.9th International CAD/CAM,Robotics and Fact of the Future Conference. (1993)

時田澄男埼玉大学, 工学部, 教授 (20008866)

[Publications] 時田澄男ら5名第1著者:Y.Kubo: "“Synthesis of 1.3-Bis(indoaniline)-derived Calix〔4〕-arene as an Optical Senor for Calcium Ion"" J.Chem.Soc.,Chem.Commun.(1993)

[Publications] 時田澄男ら4名第1著者:S.Tokita: "“INDO/S Self-Consistent Reaction Field Study of Indoaniline Dyes"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田澄男ら4名第1著者:H.Kihara: "“An Interactive Software for Predicting Electronic Spectra of Organic Compounds by Personal Computers"" Proc.2nd Int.Symp.on Chem.of Functinal Dyes. (1993)

[Publications] 時田澄男ら4名第1著者:Y.Hattori: "“Hole Drift Mobility and Electronic State of Charge Transfer Materials"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田澄男ら2名第一著者:S.Tokita: "“Synthesis and Properties of Benzo〔1,2,3-kl:4,5,6-K',l'〕diacridines"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田澄男ら2名第1著者:S.Tokita: "“Synthesis of Several Analogues of Anthra〔1,9-bc:4,10-b',c'〕dichromene and Their Photochromic Properties"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田澄男ら7名第1著者:Y.Kobayashi: "“Structural Chemistry of Photochromic Benzodixanthene and Its Sulfur Analogue"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田澄男ら6名第1著者:K.Kitahara: "“Synthesis of Soluble 2,3-Naphthalocyanines Having Ester Groups"," Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 時田澄男ら5名第1著者:時田澄男: "“ベンゾ〔1,2,3-kl;4,5,6-K'l'〕ジキサンテンの非対称型類縁体ならびにそれらのエンドペルオキシドの合成とホトクロミック特性"," 日本化学会誌. 1097-1101 (1992)

[Publications] 時田澄男ら5名第1著者:S.A.Tucker: "“Polycyclic Aromatic Nitrogen Heterocycles.Part 4.Effect of Solvent Polarity,Solvent Acidity,Nitromethane and 1,2,4-Trimethoxy benzene on the Fluores,Emission Behavior of Mono-and Diazaarenes"," Applied Spectroscopy. 46. 1630-1635 (1992)

[Publications] 時田澄男ら5名第1著者:K.Kitahara: "“Synthesis of Octasubstituted Metal Phthalocyanines"," Phosphorus,Sulfur,Silicon and Related Elements. 67. 373-376 (1992)

[Publications] 時田澄男ら3名第1著者:S.Tokita: "“Molecular Structure and Electronic Spectrum of Organic Colorants(2):Molecular Orbital Approach to Indoaniline Dyes"," J.Photopolymer Sci.and Technol. 5. 533-544 (1992)

[Publications] 時田澄男ら5名第1著者:S.A.Tucker: "“Spectroscopic Properties of Polycyclic Aromatic Compounds:Examination of Nitromethane as a Selective Fluorescence Quenching Agent for Alternant Polycyclic Aromatic Nitrogen Hetero-Atom Derivatives"," Applied Spectroscopy. 229-235 (1992)

[Publications] 野平博之ら3名第1著者:S.Nakano: "“Metastable Solution Structures of Spirobenzoselenazo-Linobenzopyranes and Their Negative Photochromic Propertiea"," Chem.Lett.13-16 (1992)

[Publications] 野平博之ら 4名第1著者:A.Miyashita: "“Susceptible Photochromic Polymers.Synthesis and Photochemical Properties of Poly(methyl methacrylate)Anchoring Spirobenzothiopirans as Side Chain" J.Material Chemistry. (1993)

[Publications] 宮下晃ら 5名第1著者:A.Miyashita: "“Synthesis and Negative Photochromic Properties of Spirobwnzoselenazolinobenzopyranes"," Chemistry Express. (1993)

[Publications] 横山泰ら 3名第1著者:Y.Yokoyama: "“Non-destructive Readout Method for Photon-mode Optical Memory.Photochromism of Protonated 5-Dimethyl-aminoindolyl fulgide"" Proc.2nd Int.Symp.on Chem.of Functional Dyes. (1993)

[Publications] 横山泰ら 8名第1著者:J.Takeda: "“Intermolecular interaction of Photochromic Furylfulgide Dispersed in a Polymer Film"" Chem.Phys.Lett.198. 609-614 (1992)

[Publications] 横山泰ら 2名第1著者:横山泰: "“光記録材料としてのホトクロミックなフルギド類"," 日本化学会誌. 998-1005 (1992)

[Publications] 横山泰ら 2名第1著者:横山泰: "“フルギドのフォトクロミズム"" 染料と薬品. 37. 143-154 (1992)

[Publications] 横山泰ら 3名第1著者:Y.Yokoyama: "“A Non-destructive Readout Method of Photochromic Optical Memory Utilizing Acid-base Equilibrium"," 14th IUPAC Symposium on Photochemistry. 284-285 (1992)

[Publications] 前川仁,井門俊二ら3名第1著者:R.J.Dong: "“A Motion Path Generation in an Environment Consists of Movable and Fixed Objects"" Proc.9th International CAD/CAM,Robotics and Fact of the Future Conference. (1993)