Development of the Novel Chemiluminescence Systems Involved in the Interface of Liquid and Metal Oxide

液体与金属氧化物界面新型化学发光系统的开发

• 批准号: 04640495
• 负责人: MAEDA Koko
• 金额: $ 0.9万
• 依托单位: Ochanomizu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640495/
• 关键词: adsorption chemiluminescence; desorption chemiluminescence; biacridinylidene; superoxide; biisoquinolidene; surface of metal oxide; activated alumina; electron-transfer; ビアクリジリデン; 電子的酸化・還元; 化学発光; ラジカル機構; 金属酸化物; アルミナ表面

N,N-Disubstituted biacridinylidene (BA) has a novel chemiluminescence in an alumina slurry, yellowish green emission (adsorption chemiluminescence) and blue emission (desorption chemiluminescence). The luminescence has been investigated to reveal the reaction mechanisms. The results obtained are as a follows :1)The emitter of the adsorption chemiluminescence was determined to be the excited singlet state of BA(BA^<**>)tenaciously adsorbed onto the alumina surface. When BA is adsorbed on the alumina surface in the nonpolar solvent slurry, electronic oxidation of BA by adsorbed molecular oxygen on the alumina surface resulted the formation of the cation radical BA^<+・> and superoxide O_2^<-・>. Following electron transfer from -O^- and/or -OH on alumina to BA^<+・> gave the excited state of BA^<**> adsorbed on the alumina surface.2)The emitter of the desorption chemiluminescence was determined to be the excited singlet state of N-substituted acridone. On addition of a polar solvent into the slurry after the adsorption chemiluminescence ceased, the second blue emission appeared. Oxygenation of BA^<2+> by O_2*gave the excited state of acridone via dioxetane intermediate upon the desorption by the polar solvent.3)Several kinds of metal oxides were also found to give adsorption chemiluminescence of BA.4)As one of the other substrates, biisoquinolidene(BIQ), the benzolog of BA, was investigated. BIQ has much higher reactivity with molecular oxygen than BA even without metal oxide in nonpolar solvents and gives light emission. It is worthwhile to reveal the reaction mechanism.

N，N-二取代联吖啶亚基（BA）在氧化铝浆中产生一种新的化学发光，即黄绿色发光（吸附化学发光）和蓝色发光（脱附化学发光）。研究了发光现象以揭示反应机理。结果表明：（1）吸附化学发光的发射体为BA（BA^**）的激发单重态，BA（BA^**）在Al 2 O3表面牢固吸附。在非极性溶剂中，BA吸附在氧化铝表面时，被吸附在氧化铝表面的分子氧电子氧化，生成阳离子自由基BA^<+·>和超氧阴离子O_2^<-·>。吸附在Al 2 O3表面的BA^<**>经电子转移后，产生激发态。2）脱附化学发光的发射体为N-取代吖啶酮的激发单重态。在吸附化学发光停止后，向浆料中加入极性溶剂，出现第二个蓝色发射。BA^<2+>被O_2 ~* 氧化后，在极性溶剂中脱附，通过二氧杂环丁烷中间体得到吖啶酮的激发态。3）几种金属氧化物也能产生BA的吸附化学发光。BIQ与分子氧的反应性比BA高得多，即使在非极性溶剂中没有金属氧化物，也能发光。这对揭示反应机理具有重要意义。

项目成果

Y.Mori: "Structure of Diiodide Salts of N-Heteroaromatic Dications" Acta Cryst.Sect.C. 49. 1398-1401 (1993)

Y.Mori：“N-杂芳族双阳离子的二碘盐的结构”Acta Cryst.Sect.C。

J.Ohkanda,Y.Mori K.Maeda,E.Osawa: "Stractural aspects of the mechanical and thermal dissociation of the central bond in bis(triarylchromenyl)" J.Chem.Soc.,Perkin Trans.2,. 59-63 (1992)

J.Okanda，Y.Mori K.Maeda，E.Osawa：“双（三芳基色烯基）中心键的机械和热解离的结构方面”J.Chem.Soc.，Perkin Trans.2，。

Y.Mori,M.Sasaki,S.Yamada,K.Maeda: "Thermochromism of 5,10,15,20-tetraarylporphyrines at low temperature" Bull.Chem.Soc.Jpn.,. 65. 3358-3361 (1992)

Y.Mori，M.Sasaki，S.Yamada，K.Maeda：“5,10,15,20-四芳基卟啉在低温下的热致变色”Bull.Chem.Soc.Jpn.，。

K.Maeda: "Photochemistry on Solid Surface" Elsevier, 585 (1989)

K.Maeda：“固体表面上的光化学”Elsevier，585 (1989)

Y.Mori: "Structures of 2,2'-Polymethylene-1,1'-biisoquinolinium Dibromides" Acta Cryst.C48. 894-897 (1992)

Y.Mori：“2,2-聚亚甲基-1,1-二异喹啉鎓二溴化物的结构”Acta Cryst.C48。