{"title":"4，4'-二羟基联苯光氧化产生的自由基。","authors":"敏彦 星, 勲 小野, 潤 大窪, 誠一 田辺, 適夫 小林","doi":"10.5111/BUNKOU.38.273","DOIUrl":null,"url":null,"abstract":"Photolysis of 4, 4'-dihydroxybiphenyl (BPH2) gave a cation radical (BPH2+·), 4-hydroxy-4'-biphenoxyradical (BPH·) and the conjugate base (BP-·) of BPH· in EPA at 77K. The absorption spectra of the radicals were measured in a wide wavelength region, 350-1000 nm, and the first electronic absorption bands of BPH2+·, BPH· and BP-·. are at 620, 649 and 787 nm, respectively. Irradiation of BPH2 in poly (vinyl alcohol) film at 103 K afforded the mixture of BPH2+· and BP-· BPH2 changed to BP-· predominantly with increasing temperature. The first bands of BPH2+.(640nm) and BP-· (823nm) are polarized along the longer molecular axes. The first transition of BPH2+· corresponds to the transitson from the half-occupied orbital to the lowest vacant orbital, and is interpreted as an intramolecular charge transfer one from the two oxygen atoms to the biphenyl skeleton. The first transition of BP-· corresponds to the transition from the highest occupied orbital to the half-occupied one.","PeriodicalId":199016,"journal":{"name":"Journal of the Spectroscopical Society of Japan","volume":"29 1","pages":"0"},"PeriodicalIF":0.0000,"publicationDate":"1989-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"4, 4'-ジヒドロキシビフェニルの光酸化により生じるフリーラジカル\",\"authors\":\"敏彦 星, 勲 小野, 潤 大窪, 誠一 田辺, 適夫 小林\",\"doi\":\"10.5111/BUNKOU.38.273\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Photolysis of 4, 4'-dihydroxybiphenyl (BPH2) gave a cation radical (BPH2+·), 4-hydroxy-4'-biphenoxyradical (BPH·) and the conjugate base (BP-·) of BPH· in EPA at 77K. The absorption spectra of the radicals were measured in a wide wavelength region, 350-1000 nm, and the first electronic absorption bands of BPH2+·, BPH· and BP-·. are at 620, 649 and 787 nm, respectively. Irradiation of BPH2 in poly (vinyl alcohol) film at 103 K afforded the mixture of BPH2+· and BP-· BPH2 changed to BP-· predominantly with increasing temperature. The first bands of BPH2+.(640nm) and BP-· (823nm) are polarized along the longer molecular axes. The first transition of BPH2+· corresponds to the transitson from the half-occupied orbital to the lowest vacant orbital, and is interpreted as an intramolecular charge transfer one from the two oxygen atoms to the biphenyl skeleton. The first transition of BP-· corresponds to the transition from the highest occupied orbital to the half-occupied one.\",\"PeriodicalId\":199016,\"journal\":{\"name\":\"Journal of the Spectroscopical Society of Japan\",\"volume\":\"29 1\",\"pages\":\"0\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1989-08-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the Spectroscopical Society of Japan\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.5111/BUNKOU.38.273\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the Spectroscopical Society of Japan","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.5111/BUNKOU.38.273","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Photolysis of 4, 4'-dihydroxybiphenyl (BPH2) gave a cation radical (BPH2+·), 4-hydroxy-4'-biphenoxyradical (BPH·) and the conjugate base (BP-·) of BPH· in EPA at 77K. The absorption spectra of the radicals were measured in a wide wavelength region, 350-1000 nm, and the first electronic absorption bands of BPH2+·, BPH· and BP-·. are at 620, 649 and 787 nm, respectively. Irradiation of BPH2 in poly (vinyl alcohol) film at 103 K afforded the mixture of BPH2+· and BP-· BPH2 changed to BP-· predominantly with increasing temperature. The first bands of BPH2+.(640nm) and BP-· (823nm) are polarized along the longer molecular axes. The first transition of BPH2+· corresponds to the transitson from the half-occupied orbital to the lowest vacant orbital, and is interpreted as an intramolecular charge transfer one from the two oxygen atoms to the biphenyl skeleton. The first transition of BP-· corresponds to the transition from the highest occupied orbital to the half-occupied one.
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