Construction of Organized Structures using Fluorinated Molecules and Creation of Photofunctional Matrials

使用氟化分子构建组织结构并创建光功能材料

基本信息

批准号：
09490023
负责人：
YANAGIDA Shozo
金额：
$ 7.68万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

Fluorination of p-terphenyl induced stepwise hypsochromic shift of its absorption, excitation and fluorescence spectrum and positive shift of electrochemical redox potentials. Fluorinated p-terphenyls worked as the photosensitizers under UV-irradiation in the presence of oxygen for one-electron oxidation of water to hydroxyl radicals scavenged by benzene to give phenol and by 5,5-dimethyl-l-pyrroline N-oxide to give its radical adduct probed by EPR measurements. The photosensitization activity was increased as increasing the number of fluorination of p-terphenyl. Ab initio molecular orbital calculations indicated that polyfluorinated photosensitizers had the attractive intermolecular interactions with benzene and water molecule.The relatively low efficiency of Nd(III) emission in organic media has been improved by 1) suppression of the radiationless transition process via vibrational excitation of the surrounding medium, 2) prevention of dipole-dipole nonradiative energy transfer processes via energy migration, 3) suppression of radiationless transition of D2O molecules in the vicinity of Nd (III) complexes (formation of twelve-coordinate Nd (III) complex with DMSO-d6), 3) allowance of electron transitions of Nd (III) by the introduction of asymmetric ligand field, 4) photosensitization by use of energy transfer from organic ligands. The luminescence of Nd (III) was observed for the first time in undeuterated acetone when Nd (III) was complexed with bis-perfluorooctylsulfonyl-aminc (pos). As to the applications of luminescent Nd (III) complexes, development of luminescent lanthanide polymers was successful.Pentafuorothiophenol, thiophenol, l-decanethiol, l-hexanethiol, benzoic acid and cyanoacetic acid, which are confirmed to bind to the surface of ZnS nanocrysllites, induce phase transition of ZnS nanocrystallites from the hexagonal to the cubic phase, with retention of the crysta-line size of 3 nm at ambient temperature and pressure.

对三联苯的氟化导致其吸收光谱、激发光谱和荧光光谱逐步向低色移动，以及电化学氧化还原电位的正向移动。氟化对三联苯作为光敏剂，在氧气存在下，在紫外线照射下，将水单电子氧化成羟基自由基，苯清除后生成苯酚，再被 5,5-二甲基-L-吡咯啉 N-氧化物清除，生成羟基自由基。通过 EPR 测量探测自由基加合物。光敏活性随着对三联苯氟化次数的增加而增加。从头算分子轨道计算表明，多氟光敏剂与苯和水分子具有有吸引力的分子间相互作用。有机介质中 Nd(III) 发射效率相对较低的问题通过以下方法得到改善：1）通过振动激发抑制无辐射跃迁过程。周围介质，2) 通过能量迁移防止偶极-偶极非辐射能量转移过程，3) 抑制 Nd (III) 配合物附近 D2O 分子的无辐射跃迁（与DMSO-d6形成十二配位Nd（III）配合物），3）通过引入不对称配体场允许Nd（III）的电子跃迁，4）利用有机配体的能量转移进行光敏化。当 Nd (III) 与双全氟辛基磺酰基胺 (pos) 络合时，首次在未氘化丙酮中观察到 Nd (III) 的发光。在发光Nd(III)配合物的应用方面，发光稀土聚合物的开发取得了成功。五氟苯硫酚、苯硫酚、l-癸硫醇、l-己硫醇、苯甲酸和氰乙酸已被证实与ZnS纳米微晶表面结合，诱导 ZnS 纳米晶从六方相到立方相的相变，并保持晶体尺寸环境温度和压力下为 3 nm。