• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ground- and Excited-State Proton Transfer and Rotamerism in 2-(2-Hydroxyphenyl)-5-phenyl-l,3,4-oxadiazole and Its O/'NH or S'-Substituted Derivatives
【24h】

Ground- and Excited-State Proton Transfer and Rotamerism in 2-(2-Hydroxyphenyl)-5-phenyl-l,3,4-oxadiazole and Its O/'NH or S'-Substituted Derivatives

机译：2-（2-羟基苯基）-5-苯基-1,3,4-恶二唑及其O /“ NH或S”取代衍生物的基态和激发态质子转移和旋转性

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The intramolecular proton-transfer process, rotational process, and optical properties of 2-(2-hydroxyphenyl)-5-phenyl-l,3,4-oxadiazole (HOXD) and its O/"NH"- and O/"S"-substituted derivatives, 2-(2-hydroxyphenyl)-5-phenyl-l,3,4-triazole (HOT) and 2-(2-hydroxyphenyl)-5-phenyl-l,3,4-thiadiazole (HOTD), respectively, have been studied. DFT (B3LYP/6-31+G**) single-point energy calculations were performed using HF- and DFT-optimized geometries in the ground state (S_0). TD-B3LYP/6-31+G** calculations using CIS-optimized geometries were carried out to investigate the properties of the first singlet excited state (S_1) and first triplet excited state (T_1). The computational results revealed that a high-energy barrier inhibits the proton transfer from cis-enol (E_c) to keto (K) form in So, whereas the proton transfer in S_1 can take place through a very-low-energy barrier. The rotation between E_c and trans-enol (Et) can occur in S_0 through a low-energy barrier, whereas it is prohibited because of the high-energy barrier in S_1 for each of the three molecules. The vertical excitation energies were calculated using the TD-B3LYP/6-31+G** method based on the HF- and CIS-optimized geometries. Absorption and fluorescence wavelengths of HOT show a hypsochromic shift (6-15 nm) relative to HOXD, while those of HOTD show a bathochromic shift (21-29 nm). The phosphorescence wavelength of HOTD shows a significant bathochromic shift relative to that of HOXD.
机译：2-（2-羟基苯基）-5-苯基-1,3,4-恶二唑（HOXD）及其O /“ NH”-和O /“ S”的分子内质子转移过程，旋转过程和光学性质-取代的衍生物2-（2-羟苯基）-5-苯基-1,3,4-三唑（HOT）和2-（2-羟苯基）-5-苯基-1,3,4-噻二唑（HOTD），分别进行了研究。 DFT（B3LYP / 6-31 + G **）单点能量计算是使用处于基态（S_0）的经过HF和DFT优化的几何图形进行的。使用CIS优化的几何结构进行TD-B3LYP / 6-31 + G **计算，以研究第一单重激发态（S_1）和第一三重激发态（T_1）的性质。计算结果表明，高能垒抑制了So中质子从顺式烯醇（E_c）到酮（K）形式的转移，而S_1中的质子转移可以通过极低能垒进行。 E_c和反式烯醇（Et）之间的旋转可以通过低能垒在S_0中发生，但由于S_1中三个分子中的高能垒而被禁止了。垂直激励能量是根据HF和CIS优化的几何形状，使用TD-B3LYP / 6-31 + G **方法计算得出的。相对于HOXD，HOT的吸收和荧光波长显示出一个七色移（6-15 nm），而HOTD的吸收和荧光波长则显示出一个红移（21-29 nm）。相对于HOXD，HOTD的磷光波长显示出显着的红移。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号