• 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 >Charge-Transfer Interaction of Aromatic Thiols with 2,3-DichIoro-5,6-dicyano-p-benzoquinone: Spectral and Quantum Mechanical Studies
【24h】

Charge-Transfer Interaction of Aromatic Thiols with 2,3-DichIoro-5,6-dicyano-p-benzoquinone: Spectral and Quantum Mechanical Studies

机译：芳香族硫醇与2,3-DichIoro-5,6-二氰基对苯醌的电荷转移相互作用：光谱和量子力学研究

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

Charge-transfer (CT) complexes formed between aromatic thiol donors (thiophenol (TP), benzene-1,4-dithiol (BDT), p-aminothiophenol (ATP), p-hydroxythiophenol (HTP), and p-toluenefhiol (TTP)) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as an acceptor were studied spectrophotometrically in dichloromethane. Addition of aromatic thiols in dichloromethane to DDQ leads to the formation of colored solutions that exhibit a very broad absorption band in the range 440-800 nm and a band in the region 300-400 nm. On the basis of the energies of LUMO and HOMO from quantum mechanical calculations, the broad band observed in the visible region was assigned to the pi~*(a_2) <- pi(b_1) transition and a band observed between 300 and 400 nm was assigned to the pi~*(a_2) <- pi(a_2) transition. The solid CT complexes of aromatic thiols and DDQ were prepared and characterized by FT-IR spectroscopy. The stoichiometry of the CT complexes was determined by Job's continuous variation method. The association constant (K_(CT)), molar extinction coefficient (epsilon), oscillator strength (f), and transition dipole moment (mu) values were calculated from the electronic spectra. The vertical ionization potentials (I~D) of the donors were calculated from their corresponding lambda_(CT). Quantum mechanical (QM) calculations were performed to determine the ionization potential and the energies of the highest occupied molecular orbital (HOMO) of donors and lowest unoccupied molecular orbital (LUMO) of an acceptor.
机译：芳族硫醇供体（硫酚（TP），苯-1,4-二硫醇（BDT），对氨基硫酚（ATP），对羟基硫酚（HTP）和对甲苯酚（TTP）之间形成的电荷转移（CT）配合物）和2,3-二氯-5,6-二氰基对苯醌（DDQ）作为受体在二氯甲烷中分光光度法进行了研究。将二氯甲烷中的芳族硫醇添加到DDQ中会导致形成有色溶液，该溶液在440-800 nm范围内具有非常宽的吸收带，在300-400 nm范围内具有吸收带。根据来自量子力学计算的LUMO和HOMO的能量，在可见光区观察到的宽带被分配给pi〜*（a_2）<-pi（b_1）跃迁，并且在300至400 nm之间观察到的谱带为分配给pi〜*（a_2）<-pi（a_2）过渡。制备了芳香族硫醇和DDQ的固体CT配合物，并通过FT-IR光谱进行了表征。 CT复合物的化学计量是通过Job的连续变化法确定的。由电子光谱计算缔合常数（K_（CT）），摩尔消光系数（ε），振子强度（f）和跃迁偶极矩（μ）值。从它们的相应的λ（CT）计算出施主的垂直电离势（I〜D）。进行量子力学（QM）计算，以确定供体的最高电离分子轨道（HOMO）和受体的最低空分子轨道（LUMO）的电离势和能量。

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