Structural Analysis and Excited-State Dynamics of Highly Polar Aromatic Species Multiply and Selectively Labeled by Stable Isotopes.

高极性芳香族物质增殖和稳定同位素选择性标记的结构分析和激发态动力学。

• 批准号: 12640491
• 负责人: NAKAGAKI Ryoichi
• 金额: $ 2.43万
• 依托单位: Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640491/
• 关键词: DMABN; ^<15>N; ^<13>C; ^2H; Vibrational Analvsis; Benzenoid; Quinoid; DMABN-F_4

Vibrational Analysis of p -N,N- dimethylaminobenzonitrile (DMABN) has been performed for a series of isotope-substituted DMABNs in the ground saate. Infrared and Raman spectra of DMABNs have been recorded and analyzed on the basis of normal coordinate calculation on an empirical force field and of the Hartree-Fock and the density functional calculations. It has been found that a strong interaction between the dimethylamino group and the aromatic ring is directly reflected in the force field.Picosecond transient infrared spectra have been recorded for the excited singlet state of a series of isotope-substituted DMABNs in the fingerprint region. The band at 1276cm^<-1> for normal species shifts to low frequencies on ^<15>N, ^<13>C, and ^2H substitution of the dimethylamino group, and therefore assigned to the ring C-N(CH_8)_2 single-bond stretching. Other bands observed are attributable to vibrational modes of the benzonitrile moiety. The observed results suggest that the electronic structure of the charge-transfer excited singlet state is basically of the benzenoid nature with a significant contribution from the quinoid structure.

对研磨状态中的一系列同位素取代的 DMABN 进行了振动分析。基于经验力场的法向坐标计算以及 Hartree-Fock 和密度泛函计算，记录并分析了 DMABN 的红外和拉曼光谱。研究发现二甲氨基与芳香环之间的强相互作用直接反映在力场中。在指纹区记录了一系列同位素取代的DMABNs的激发单线态的皮秒瞬态红外光谱。正常物质的 1276cm^<-1> 谱带在二甲基氨基的 ^<15>N、^<13>C 和 ^2H 取代上移至低频，因此分配给环 C-N(CH_8)_2 单环-键拉伸。观察到的其他谱带可归因于苯甲腈部分的振动模式。观察到的结果表明，电荷转移激发单重态的电子结构基本上是苯型结构，其中醌型结构的贡献很大。

项目成果

中垣良一: "Magnetic Field and Magnetic Isotope Effecte upon Photochemistry of Bifunctional Chain Molecules Containing Nitroaryloxy and Anilino Chromophores"RIKEN Review. 44. 63-65 (2002)

Ryoichi Nakagaki：“磁场和磁同位素对含有硝基芳氧基和苯胺发色团的双功能链分子光化学的影响”RIKEN Review 44. 63-65 (2002)。

中垣良一 他4名: "Infrared and Raman spectra of 4-(dimethylamino) benzonitrile and isotopomers in the ground state and vibrational analysis"Chemical Physics. 260. 193-214 (2000)

Ryoichi Nakagaki 等 4 人：“4-(二甲氨基)苯甲腈和同位素异构体在基态下的红外和拉曼光谱及振动分析”化学物理 260. 193-214 (2000)。

中垣 良一他4名: "Infrared and Raman Spectra of 4-(Dimethylamino)benzonitrile and Isotopomers in the Ground State and Vibrational Analysis"Chem. Phys.. 260. 193-214 (2000)

Ryoichi Nakagaki 等 4 人：“4-(二甲氨基)苯甲腈和同位素在基态下的红外和拉曼光谱及振动分析”Chem. Phys. 260. 193-214 (2000)

中垣 良一: "Magnetic Field and Magnetic Isotope Effects upon Photochemistry of Bifunctional Chain Molecules Containing Nitroalyloxy and Anilino Chromophores"RIKEN Review. 44. 63-65 (2002)

Ryoichi Nakagaki：“磁场和磁同位素对含有硝基丙烯氧基和苯胺发色团的双功能链分子光化学的影响”RIKEN Review 44. 63-65 (2002)。

中垣良一他5名: "Evidence for Electric Field Assisted Back-electron Transfer through a Methylene Bond in a Linked Compound of Phenanthrene and Phthalimide in Polymer Film"J. Chem. Phys.. 114. 7723-7726 (2001)

Ryoichi Nakagaki 等 5 人：“聚合物薄膜中菲和邻苯二甲酰亚胺连接化合物中电场辅助反向电子转移的证据”J. Chem. 114. 7723-7726 (2001)