An infrared spectroscopic study on CH/π Ieractions in molecular clusters

分子簇中CH/π相互作用的红外光谱研究

• 批准号: 14540462
• 负责人: FUJII Asuka
• 金额: $ 2.5万
• 依托单位: Tohoku university
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540462/
• 关键词: CH; π interaction; infrared spectroscopy; cluster; intermolecular interaction; hydrogen bond; dispersion force; acetylene; benzene; CH-π相互作用; 赤外分光法; 二重共鳴法

CH stretching vibrations of jet-cooled benzene-acetylene and several aromatics-acetylene clusters were observed for the characterization of the intermolecular interaction, so-called activated CH/π interaction between the acidic CH group and π-electrons, under the well-defined condition. The infrared-ultraviolet double resonance spectroscopic techniques were used to measure Infrared spectra of the jet-cooled clusters. The antisymmetric CH stretching vibration of the acetylene moiety exhibits substantial low-frequency shifts upon the cluster formation with the aromatic molecules, indicating such cluster structures that acetylenic CH Is bound to the π-electrons of the aromatic ring. The magnitude of the low-frequency shifts Increased with increase of the π-electron density of the ring, as expected for an ordinary π-hydrogen bond. On the other hand, the polarizability of the proton accepting molecules showed a weakly negative correlation with the CN frequency shifts.

在一定条件下，观察到了苯-乙炔和几种芳烃-乙炔簇合物的CH伸缩振动，以表征分子间的相互作用，即酸性CH基团与π电子之间的活化CH/π相互作用.用红外-紫外双共振光谱技术测量了喷流冷却团簇的红外光谱。乙炔部分的反对称CH伸缩振动在与芳族分子形成簇时表现出显著的低频位移，表明乙炔CH与芳环的π电子结合的簇结构。低频位移的大小随环上π电子密度的增加而增加，与普通π氢键的结果一致。另一方面，质子接受分子的极化率与CN频移呈弱负相关。

项目成果

M.Honda, A.Fujii, E.Fujimaki, T.Ebata, N.Mikami: "NH stretching vibrations of jet-cooled aniline and its derivatives in the neutral and cationic ground states"Journal of Physical Chemistry A. 107. 3678-3686 (2003)

M.Honda、A.Fujii、E.Fujimaki、T.Ebata、N.Mikami：“喷射冷却苯胺及其衍生物在中性和阳离子基态下的 NH 伸缩振动”物理化学杂志 A. 107. 3678-

A.Fujii, G.N.Patwari, T.Ebata, N.Mikami: "Vibrational spectroscopic evidence of unconventional hydrogen bonds"International Journal of Mass Spectrometry. 220. 289-312 (2002)

A.Fujii、G.N.Patwari、T.Ebata、N.Mikami：“非常规氢键的振动光谱证据”国际质谱杂志。

A.Fujii, T.Ebata, N.Mikami: "An infrared study of π-hydrogen bonds in microsolvated phenol"Journal of Physical Chemistry A. 106. 8554-8560 (2002)

A.Fujii、T.Ebata、N.Mikami：“微溶剂化苯酚中 π-氢键的红外研究”物理化学杂志 A. 106. 8554-8560 (2002)

A.Fujii, T.Ebata, N.Mikami: "Direct observation of weak hydrogen bonds in microsolvated phenol"Journal of Physical Chemistry A. 106・43. 10124-10129 (2002)

A.Fujii、T.Ebata、N.Mikami：“微溶剂化苯酚中弱氢键的直接观察”物理化学杂志 A. 106・43 (2002)。

A.Fujii, T.Ebata, N.Mikami: "Direct observation of weak hydrogen bonds in microsolvated phenol"Journal of Physical Chemistry A. 106. 10124-10129 (2002)

A.Fujii、T.Ebata、N.Mikami：“微溶剂化苯酚中弱氢键的直接观察”物理化学杂志 A. 106. 10124-10129 (2002)