Laser spectroscopic research on unconventional hydrogen bonds involving borane

硼烷非常规氢键的激光光谱研究

基本信息

  • 批准号:
    14204057
  • 负责人:
  • 金额:
    $ 36.44万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
  • 财政年份:
    2002
  • 资助国家:
    日本
  • 起止时间:
    2002 至 2004
  • 项目状态:
    已结题

项目摘要

1.Geometric structures and the excited-state proton-dislocation in size-selected clusters of salicylic acids (salicylic acid and 5-methoxysalicylic acid) with water or methanol were studied by using laser spectroscopic techniques. Fluorescence excitation, dispersed fluorescence, and infrared (IR) spectra of those clusters in supersonic jets were examined for both the electronic ground and first excited states. The geometric structures of the clusters were determined on the basis of the IR spectra of the OH stretch region with a help of quantum chemical calculations. The hydroxyl group of the water or methanol moiety in the clusters forms a ring involving the carboxylic group of the salicylic acid moiety. The intramolecular hydrogen bond in the salicylic acid moiety is still held upon the cluster formation. The puzzling IR spectra in the electronic excited state were analyzed in combination with a partial deuteration study. The IR spectra in the excited state and dispersed fluorescence … More spectra indicated that the intramolecular excited state proton dislocation is hardly affected by the microsolvation with water or methanol, in contrast with the strong suppression of the dislocation in the self-salvation. A drastic reduction of the acidity of the carboxylic OH upon the electronic excitation was also found.2.Substitution effects on the excited state intramolecular proton transfer (ESIPT) in the salicylic acid (SA) frame were studied by electronic and infrared spectroscopy of jet-cooled 5-methoxylsalicylic acid (5-McOSA), 5-methylsalicylic acid (5-MeSA), 5-fluorosalicylic acid (5-FSA), 6-fluorosalicylie acid (6-FSA), and methyl salicylate (MS). Infrared spectra were measured in the 3 mm region for both the electronic ground (S_0) and first excited (S_1) states. The electronic excitation/emission spectra of 5-MeSA and 6-FSA showed the typical spectral features of ESIPT, which have been found in the spectra of SA. On the other hand, 5-MeOSA and 5-FSA exhibit a mirror-image relation between their excitation and emission spectra, which has been regarded as a result of the suppression of ESIPT. Despite of such a remarkable difference among the electronic spectra, IR spectroscopy exhibits that a drastic change of the phenolic OH stretching vibration does occur upon the electronic excitation of all the substituted SAs, that is, the phenolic OH band of all the SAs disappears from the 3 mm region, indicating a large elongation of the phenolic O-H bond (over 0.1 Å) in S_1. This result represents that the intramolecular hydrogen-bond strength is remarkably enhanced upon the electronic excitation in all the substituted SAs. Substitution effects on ESIPT in dimers are also discussed. Less
1.用激光光谱技术研究了水杨酸(水杨酸和5-甲氧基水杨酸)与水或甲醇的尺寸选择性团簇的几何结构和激发态质子位错。这些簇在超音速射流的荧光激发,分散的荧光和红外(IR)光谱的电子基态和第一激发态进行了检查。根据OH伸缩区的红外光谱,借助量子化学计算确定了簇合物的几何结构。簇中的水或甲醇部分的羟基形成涉及水杨酸部分的羧基的环。水杨酸部分中的分子内氢键在簇形成时仍然保持。结合部分氘代研究,分析了电子激发态下令人困惑的红外光谱。激发态和分散荧光的红外光谱 ...更多信息 光谱表明,与自溶剂化过程中的位错被强烈抑制相反,分子内激发态质子位错几乎不受水或甲醇的微溶剂化作用的影响. 2.用电子光谱和红外光谱研究了5-甲基水杨酸(5-McOSA)、5-甲基水杨酸(5-MeSA)、5-氟水杨酸(5-FSA)、5-甲基水杨酸(5-MeSA)和5-氟水杨酸(5-FSA)的取代效应对水杨酸(SA)框架内激发态分子内质子转移(ESIPT)的影响。6-氟水杨酸(6-FSA)和水杨酸甲酯(MS)。在3mm区域测量了电子基态(S_0)和第一激发态(S_1)的红外光谱。5-MeSA和6-FSA的电子激发/发射光谱显示出典型的ESIPT光谱特征,这些特征在SA的光谱中已被发现。另一方面,5-MeOSA和5-FSA的激发光谱和发射光谱之间呈现镜像关系,这被认为是抑制ESIPT的结果。尽管电子光谱之间存在着显著的差异,但红外光谱表明,所有取代的SA在电子激发时都发生了酚羟基伸缩振动的剧烈变化,即所有SA的酚羟基振动带都从3mm区域消失,表明S_1中酚羟基的O-H键有很大的伸长(超过0.1 Ω)。这一结果表明,分子内氢键强度显着增强后,在所有取代的SA的电子激发。本文还讨论了二聚体中取代基对ESIPT的影响。少

项目成果

期刊论文数量(22)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Infrared spectroscopy of size-selected benzene-water cluster cations [C_6H_6-(H_2O)_n]^+ (n=1-23):Hydrogen bond network evolution and microscopic hydrophobicity
尺寸选定的苯-水簇阳离子[C_6H_6-(H_2O)_n]^ (n=1-23)的红外光谱:氢键网络演化和微观疏水性
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    Otsuka;Y.;K.Shiokawa;T.Ogawa;P.Wilkinson;M.Miyazaki et al.
  • 通讯作者:
    M.Miyazaki et al.
Morphology of protonated methanol clusters: an infrared spectroscopic study of hydrogen bond networks of H+(CH3OH)n (n = 4-15).
  • DOI:
    10.1021/jp0463464
  • 发表时间:
    2005-01
  • 期刊:
  • 影响因子:
    0
  • 作者:
    A. Fujii;S. Enomoto;M. Miyazaki;N. Mikami
  • 通讯作者:
    A. Fujii;S. Enomoto;M. Miyazaki;N. Mikami
Toshihiko Maeyama: "Characteristic distributions of negatively charged A'-monosubstituted amide clusters generated by electron attachment in supersonic expansions"Phys.Chem.Chem.Phys.. (印刷中).
Toshihiko Maeyama:“超音速膨胀中电子附着产生的带负电的 A-单取代酰胺簇的特征分布”Phys.Chem.Chem.Phys..(出版中)。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
G.Naresh Patwari, T.Ebata, N.Mikami: "Vibrational spectroscopic investigation of dihydrogen bonds in gas phase"Bulletin of the Polish Academy of Science. 50・4. 423-434 (2002)
G. Naresh Patwari、T. Ebata、N. Mikami:“气相中二氢键的振动光谱研究”波兰科学院通报 50・4 (2002)。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
A direct experimental evidence for an aromatic C-H⋯O hydrogen bond by fluorescence-detected infrared spectroscopy
  • DOI:
    10.1016/j.cplett.2004.06.101
  • 发表时间:
    2004-08
  • 期刊:
  • 影响因子:
    2.8
  • 作者:
    V. Venkatesan;A. Fujii;T. Ebata;N. Mikami
  • 通讯作者:
    V. Venkatesan;A. Fujii;T. Ebata;N. Mikami
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FUJII Asuka其他文献

FUJII Asuka的其他文献

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{{ truncateString('FUJII Asuka', 18)}}的其他基金

An infrared spectroscopic study on microscopic phase separation in large-sized water-alcohol clusters
大尺寸水-醇团簇微观相分离的红外光谱研究
  • 批准号:
    22350001
  • 财政年份:
    2010
  • 资助金额:
    $ 36.44万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Study on large-scaled hydrogen bond network structures of water by infrared spectroscopy of large-sized clusters
大尺寸团簇红外光谱研究水的大尺寸氢键网络结构
  • 批准号:
    19205001
  • 财政年份:
    2007
  • 资助金额:
    $ 36.44万
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
Direct Observation of the Condensed Phase Development Processes by Infrared Spectroscopy of Giant Clusters
用红外光谱直接观察巨星团凝聚相的形成过程
  • 批准号:
    17310057
  • 财政年份:
    2005
  • 资助金额:
    $ 36.44万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
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
  • 财政年份:
    2002
  • 资助金额:
    $ 36.44万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Development of Autoionization-Detected Infrared Spectroscopy for Molecular Cations
分子阳离子自电离检测红外光谱的发展
  • 批准号:
    09640591
  • 财政年份:
    1997
  • 资助金额:
    $ 36.44万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
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