Hydrogen bond migration between molecular sites observed with ultrafast 2D IR chemical exchange spectroscopy.
Hydrogen bond migration between molecular sites observed with ultrafast 2D IR chemical exchange spectroscopy.
复制标题
DOI：
10.1021/jp911452z
复制
发表时间：
2010-02-25
期刊：
影响因子：
--
通讯作者：
Fayer MD
中科院分区：
文献类型：
--
作者：
Rosenfeld DE;Kwak K;Gengeliczki Z;Fayer MD
用超快二维红外(2D IR)化学交换光谱研究了苯酚与苯乙炔的氢键络合物。苯乙炔有两个可能的π氢键受体位置(苯基或乙炔)，它们在室温下的溶液中竞争氢键供体。重氢苯酚的OD伸展频率与其结合的受体位置有关。二维红外光谱中两个振动频率之间的非对角峰的出现反映了苯酚-苯乙炔络合物在苯乙炔溶剂中两个竞争氢键中心之间的交换过程。化学交换过程发生在∼5PS中，并被认为是沿着苯乙炔分子的直接氢键迁移。通过对苯乙炔/四氯化碳混合溶剂中苯酚的2D IR实验，排除了其他非迁移机理。氢键直接迁移现象的观察对大分子体系有一定的意义。
Hydrogen bonded complexes between phenol and phenylacetylene are studied using ultrafast two-dimensional infrared (2D IR) chemical exchange spectroscopy. Phenylacetylene has two possible π hydrogen bonding acceptor sites (phenyl or acetylene) that compete for hydrogen bond donors in solution at room temperature. The OD stretch frequency of deuterated phenol is sensitive to which acceptor site it is bound. The appearance of off-diagonal peaks between the two vibrational frequencies in the 2D IR spectrum reports on the exchange process between the two competitive hydrogen bonding sites of phenol-phenylacetylene complexes in the neat phenylacetylene solvent. The chemical exchange process occurs in ∼5 ps, and is assigned to direct hydrogen bond migration along the phenylacetylene molecule. Other non-migration mechanisms are ruled out by performing 2D IR experiments on phenol dissolved in the phenylacetylene/carbon tetrachloride mixed solvent. The observation of direct hydrogen bond migration can have implications for macromolecular systems.
登录
查看更多内容
影响因子：
2.9
作者：
Singh, Prashant Chandra;Bandyopadhyay, Biswajit;Patwari, G. Naresh
通讯作者：
Patwari, G. Naresh
影响因子：
4.4
作者：
TSUBOMURA, H
通讯作者：
TSUBOMURA, H
影响因子：
3.3
作者：
Kwak, Kyungwon;Rosenfeld, Daniel E.;Chung, Jean K.;Fayer, Michael D.
通讯作者：
Fayer, Michael D.
影响因子：
15
作者：
Sinnokrot, MO;Sherrill, CD
通讯作者：
Sherrill, CD
影响因子：
15
作者：
HUNTER, CA;SANDERS, JKM
通讯作者：
SANDERS, JKM