Ling Yun,Xie Wen Chang,Liu Guo Kun,Yan Run Wen,Wu De Yin,Tang Jing
Inter- and intra- molecular hydrogen bonding plays important role in determining molecular structure, physical and chemical properties, which may be easily ignored for molecules with a non-typical hydrogen bonding structure. We demonstrated in this paper that the hydrogen bonding is responsible for the different Raman spectra in solid and solution states of p-Nitrothiophenol (PNTP). The consistence of the theoretical calculation and experiment reveals that the intermolecular hydrogen bonding yields an octatomic ring structure (8) of PNTP in the solid state, confirmed by the characteristic S-H---O stretching vibration mode at 2550 cm −1 ; when it comes to the solution state, the breakage of hydrogen bond of S-H---O induced the S-H stretching vibration at 2590 cm −1 . Our findings may provide a simple and fast method for identifying the intermolecular hydrogen bonding.
Binbin Zhou,Weihui Ou,Junda Shen,Chenghao Zhao,Jing Zhong,Peng Du,Haidong Bian,Pan Li,Liangbao Yang,Jian Lu,Yang Yang Li
Plasmon-mediated chemical reactions (PMCRs) possess desirable opportunities for manipulating the reaction outcomes due to the unique impact from surface plasmons. However, achieving PMCR product selectivity by tuning the light wavelength has rarely been demonstrated and the underlying mechanism of product selectivity remains elusive. This work studies the reaction mechanism of one classical type of PMCR, plasmon-aided reduction of p-nitrothiophenol (PNTP), and discovers that the reduction product of PNTP can be easily manipulated by adjusting the excitation light wavelength due to the different thermal and hot-electron effects induced by the different wavelengths. Specifically, the sole product of p,p′-dimercaptoazobenzene is obtained under 514 nm light due to the dominant thermal effect thus created, whereas p-aminothiophenol is more favorably produced under 785 nm light, which enables more efficient generation of hot electrons.
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