物理化学学报 >> 2016, Vol. 32 >> Issue (3): 683-690.doi: 10.3866/PKU.WHXB201512302

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铀酰-Salophen受体对α, β-不饱和羰基化合物及手性客体的分子识别

高莎,兰文波,林英武,廖力夫,聂长明*()   

  • 收稿日期:2015-11-10 发布日期:2016-03-04
  • 通讯作者: 聂长明 E-mail:niecm196132@163.com
  • 基金资助:
    国家自然科学基金(11275090);湖南省自然科学基金(12JJ9006, 2015JJ1012);湖南省教育厅科学研究基金(12A116)

Molecular Recognition of α, β-Unsaturated Carbonyl Compounds and Chiral Guests by Uranyl-Salophen Receptors

Sha GAO,Wen-Bo LAN,Ying-Wu LIN,Li-Fu LIAO,Chang-Ming NIE*()   

  • Received:2015-11-10 Published:2016-03-04
  • Contact: Chang-Ming NIE E-mail:niecm196132@163.com
  • Supported by:
    the National Natural Science Foundation of China(11275090);Natural Science Foundation of Hunan Province, China(12JJ9006, 2015JJ1012);Scientific Research Fund of Hunan Provincial Education Department, China(12A116)

摘要:

基于密度泛函理论(DFT)的计算方法,研究了不对称铀酰-salophen受体对α, β-不饱和羰基化合物客体及手性小分子的分子识别。理论计算结果表明:配合物中受体的U原子与客体的O3原子配位,且受体与客体之间结合能随受体上芳环取代基的增大而增大; R2, R3-系列配合物中U―O3键的稳定性比R1-系列的更强;配位后的α, β-不饱和羰基化合物中C=C与C=O之间的共轭效应减弱。而且,通过圆二色谱(CD)及结合能计算表明:芘基铀酰-salophen (受体3)对(R)-1-(2-萘基)乙胺的分子识别选择性优于(S)-1-(2-萘基)乙胺。因而,这些研究结果为不对称铀酰-salophens具有分子识别能力提供了新的信息。

关键词: 密度泛函理论, 铀酰-salophen, α, β-不饱和羰基化合物, 分子识别

Abstract:

Based on density functional theory (DFT) calculations, the molecular recognition of α, β-unsaturated carbonyl compounds and chiral molecules by uranyl-salophen receptors was investigated theoretically. The results showed that the U atom of the receptors was coordinated by the O3 atom of the guests, and the binding energies between receptors and guests increased with the enlargement of the aromatic substituent of the uranylsalophen receptors. In addition, the U―O3 coordination bonds of R2-and R3-series complexes are more stable than those of R1-series complexes, and the conjugation between the C=C and C=O bonds of the α, β-unsaturated carbonyl compounds in the coordination complexes was weakened. Moreover, according to circular dichroism (CD) spectra and binding-energy calculations, the molecular-recognition selectivity of an asymmetrical pyrenyl uranyl-salophen (receptor 3) for (R)-1-(2-naphthyl)ethylamine was much higher than that for (S)-1-(2-naphthyl)ethylamine. These results shed new light on the recognition ability of asymmetric uranyl-salophens.

Key words: Density functional theory, Uranyl-salophen, α, β-Unsaturated carbonyl compound, Molecular recognition

MSC2000: 

  • O641