Liu Yan-Zhi, Yuan Kun, Lv Ling-Ling, Zhu Yuan-Cheng, Yuan Zhao
†College of Chemical Engineering and Technology, Key Laboratory for New Molecule Materials Design and Function of Gansu Universities, Tianshui Normal University, Tianshui 741001, China.
§Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
J Phys Chem A. 2015 Jun 4;119(22):5842-52. doi: 10.1021/acs.jpca.5b02952. Epub 2015 May 13.
A novel urea-based anion receptor with an electron-deficient aromatic structural unit, N-p-nitrophenyl-N-(4-vinyl-2-five-fluoro-benzoic acid benzyl ester)-phenyl-urea (FUR), was designed to probe the potential for halide-anion recognition through the cooperation of two distinct noncovalent interactions including hydrogen bonds and anion-π in this work. The nature of the recognition interactions between halide-anion and the designed receptor was theoretically investigated at the molecular level. The geometric features of the hydrogen bond and anion-π of the FUR@X(-) (X = F, Cl, Br, and I) systems were thoroughly investigated. The binding energies and thermodynamic information on the halide-anion recognitions show that the presently designed FUR might selectively recognize anion F(-) based on the cooperation of the N-H···F(-) hydrogen bond and anion-π interactions both in vacuum and in solvents. IR and UV-visible spectra of free FUR and FUR@F(-) have been simulated and discussed qualitatively, which may be helpful for further experimental investigations in the future. Additionally, the electronic properties and behaviors of the FUR@X(-) systems were discussed according to the calculations on the natural bond orbital (NBO) data, molecular electrostatic potential (MEP), and weak interaction regions.
在本研究中，设计了一种具有缺电子芳香结构单元的新型基于尿素的阴离子受体，即N-对硝基苯基-N-(4-乙烯基-2,5-二氟苯甲酸苄酯)-苯基脲（FUR），以通过氢键和阴离子-π两种不同非共价相互作用的协同作用来探究卤化物阴离子识别的可能性。在分子水平上从理论上研究了卤化物阴离子与设计受体之间识别相互作用的本质。深入研究了FUR@X(-)（X = F、Cl、Br和I）体系中氢键和阴离子-π的几何特征。卤化物阴离子识别的结合能和热力学信息表明，目前设计的FUR在真空和溶剂中可能基于N-H···F(-)氢键和阴离子-π相互作用的协同作用选择性识别阴离子F(-)。对游离FUR和FUR@F(-)的红外光谱和紫外可见光谱进行了模拟并进行了定性讨论，这可能有助于未来进一步的实验研究。此外，根据自然键轨道（NBO）数据、分子静电势（MEP）和弱相互作用区域的计算，讨论了FUR@X(-)体系的电子性质和行为。
