Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Ren Min Street No. 5268, Changchun, Jilin 130024, PR China.
J Mol Graph Model. 2013 Jul;44:26-32. doi: 10.1016/j.jmgm.2013.05.001. Epub 2013 May 10.
The ultraviolet-visible and electronic circular dichroism (UV-vis/ECD) spectra of diphosphonate-functionalized asymmetric cantilever-type chiral polyoxomolybdate (POM) enantiomer R-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-) (R) were systematically investigated using time-dependent density functional theory (TDDFT) method. From the view of molecular structure and relative energy, we inferred that there is likely a structural conversion from enantiomers R to S-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-) (S) via the intermediate configuration (IN). The ECD spectra of the enantiomer R were produced over the range of 3.0-6.3eV. The UV-vis and ECD spectra of enantiomer R in the gas phase and different solvents were calculated. The results reveal that the UV-vis and ECD spectra of the chiral POM in gas phase, polar solvent, or non-polar solvent are different. The calculated electron density difference maps (EDDMs) display that the POM cluster is a chiroptical chromophore in studied compound.
采用含时密度泛函理论（TDDFT）方法系统研究了手性二膦酸功能化不对称悬臂型多金属氧酸盐（POM）对映体 R-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-)（R）的紫外-可见和电子圆二色性（UV-vis/ECD）光谱。从分子结构和相对能量的角度来看，我们推断可能会通过中间体构型（IN）从对映体 R 转变为 S-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-)（S）。对映体 R 的 ECD 光谱在 3.0-6.3eV 范围内产生。计算了对映体 R 在气相和不同溶剂中的 UV-vis 和 ECD 光谱。结果表明，手性 POM 在气相、极性溶剂或非极性溶剂中的 UV-vis 和 ECD 光谱不同。计算的电子密度差图（EDDMs）显示 POM 簇是研究化合物中手性发色团。
