Navrátilová Tereza, Dobšíková Kristýna, Králík František, Havlík Martin, Tatar Ameneh, Drozdová Michaela, Anzenbacher Pavel, Dolenský Bohumil
Department of Analytical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28 Praha, Czech Republic.
Department of Chemistry, Bowling Green State University, Bowling Green, OH 43403, USA.
Spectrochim Acta A Mol Biomol Spectrosc. 2024 Aug 5;316:124308. doi: 10.1016/j.saa.2024.124308. Epub 2024 Apr 17.
The chiral properties of nickel(II) complexes of porphyrin-porphyrin Tröger's base and porphyrin-chlorin spiro-Tröger's base with phenyl or 3-methoxyphenyl substitutions in their meso-positions were studied. Enantioseparation of racemic mixtures was investigated via high-performance liquid chromatography (HPLC) on an analytical ReproSil Chiral-NR column. The optimal conditions were utilized for a multimilligram scale isolation with a semipreparative column. The purity of the isolated enantiomers was determined by HPLC and UV-Vis spectroscopy. The absolute configurations of the isolated enantiomers were determined by evaluating the Cotton effect in electronic circular dichroism spectra. The determination was supported by TDDFT calculations, in which good agreement was achieved between the experimental and simulated spectra. The maximum molar ellipticity values, [θ] given in deg ∙ cm ∙ dmol, were [θ] = 1.73 ∙ 10 for phenyl spiroTB and [θ] = 1.24 ∙ 10 and [θ] = 2.15 ∙ 10 for 3-methoxyphenyl TB and spiroTB, respectively.
研究了卟啉-卟啉特罗格碱以及卟啉-二氢卟吩螺环特罗格碱的镍（II）配合物在中位带有苯基或3-甲氧基苯基取代基时的手性性质。通过在分析型ReproSil Chiral-NR柱上进行高效液相色谱（HPLC）研究了外消旋混合物的对映体分离。利用最佳条件通过半制备柱进行多毫克规模的分离。通过HPLC和紫外-可见光谱法测定分离出的对映体的纯度。通过评估电子圆二色光谱中的科顿效应来确定分离出的对映体的绝对构型。该测定得到了含时密度泛函理论（TDDFT）计算的支持，实验光谱与模拟光谱之间取得了良好的一致性。以度∙厘米∙dmol给出的最大摩尔椭圆率值[θ]，对于苯基螺环特罗格碱为[θ]=1.73∙10，对于3-甲氧基苯基特罗格碱和螺环特罗格碱分别为[θ]=1.24∙10和[θ]=2.15∙10。
