PI-SCF STUDIES OF CIRCULAR DICHROISM AND ELECTRONIC SPECTRA OF ALKALOIDS CONTAINING ANILINE CHROMOPHORE - STEREOCHEMICAL CONFIGURATION OF CALYCANTHINE AND CARACURINE-II
PI-SCF STUDIES OF CIRCULAR DICHROISM AND ELECTRONIC SPECTRA OF ALKALOIDS CONTAINING ANILINE CHROMOPHORE - STEREOCHEMICAL CONFIGURATION OF CALYCANTHINE AND CARACURINE-II
复制标题
DOI：
10.1039/j29710000691
复制
发表时间：
1971-01-01
期刊：
影响因子：
--
通讯作者：
ROBERTS, DR
中科院分区：
文献类型：
--
作者：
BRICKELL, WS;MASON, SF;ROBERTS, DR
吸收和 c.d.花萼花碱和箭毒碱-II 的光谱已扩展至 53 kK，并且使用偶极速度程序在 π-SCF 近似中计算了两种生物碱的 π→π* 跃迁能以及偶极和旋转强度。理论吸收和 c.d.通过使用高斯带形函数的曲线绘图仪，从计算量中获得了生物碱的光谱。针对先前分配的两种生物碱的构型计算的光谱再现了具有正确顺序的量值的实验曲线的定性形式。发现 π-SCF 计算支持电子态的点偶极激子处理和手性二聚 π 系统的立体化学构型的一般特征，在后一种方法适用的情况下，例如calycanthine，但前一种方法范围更广，涵盖案例，例如卡拉库林-II，后者失败。
The absorption and c.d. spectra of calycanthine and caracurine-II have been extended to 53 kK, and the π→π* transition energies and dipole and rotational strengths of the two alkaloids have been calculated in the π-SCF approximation using the dipole-velocity procedure. Theoretical absorption and c.d. spectra have been obtained for the alkaloids from the calculated quantities with a curve-plotter using a Gaussian band-shape function. The spectra computed for the previously assigned configurations of the two alkaloids reproduce the qualitative form of the experimental curves with magnitudes of the correct order. The π-SCF calculations are found to support the general features of the point–dipole exciton treatment of the electronic states and stereochemical configuration of chiral dimeric π-systems in cases where the latter method is applicable, e.g. calycanthine, but the former method is of wider scope and covers cases, e.g. caracurine-II where the latter fails.