...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Origins of the Electronic Modulations of Bacterio- and Isobacteriodilactone Regioisomers
【24h】

Origins of the Electronic Modulations of Bacterio- and Isobacteriodilactone Regioisomers

机译：细菌和异丙嘧啶的电子调节的起源

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

( )Advances in the utilization of porphyrinoids for photomedicine, catalysis, and artificial photosynthesis require a fundamental understanding of the relationships between their molecular connectivity and resulting electronic structures. Herein, we analyze how the replacement of two pyrrolic C-beta=C-beta bonds of a porphyrin by two lactone (O=C-O) moieties modulates the ground-state thermodynamic stability and electronic structure of the resulting five possible pyrrole-modified porphyrin isomers. We made these determinations based on density functional theory (DFT) and timedependent DFT computations of the optical spectra of all regioisomers. We also analyzed the computed magnetically induced currents of their aromatic pi-systems. All regioisomers adopt the tautomeric state that maximizes aromaticity, whether or not transannular steric strains are incurred. In all isomers, the O=C-beta-O-beta bonds were found to support a macrocycle diatropic ring current. We attributed this to the delocalization of nonbonding electrons from the ring oxa- and oxo-atoms into the macrocycle. As a consequence of this delocalization, the dilactone regioisomers are as-or even more-aromatic than their hydroporphyrin congeners. The electronic structures follow different trends for the bacteriochlorin- and isobacteriochlorin-type isomers. The presence of either oxo- or oxa-oxygens conjugated with the macrocyclic pi-system was found to be the minimal structural requirement for the regioisomers to exhibit distinct electronic properties. Our computational methods and mechanistic insights provide a basis for the systematic exploration of the physicochemical properties of porphyrinoids as a function of the number, relative orientation, and degree of macrocycle-pi-conjugation of beta-substituents, in general, and for dilactone-based porphyrinic chromophores, in particular.
机译：（）进展在利用卟啉卟啉，用于光学麦嘌呤，催化和人造光合作用需要对其分子连通性和导致电子结构之间的关系的基本理解。在此，通过两个内酯（O = CO）部分分析卟啉的两个吡咯型C-β= C-β键的替代方法是如何调节所得五种可能的吡咯改性卟啉异构体的地 - 状态热力学稳定性和电子结构。我们基于密度泛函理论（DFT）和所有测定的光谱的定期依赖性DFT计算来实现这些测定。我们还分析了计算的磁性诱导的芳香PI-Systems的电流。所有测定剂采用互变异构质状态，最大化芳香性，无论是无周无形的空间菌株是否都是如此。在所有异构体中，发现o = C-β-O-β键支持大环倾角环电流。我们将其归因于从戒指和氧代原子中的非合金电子的临近化，进入宏循环。由于这种临床化的结果，稀释酮的测定剂比其水多滤液同源物如 - 或甚至更芳香。电子结构遵循菌种和异丙菌型异构体的不同趋势。发现与大环PI-System缀合的氧代或氧气 - 氧式的存在是具有表现出不同电子性质的最小结构要求。我们的计算方法和机械洞察力为β-取代基的常规，相对取向和β-取代基的宏细胞缀合度的函数提供了系统探索的基础，通常，以及基于稀释酮卟啉发色团，特别是。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号