Abstract

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.

中文翻译：

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双卟啉钳用于对映体过量的多通道光谱分析

摘要

制备手性1,1'-联萘连接的双卟啉镊子（R）-1 /（S）-1和相应的锌（II）络合物（R）-2 /（S）-2作为手性宿主分子，并评估了其在手性分析中的效用（尤其是对映体过量（ee）的测定）。三（1- n-十二烷基）卟啉首次用作相互作用单元。用（R，R）-和（S，S滴定法）研究了卟啉镊的宿主能力。）-环己烷-1,2-二胺（CHDA）。通过使用紫外可见，圆二色性（CD），荧光发射和¹ H核磁共振（¹ H-NMR）方法，宿主分子可用作ee的多通道探针。手性构型也可以使用CD或¹ H-NMR光谱进行区分。所有这三个光学技术得到良好的分辨率EE与合理的灵敏度考虑所使用的低浓度（约10 ^-6莫尔^-1）。该ee值使用NMR光谱法CHDA对映体的确定也是可能的，因为在（情况下的合理的良好分离的共振- [R ，- [R）和（S，S）-CHDA。非金属化（R）-1 /（S）-1宿主不能用于检测强酸性手性客体中的手性信息。这项工作证明了1,1'-联萘基连接的手性宿主在对位相互作用的对映异构体的手性分析中的实用性。