Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess
Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess
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DOI：
10.1007/s11705-019-1869-1
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发表时间：
2020-01
影响因子：
4.5
通讯作者：
D. Payne;M. Chahal;Václav Březina;Whitney A Webre;K. Ariga;F. D’Souza;J. Labuta;Jonathan P. Hill
中科院分区：
文献类型：
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作者：
D. Payne;M. Chahal;Václav Březina;Whitney A Webre;K. Ariga;F. D’Souza;J. Labuta;Jonathan P. Hill
合成了手性1，1 ′-联萘双卟啉“镊子”（R）-1/（S）-1和相应的锌（II）配合物（R）-2/（S）-2，并评价了它们在手性分析（特别是对映体过量（ee）测定）中的应用。三（1-正十二烷基）卟啉首次被用作相互作用单元。用（R，R）-和（S，S）-环己烷-1，2-二胺（CHDA）滴定法研究了双卟啉镊子的主体性能。通过紫外-可见光谱、圆二色性（CD）、荧光发射光谱和核磁共振氢谱（1H-NMR）等方法，可以将主体分子用作多通道探针。手性构型也可以使用CD或1H-NMR光谱进行区分。考虑到所用的低浓度，所有三种光学技术都能以合理的灵敏度提供良好的分辨率。10 - 6mol·L-1）。由于（R，R）-和（S，S）-CHDA的共振峰分离得相当好，因此用NMR光谱法测定CHDA对映体也是可能的。非金属化的（R）-1/（S）-1主体不能用于检测强酸性手性客体中的手性信息。本工作证明了1，1 '-联萘手性主体在手性分析中的应用。
Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1and the corresponding zinc(II) complexes (R)-2/(S)-2were 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 ofeeby using UV-vis, circular dichroism (CD), fluorescence emission and1H nuclear magnetic resonance (1H-NMR) methods. Chiral configurations could also be differentiated using CD or1H-NMR spectroscopy. All three optical techniques give good resolution ofeewith reasonable sensitivity considering the low concentrations used (ca. 10−6mol·L−1). Theeedetermination 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)-1hosts 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.