当前位置：
X-MOL 学术
›
Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Complexation of Chiral Zinc(II)Porphyrin Tweezer with Chiral Guests: Control, Discrimination and Rationalization of Supramolecular Chirality.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-05-08 , DOI: 10.1021/acs.inorgchem.0c00877 Bapan Saha 1 , Sk Asif Ikbal 1 , Sankar Prasad Rath 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-05-08 , DOI: 10.1021/acs.inorgchem.0c00877 Bapan Saha 1 , Sk Asif Ikbal 1 , Sankar Prasad Rath 1
Affiliation
|
A series of 1:1 sandwich complexes consisting of chiral zinc(II) bisporphyrin hosts and a series of chiral guests has been synthesized and has rationalized the underpinning mechanism of chirality transfer in the host–guest supramolecular assemblies. The number of stereogenic centers is also varied in both the host and guests, which provides insight into the overall helicity of the assembly. The interactions between the chiral host and chiral guests have been investigated by UV–visible, CD, and 1H NMR spectroscopic titrations along with extensive DFT studies. Interestingly, CD spectral changes are very different between chiral guests with one and two chiral centers. It has been observed that the sign of the CD couplet of the host–guest complexes is dictated by the chirality of the host only with guests having one chiral center. The match and mismatch of the chirality of the guest only affects the amplitude of the CD signal; the sign, however, remains intact. In sharp contrast, the helicity of the 1:1 sandwich complex is dictated by the chirality of the guests having two chiral centers. However, amplification of the CD couplet is observed upon matching of the chirality between the host and guest, while a mismatch leads to an inversion of the CD couplet. The enantiomeric host also displays similar trends with chiral guests but with opposite sign. The enantioselective host also displays excellent chiral discrimination ability toward enantiomeric guests with two chiral centers. The guest with the same chirality as the host binds much stronger as compared to its enantiomer. Remarkable enantiodiscrimination effects were also detected in the 1H NMR spectra of the diastereomeric complexes in which well-resolved separation of the signals is clearly visible. The theoretical calculations are consistent with those of the experiment.
中文翻译：
手性客人手性锌（II）卟啉镊子的络合物：超分子手性的控制，区分和合理化。
合成了由手性锌（II）双卟啉主体和一系列手性客体组成的一系列1：1夹心复合物，并使主体-客体超分子组装中的手性转移的基础机制合理化。在主持人和来宾中，立体生成中心的数量也各不相同，这使您可以深入了解程序集的整体螺旋度。通过紫外可见光，CD和1研究了手性宿主与手性客人之间的相互作用H NMR光谱滴定以及广泛的DFT研究。有趣的是，具有一个和两个手性中心的手性客人的CD光谱变化非常不同。已经观察到，只有客体具有一个手性中心时，主体-客体复合物的CD偶联的体征是由主体的手性决定的。客体手性的匹配和不匹配只会影响CD信号的幅度；但是，该标志保持不变。形成鲜明对比的是1：1三明治的螺旋度复杂性由拥有两个手性中心的客人的手性决定。但是，当宿主和客体之间的手性匹配时，会观察到CD对的扩增，而错配会导致CD对的反转。对映体宿主也表现出与手性客人相似的趋势，但符号相反。对映体选择性宿主对具有两个手性中心的对映体客人也显示出优异的手性鉴别能力。与主体具有相同手性的客体与其对映体相比，结合力更强。在1中还发现了显着的对映歧化作用非对映异构体配合物的1 H NMR光谱清晰可见。理论计算与实验一致。
更新日期：2020-05-08
中文翻译：
手性客人手性锌（II）卟啉镊子的络合物：超分子手性的控制，区分和合理化。
合成了由手性锌（II）双卟啉主体和一系列手性客体组成的一系列1：1夹心复合物，并使主体-客体超分子组装中的手性转移的基础机制合理化。在主持人和来宾中，立体生成中心的数量也各不相同，这使您可以深入了解程序集的整体螺旋度。通过紫外可见光，CD和1研究了手性宿主与手性客人之间的相互作用H NMR光谱滴定以及广泛的DFT研究。有趣的是，具有一个和两个手性中心的手性客人的CD光谱变化非常不同。已经观察到，只有客体具有一个手性中心时，主体-客体复合物的CD偶联的体征是由主体的手性决定的。客体手性的匹配和不匹配只会影响CD信号的幅度；但是，该标志保持不变。形成鲜明对比的是1：1三明治的螺旋度复杂性由拥有两个手性中心的客人的手性决定。但是，当宿主和客体之间的手性匹配时，会观察到CD对的扩增，而错配会导致CD对的反转。对映体宿主也表现出与手性客人相似的趋势，但符号相反。对映体选择性宿主对具有两个手性中心的对映体客人也显示出优异的手性鉴别能力。与主体具有相同手性的客体与其对映体相比，结合力更强。在1中还发现了显着的对映歧化作用非对映异构体配合物的1 H NMR光谱清晰可见。理论计算与实验一致。
京公网安备 11010802027423号