Hu Tingting, Hu Chuanjiang, Wang Yong, Young David James, Lang Jian-Ping
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, P. R. China.
Dalton Trans. 2018 Apr 17;47(15):5503-5512. doi: 10.1039/c8dt00326b.
We have designed and synthesized a novel amide-linked bisporphyrin with a 2-naphthalenecarboxamide substituent on the linker. The chirality sensing ability of this zinc porphyrinate towards chiral monoamines has been examined. Circular dichroism studies indicate chirality transfer from chiral monoamines to the corresponding host-guest complexes. Interestingly, when optically pure 1-(1-naphthyl)ethylamine is used as a guest, stoichiometrically controlled chirality inversion occurs in the formation of the corresponding zinc bisporphyrinate-monoamine complexes. Both CD and NMR spectra indicate that 1 : 1 and 1 : 2 complexes are formed in solution. DFT calculations suggest that steric interactions between the substituent of the linker and the guest in the 1 : 2 complex are responsible for this unprecedented observation. Our studies provide a unique bisporphyrin system for demonstrating that chirality transfer to the host can be tuned by changing the substituent of the linker.
我们设计并合成了一种新型的酰胺连接双卟啉，其连接基团上带有2-萘甲酰胺取代基。研究了这种锌卟啉对手性单胺的手性传感能力。圆二色性研究表明手性从手性单胺转移到相应的主客体配合物中。有趣的是，当使用光学纯的1-(1-萘基)乙胺作为客体时，在相应的双锌卟啉-单胺配合物形成过程中会发生化学计量控制的手性反转。CD和NMR光谱均表明在溶液中形成了1:1和1:2的配合物。DFT计算表明，1:2配合物中连接基团的取代基与客体之间的空间相互作用是造成这一前所未有的现象的原因。我们的研究提供了一个独特的双卟啉体系，用于证明可以通过改变连接基团的取代基来调节向主体的手性转移。
