Control over geometric curvature and chirality of assemblies in pure aqueous media is key to the design of responsive materials and molecular machines.Here we show how aggregate geometric curvature and chirality of mo...Control over geometric curvature and chirality of assemblies in pure aqueous media is key to the design of responsive materials and molecular machines.Here we show how aggregate geometric curvature and chirality of motor amphiphiles could be switched from bicontinuous calabashes to nanoribbons or from vesicles to nanoribbons by modulating rotor orientation direction with dual light/heat stimuli to influence spontaneous curvature in assemblies.The photoisomerization and thermal helix inversion processes of molecular motors have been studied at the molecular level,and the transformation of supramolecular assemblies has been investigated at the microscopic level.The morphological evolution of the calabash-shaped assembly can be kinetically captured,suggesting that the bicontinuous calabash-shaped structures are different from the bowl-shaped aggregates based on solvent-driven assembly upon the addition of non-solvent or solvent.The investigation of dual optical/thermal control of rotor orientation can provide a new strategy for tuning the geometric curvature and chirality of nanoassemblies at the nanoscale,arriving ultimately the clusteroluminescence through-space electronic communication at responsive supramolecular nanosystems.展开更多
Chiral molecules, which may contain one or more different type（s） of stereocentres, such as central, axial, planar, and helical chiralities, etc., are indispensable in chemistry, pharmaceutical industry, and life sc...Chiral molecules, which may contain one or more different type（s） of stereocentres, such as central, axial, planar, and helical chiralities, etc., are indispensable in chemistry, pharmaceutical industry, and life science. Despite many advances for the preparation of chiral molecules usually with a single type of chirality have been realized, simultaneous construction of different types of chiralities is still a significant challenge. Here, we wish to report a protocol for preparation of chiral allenes with both central and axial chiralities via a catalytic asymmetric allenylation of different biologically or syn- thetically useful fluorinated or non-fluorinated nucleophiles with readily available racemic allenes by using a single chiral ligand. An echoing between the central chirality and axial chirality for the enantioselectivity was observed. This strategy provides a general and practical approach to functionalized optically active allenes bearing both central and axial chiralities with an excellent enantioselectivity under mild conditions.展开更多
基金Science and Technology Program of Guangzhou,Grant/Award Number:201804010017National Natural Science Foundation of China,Grant/Award Number:21374137+1 种基金Natural Science Foundation of Guangdong Province,Grant/Award Number:2014A030313194Science and Technology Program of Guangdong Province,Grant/Award Number:2017A050506021。
文摘Control over geometric curvature and chirality of assemblies in pure aqueous media is key to the design of responsive materials and molecular machines.Here we show how aggregate geometric curvature and chirality of motor amphiphiles could be switched from bicontinuous calabashes to nanoribbons or from vesicles to nanoribbons by modulating rotor orientation direction with dual light/heat stimuli to influence spontaneous curvature in assemblies.The photoisomerization and thermal helix inversion processes of molecular motors have been studied at the molecular level,and the transformation of supramolecular assemblies has been investigated at the microscopic level.The morphological evolution of the calabash-shaped assembly can be kinetically captured,suggesting that the bicontinuous calabash-shaped structures are different from the bowl-shaped aggregates based on solvent-driven assembly upon the addition of non-solvent or solvent.The investigation of dual optical/thermal control of rotor orientation can provide a new strategy for tuning the geometric curvature and chirality of nanoassemblies at the nanoscale,arriving ultimately the clusteroluminescence through-space electronic communication at responsive supramolecular nanosystems.
文摘Chiral molecules, which may contain one or more different type（s） of stereocentres, such as central, axial, planar, and helical chiralities, etc., are indispensable in chemistry, pharmaceutical industry, and life science. Despite many advances for the preparation of chiral molecules usually with a single type of chirality have been realized, simultaneous construction of different types of chiralities is still a significant challenge. Here, we wish to report a protocol for preparation of chiral allenes with both central and axial chiralities via a catalytic asymmetric allenylation of different biologically or syn- thetically useful fluorinated or non-fluorinated nucleophiles with readily available racemic allenes by using a single chiral ligand. An echoing between the central chirality and axial chirality for the enantioselectivity was observed. This strategy provides a general and practical approach to functionalized optically active allenes bearing both central and axial chiralities with an excellent enantioselectivity under mild conditions.
