The study of the chiroptical properties of thin-film samples of two chiral benzo[1,2-b:4,5-b’]dithiophene-based oligothiophenes with optoelectronic properties was carried out at Diamond B23 beamline using the synchro...The study of the chiroptical properties of thin-film samples of two chiral benzo[1,2-b:4,5-b’]dithiophene-based oligothiophenes with optoelectronic properties was carried out at Diamond B23 beamline using the synchrotron radiation electronic circular dichroism imaging(SR-ECDi)facility.The experimental results support the hypothesis that the non-reciprocal circularly polarized absorption observed in these materials is due to the combined linear dichroism and linear birefringence contributions.The mapping at 50-μM spatial resolution revealed that several species coexist in the mesoscopic chiral domains likely due to different aggregated phases,which were identified in the films by SR-ECDi but could not be detected with benchtop ECD instruments.展开更多
A highly distorted chiral nanographene structure composed of triple corannulene-fused[5]helicenes is prepared with the help of the Heck reaction and oxidative photocyclization with an overall isolated yield of 28%.The...A highly distorted chiral nanographene structure composed of triple corannulene-fused[5]helicenes is prepared with the help of the Heck reaction and oxidative photocyclization with an overall isolated yield of 28%.The complex three-dimensional(3D)structure of the bowl-helix hybrid nanostructure is studied by a combination of noncontact atomic force microscopy(AFM)and scanning tunneling microscopy(STM)on the Cu(111)surface,density functional theory calculations,AFM/STM simulations,and high-performance liquid chromatography-electronic circular dichroism analysis.This examination reveals a molecular structure in which the three bowl-shaped corannulene bladesd position themselves in a C3-symmetric fashion around a highly twisted triphenylene core.The molecule appears to be shaped like a propeller in which the concave side of the bowls face away from the connected[5]helicene motif.The chirality of the nanostructure is confirmed by the direct visualization of both MMM and PPP enantiomers at the single-molecule level by scanning probe microscopies.These results underline that submolecular resolution imaging by AFM/STM is a powerful real-space tool for the stereochemical characterization of 3D curved chiral nanographene structures.展开更多
文摘The study of the chiroptical properties of thin-film samples of two chiral benzo[1,2-b:4,5-b’]dithiophene-based oligothiophenes with optoelectronic properties was carried out at Diamond B23 beamline using the synchrotron radiation electronic circular dichroism imaging(SR-ECDi)facility.The experimental results support the hypothesis that the non-reciprocal circularly polarized absorption observed in these materials is due to the combined linear dichroism and linear birefringence contributions.The mapping at 50-μM spatial resolution revealed that several species coexist in the mesoscopic chiral domains likely due to different aggregated phases,which were identified in the films by SR-ECDi but could not be detected with benchtop ECD instruments.
基金Financial support from the Ministry of Education Singapore under the AcRF Tier 1(MOE T1 RG11/21)and AcRF Tier 2(MOE-T2EP10221-0002)The Deutsche Forschungsgemeinschaft via grants(nos.SCHI 619/13 and EB535/1-1)+5 种基金the GRK(Research Training Group)2204“Substitute Materials for Sustainable Energy Technologies”the LOEWE Program of Excellence of the Federal State of Hesse(LOEWE Focus Group PriOSS“Principles of On-Surface Synthesis”)the National Natural Science Foundation of China(grant nos.21790053,51821002,and 22072103)the National Major State Basic Research Development Program of China(grant nos.2017YFA0205000 and 2017YFA0205002)the Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 Project are also acknowledged for their financial support.
文摘A highly distorted chiral nanographene structure composed of triple corannulene-fused[5]helicenes is prepared with the help of the Heck reaction and oxidative photocyclization with an overall isolated yield of 28%.The complex three-dimensional(3D)structure of the bowl-helix hybrid nanostructure is studied by a combination of noncontact atomic force microscopy(AFM)and scanning tunneling microscopy(STM)on the Cu(111)surface,density functional theory calculations,AFM/STM simulations,and high-performance liquid chromatography-electronic circular dichroism analysis.This examination reveals a molecular structure in which the three bowl-shaped corannulene bladesd position themselves in a C3-symmetric fashion around a highly twisted triphenylene core.The molecule appears to be shaped like a propeller in which the concave side of the bowls face away from the connected[5]helicene motif.The chirality of the nanostructure is confirmed by the direct visualization of both MMM and PPP enantiomers at the single-molecule level by scanning probe microscopies.These results underline that submolecular resolution imaging by AFM/STM is a powerful real-space tool for the stereochemical characterization of 3D curved chiral nanographene structures.
