摘要
In the field of metallo-organic helicates,the controlled synthesis of low-symmetric structures remains a significant challenge due to the need for the precise control over the self-assembly process due to their thermodynamically disfavored nature,compared to highly symmetric forms.This study introduces an effective strategy by shifting the design focus from ligands to metal centers.Through precise regulation of the stereoconfiguration,two metal centers are directed to adopt opposite handedness,affording a mesomeric and C_(1) symmetric helicate structure S,fully characterized by ^(1)H NMR,ESI-MS and SC-XRD analyses.The resulting helicate structure features a well-defined square cavity with an 8.5Å distance between the roof and the floor,capable of accommodating planar polycyclic aromatic hydrocarbons(PAHs)via π-π stacking interactions within the optimal range after slight compression.More importantly,the binding constants show a proportional enhancement with the increase in the number of π-electrons and π-areas in PAH vips.This work points toward a new direction for developing functional low-symmetric metallo-organic supramolecular assemblies.In addition,the clear structure-function relationship highlights their potential applications in molecular separation and sensing.
基金
supported by the National Natural Science Foundation of China(22471047 to Z.Z.,22401054 to T.W.)
the National Key Research and Development Program(2024YFC3907900 to P.W.)
the Major Science and Technology Projects of Yunnan Province(202302AB080016 to P.W.)
the Natural Science Foundation of Guangdong Province-Youth Enhancement Programme(2024A1515030235 to Z.Z.)
the Guangdong Basic and Applied Basic Research Foundation(2023A1515110911 to T.W.)
the 2023 Educational Quality and Teaching Reform Project(23Y2401JG2412X008 to Q.L.)
2024 Guangzhou University Instrument and Equipment Open Sharing Fund.
