Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designi...Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge.Here we report two discrete trefoil-shaped metallacycle S1 and metallacage s2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands.The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic'Mitsubishi motif.The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2.The formed metallacage S2 possesses a molecular weight up to 36 kDa,diameter 6.6 nm and height 3.0 nm.All supramolecular coordination complexes were fully characterized by NMR spectroscopy(^(1)H NMR,2D COSY,2D NOESY,2D DOSY),high-resolution electrospray ionization mass sectrometry ESI-MS.ESI-TWIM-MS,TEM and AFM.展开更多
A trefoil-like two-dimensional(2D)C_(3v) symmetric organic[12]-imidazolium cation H_(12)-2(PF_(6))_(12) featuring three[4]-imidazolium macrocycles was synthesized in three steps.The reaction of a dodecakis H_(12)-1(PF...A trefoil-like two-dimensional(2D)C_(3v) symmetric organic[12]-imidazolium cation H_(12)-2(PF_(6))_(12) featuring three[4]-imidazolium macrocycles was synthesized in three steps.The reaction of a dodecakis H_(12)-1(PF_(6))_(12) imidazolium salt with Ag_(2)O resulted in the formation of a hexanuclear AgI dodecacarbene assembly[Ag_(6)(1)](PF_(6))_(6).Upon UV irradiation,the photodimerization of the cinnamic ester pendants of[Ag_(6)(1)](PF_(6))_(6) led to the generation of a trefoil-like complex[Ag_(6)(2)](PF_(6))_(6) containing three closed metallacycles.Removal of metal ions allowed for the synthesis of the target molecule.All complexes were fully characterized by NMR spectroscopy(^(1)H,^(13)C{^(1)H}and 2D NMR)and high-resolution electrospray ionization mass spectrometry(HR-ESI-MS).展开更多
基金supported by the National Natural Science Foundation of China(Nos.22101060 for M.C.,and 21971257 for P.w.)the Guangdong Natural Science Foundation(No.2022A1515012187 to M.C.)the Science and Technology Research Project of Guangzhou(Nos.202201020201 for M.C.and 202102010432 for ZJ..Science and technology support plan of Guizhou Province[2019]2860 for W.L.The authors gratefully acknowledge the Center for Advanced Research in CSU for the NMR measurements.
文摘Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge.Here we report two discrete trefoil-shaped metallacycle S1 and metallacage s2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands.The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic'Mitsubishi motif.The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2.The formed metallacage S2 possesses a molecular weight up to 36 kDa,diameter 6.6 nm and height 3.0 nm.All supramolecular coordination complexes were fully characterized by NMR spectroscopy(^(1)H NMR,2D COSY,2D NOESY,2D DOSY),high-resolution electrospray ionization mass sectrometry ESI-MS.ESI-TWIM-MS,TEM and AFM.
基金financial support from the National Natural Science Foundation of China(Nos.22025107,21722105,22101225)the National Youth Top-notch Talent Support Program of China+1 种基金the Key Science and Technology Innovation Team of Shaanxi Province(Nos.2019TD-007,2019JLZ-02)the FM&EM International Joint Laboratory of Northwest University.
文摘A trefoil-like two-dimensional(2D)C_(3v) symmetric organic[12]-imidazolium cation H_(12)-2(PF_(6))_(12) featuring three[4]-imidazolium macrocycles was synthesized in three steps.The reaction of a dodecakis H_(12)-1(PF_(6))_(12) imidazolium salt with Ag_(2)O resulted in the formation of a hexanuclear AgI dodecacarbene assembly[Ag_(6)(1)](PF_(6))_(6).Upon UV irradiation,the photodimerization of the cinnamic ester pendants of[Ag_(6)(1)](PF_(6))_(6) led to the generation of a trefoil-like complex[Ag_(6)(2)](PF_(6))_(6) containing three closed metallacycles.Removal of metal ions allowed for the synthesis of the target molecule.All complexes were fully characterized by NMR spectroscopy(^(1)H,^(13)C{^(1)H}and 2D NMR)and high-resolution electrospray ionization mass spectrometry(HR-ESI-MS).
