Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by...Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half-sandwich binuclear rhodium(III)/iridium(III) building blocks.The selective synthesis was realized by adjusting the length of dipyridyl arms.The utilization of curved U-shaped bipyridyl ligand L1 led to tweezer-like molecular assemblies.Subsequently,olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2.The ligand L2 has two stable conformations,U-shape and Z-shape,which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work.These structures in solid and solution all have been further confirmed by single-crystal X-ray diffraction,NMR analysis,and mass spectrometry.In addition,as an important driving force,π-π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution.The experimental results demonstrated that compounds 1a and 2 had good NIR photothermal conversion efficiency (11.83% and 17.76%),and further analysis found the photothermal conversion efficiency had a gradual increase in the trend with the π-π stacking interactions increasing.This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.展开更多
series of Cp＊Rh-based molecular Borromean rings （BRs） are prepared from naphthazarine or metallaligand. Some of as-synthesized BRs display high stability and are formed in high yields in solution. The reason is rel...series of Cp＊Rh-based molecular Borromean rings （BRs） are prepared from naphthazarine or metallaligand. Some of as-synthesized BRs display high stability and are formed in high yields in solution. The reason is related to the length ratio of the long-arm linker and short-arm linker, where smaller aspect ratios of the metallarectangles promote improved stability and yields of the BRs in solution, increasing the width of the metallaligand or pyridyl ligand hinders the formation of BRs and leads to unoccupied monomeric rectangles, which were further used as catalysts for the acyl transfer reaction between N-acetylimidazole and （4-（pyridin-4-yl）phenyl） methanol.展开更多
Herein,we report an artificially assembled interlocked system that features adaptive self-assembly and induced-fit transformation properties in the presence of appropriate guest molecules.By careful choice of solvent ...Herein,we report an artificially assembled interlocked system that features adaptive self-assembly and induced-fit transformation properties in the presence of appropriate guest molecules.By careful choice of solvent and guests,a molecular Borromean rings complex based on organometallic half-sandwich units could be transformed in a stepwise manner to a ring-in-ring complex and a monomeric rectangle,leading to a conversion cycle between these structures.This adaptive self-assembly method was further applied to the construction of a Russian dolls complex,forming another conversion cycle composed of a molecular Borromean rings complex,a Russian dolls complex and a monomeric rectangle.A comprehensive map showing all of the structural transformations between these metallarectangles and interlocked species is drawn up,representing a recoverable and recyclable transformation mechanism.展开更多
We have carried out calculations to search Borromean windows(BWs) for 11 different three-body systems interacting with screened Coulomb(Yukawa-type) potentials using Hylleraas-type wave functions within the framework ...We have carried out calculations to search Borromean windows(BWs) for 11 different three-body systems interacting with screened Coulomb(Yukawa-type) potentials using Hylleraas-type wave functions within the framework of a variational approach. The critical values of the screening parameters for the ground states of the systems under consideration are reported for which the three-body systems are stable, while all the possible fragments are unbound;that is, it shows windows for Borromean binding.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22031003,21720102004)the Shanghai Science Technology Committee(No.19DZ2270100)G.-X.J.thanks the Alexander von Humboldt Foundation for a Humboldt Research Award.
文摘Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half-sandwich binuclear rhodium(III)/iridium(III) building blocks.The selective synthesis was realized by adjusting the length of dipyridyl arms.The utilization of curved U-shaped bipyridyl ligand L1 led to tweezer-like molecular assemblies.Subsequently,olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2.The ligand L2 has two stable conformations,U-shape and Z-shape,which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work.These structures in solid and solution all have been further confirmed by single-crystal X-ray diffraction,NMR analysis,and mass spectrometry.In addition,as an important driving force,π-π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution.The experimental results demonstrated that compounds 1a and 2 had good NIR photothermal conversion efficiency (11.83% and 17.76%),and further analysis found the photothermal conversion efficiency had a gradual increase in the trend with the π-π stacking interactions increasing.This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.
基金This work was supported by the National Natural Science Foundation of China （21531002, 21720102004）, the Program for Changjiang Scholars and Innovative Research Team in University （IRT-15R12） and the Shanghai Science Technology Committee （13JC1400600） and China Postdoctoral Science Foundation （2015M581517） GXJ thanks the Alexander von Humboldt Foundation for a Humboldt Research Award.
文摘series of Cp＊Rh-based molecular Borromean rings （BRs） are prepared from naphthazarine or metallaligand. Some of as-synthesized BRs display high stability and are formed in high yields in solution. The reason is related to the length ratio of the long-arm linker and short-arm linker, where smaller aspect ratios of the metallarectangles promote improved stability and yields of the BRs in solution, increasing the width of the metallaligand or pyridyl ligand hinders the formation of BRs and leads to unoccupied monomeric rectangles, which were further used as catalysts for the acyl transfer reaction between N-acetylimidazole and （4-（pyridin-4-yl）phenyl） methanol.
基金This work was supported by the National Science Foundation of China(Nos.21531002,21720102004,21801045,22031003)the Shanghai Science and Technology Committee(No.19DZ2270100).
文摘Herein,we report an artificially assembled interlocked system that features adaptive self-assembly and induced-fit transformation properties in the presence of appropriate guest molecules.By careful choice of solvent and guests,a molecular Borromean rings complex based on organometallic half-sandwich units could be transformed in a stepwise manner to a ring-in-ring complex and a monomeric rectangle,leading to a conversion cycle between these structures.This adaptive self-assembly method was further applied to the construction of a Russian dolls complex,forming another conversion cycle composed of a molecular Borromean rings complex,a Russian dolls complex and a monomeric rectangle.A comprehensive map showing all of the structural transformations between these metallarectangles and interlocked species is drawn up,representing a recoverable and recyclable transformation mechanism.
基金Supported by the National Natural Science Foundation of China under Grant No.11304086the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province of China under Grant No.UNPYSCT-2015019the Natural Science Foundation for Distinguished Young Scholars in Heilongjiang University under Grant No.JCL201503
文摘We have carried out calculations to search Borromean windows(BWs) for 11 different three-body systems interacting with screened Coulomb(Yukawa-type) potentials using Hylleraas-type wave functions within the framework of a variational approach. The critical values of the screening parameters for the ground states of the systems under consideration are reported for which the three-body systems are stable, while all the possible fragments are unbound;that is, it shows windows for Borromean binding.
