Dynamic adaptability is a key feature in biological macromolecules,enabling selective binding and catalysis[1].From DNA supercoiling to enzyme conformational changes,biological systems have evolved intricate ways to d...Dynamic adaptability is a key feature in biological macromolecules,enabling selective binding and catalysis[1].From DNA supercoiling to enzyme conformational changes,biological systems have evolved intricate ways to dynamically adjust their structures to accommodate functional needs.Mimicking this adaptability in synthetic systems is an ongoing challenge in supramolecular chemistry.展开更多
Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric de...Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl) phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1C1C2N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units RhB1, RhB2, RhB3, and RhB4 featuring Cp*^(Rh^(Ⅲ)) (Cp* = η^(5)-pentam-ethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh 3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through pro-gramming different combination of noncovalent interactions (π-x stacking, CH..π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp*^(Irl^(Ⅲ)) analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.展开更多
A novel macrocycle based on conformation-adaptive and electron-rich dihydrophenazine was designed and synthesized.On the one hand,the macrocycle showed host-vip interactions with tetracyanoquinodimethane(TCNQ)drivin...A novel macrocycle based on conformation-adaptive and electron-rich dihydrophenazine was designed and synthesized.On the one hand,the macrocycle showed host-vip interactions with tetracyanoquinodimethane(TCNQ)driving by charge transfer interaction between them.Meanwhile,host-vip complexation was accompanied by fluorescence quenching and conformational change of the macrocycle.On the other hand,the oxidation of the macrocycle resulted in its diradical cation analogue and induced the release of the vip molecule TCNQ,thereby accomplishing reversible binding dynamics.Therefore,this work wellillustrates the chemical and structural versatility of dihydrophenazine in the synthesis of macrocycles and their host-vip chemistry.展开更多
The assembly of metal ions with peptides to create protein mimics has attracted considerable attention in synthetic chemistry.Despite progress in designing metal-peptide assemblies(MPAs),challenges remain in replicati...The assembly of metal ions with peptides to create protein mimics has attracted considerable attention in synthetic chemistry.Despite progress in designing metal-peptide assemblies(MPAs),challenges remain in replicating the complexity of natural proteins,particularly in regulating subunit conformations and constructing large cavities.Herein,we report the successful construction of a giant chiral metalpeptide cage,D/L-Ni_(45)_L_(30),achieved through the deprotonation-driven self-assembly of Gly-D/L-Leu dipeptide-derived ligands and Ni2+ions.The cage is composed of 15[Ni_(3)L_(2)]subunits arranged with fivefold symmetry,forming a composite polyhedron that resembles a pentagonal prism with five quadrangular pyramids.Structural analysis reveals that the peptide ligands display conformational diversity,with distinct V-shaped[Ni_(3)L_(2)]subunits coexisting within the structure.The adaptability of these subunits is driven by hydrophobic interactions and steric hindrance,an exceptional feature in artificial MPAs.Through chiral transfer from the peptide,the metal-peptide cage acquires strong chiroptical properties,manifesting as circular dichroism signals that extend from the visible into the near-infrared regime.展开更多
基金the Natural Science Foundation of China(No.22301131)the Natural Science Foundation of Jiangsu Province(Nos.BK20220781,BK20240679)the National Key Research and Development Program of China(No.2024YFB3815700)are greatly acknowledged.
文摘Dynamic adaptability is a key feature in biological macromolecules,enabling selective binding and catalysis[1].From DNA supercoiling to enzyme conformational changes,biological systems have evolved intricate ways to dynamically adjust their structures to accommodate functional needs.Mimicking this adaptability in synthetic systems is an ongoing challenge in supramolecular chemistry.
基金Department of Chemistry,Fudan Uni-versity,the National Natural Science Foundation of China(22031003,21720102004)the Shanghai Science Technology Committee(19DZ227010O)the Alexander von Humboldt Foundation for a Humboldt Research Award.
文摘Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl) phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1C1C2N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units RhB1, RhB2, RhB3, and RhB4 featuring Cp*^(Rh^(Ⅲ)) (Cp* = η^(5)-pentam-ethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh 3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through pro-gramming different combination of noncovalent interactions (π-x stacking, CH..π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp*^(Irl^(Ⅲ)) analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.
基金supported by the NSFC,China(No.22071061)the Shanghai Natural Science Foundation(No.22ZR1420600).
文摘A novel macrocycle based on conformation-adaptive and electron-rich dihydrophenazine was designed and synthesized.On the one hand,the macrocycle showed host-vip interactions with tetracyanoquinodimethane(TCNQ)driving by charge transfer interaction between them.Meanwhile,host-vip complexation was accompanied by fluorescence quenching and conformational change of the macrocycle.On the other hand,the oxidation of the macrocycle resulted in its diradical cation analogue and induced the release of the vip molecule TCNQ,thereby accomplishing reversible binding dynamics.Therefore,this work wellillustrates the chemical and structural versatility of dihydrophenazine in the synthesis of macrocycles and their host-vip chemistry.
基金supported by the National Natural Science Foundation of China(grant nos.92461305,92361301,and 92161203).
文摘The assembly of metal ions with peptides to create protein mimics has attracted considerable attention in synthetic chemistry.Despite progress in designing metal-peptide assemblies(MPAs),challenges remain in replicating the complexity of natural proteins,particularly in regulating subunit conformations and constructing large cavities.Herein,we report the successful construction of a giant chiral metalpeptide cage,D/L-Ni_(45)_L_(30),achieved through the deprotonation-driven self-assembly of Gly-D/L-Leu dipeptide-derived ligands and Ni2+ions.The cage is composed of 15[Ni_(3)L_(2)]subunits arranged with fivefold symmetry,forming a composite polyhedron that resembles a pentagonal prism with five quadrangular pyramids.Structural analysis reveals that the peptide ligands display conformational diversity,with distinct V-shaped[Ni_(3)L_(2)]subunits coexisting within the structure.The adaptability of these subunits is driven by hydrophobic interactions and steric hindrance,an exceptional feature in artificial MPAs.Through chiral transfer from the peptide,the metal-peptide cage acquires strong chiroptical properties,manifesting as circular dichroism signals that extend from the visible into the near-infrared regime.
