Artificial light-harvesting systems(LHSs) have drawn increasing research interest in recent times due to the energy crisis worldwide. Concurrently, macrocycle-based host–guest interactions have played an important ro...Artificial light-harvesting systems(LHSs) have drawn increasing research interest in recent times due to the energy crisis worldwide. Concurrently, macrocycle-based host–guest interactions have played an important role in the development of supramolecular chemistry. In recent years, studies towards artificial LHSs driven by macrocycle-based host–guest interactions are gradually being disclosed. In this mini-review, we briefly introduce the burgeoning progress of artificial LHSs driven by host–guest interactions. We believe that an increasing number of reports of artificial LHSs driven by host–guest interactions will appear in the near future and will provide a viable alternative for the future production of renewable energy.展开更多
The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus ...The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.展开更多
Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids...Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids is a strong intermolecular force and has directionality and saturation,which plays a very important role in the self-assembly and regulation of aromatic carboxylic acids.In this review,we introduce surface organization formed by aromatic carboxylic acids with the aid of scanning tunneling microscopy(STM).These two-dimensional structures include molecular templates,host-guest systems,and photo-isomerization structures.We also emphasize the thermodynamics and dynamics,which are important research topics of current and future study.展开更多
Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axia...Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axial chiral lanthanide metal clusters.In the structure,rare four-pointed star coordination mode of oxalic acid is reported by this work.In addition,as a fluorescence sensor,the complex 2 exhibits high enantioselectivity for R-/S-BINOL-TF_(2)(EF=2.87)and other chiral binaphthyl derivatives.展开更多
Three-component framework of cucurbit[6]uril, 3-（1-methylimidazolium-3-yl）propane-l-sulfonate and boric acid has been constructed. The crystal structure reveals 1 ： 2 host-guest motif of cucurbit[6]uril and 3-（1-m...Three-component framework of cucurbit[6]uril, 3-（1-methylimidazolium-3-yl）propane-l-sulfonate and boric acid has been constructed. The crystal structure reveals 1 ： 2 host-guest motif of cucurbit[6]uril and 3-（1-methyl- imidazolium-3-yl）propane-l-sulfonate, demonstrating both cation binding of imidazolium moiety and anion binding of sulfonate moiety for the first time. Incorporation of dimeric boric acid facilitates the formation of metal-free three-dimensional framework.展开更多
Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules ...Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.展开更多
The construction of multi-responsive supramolecular systems for drug delivery is a challenging task.In this work,a Pd_(2)L_(4) metallacage 1·([BF_(4)]^(−))_(4) with four pyrene units was first designed and synthe...The construction of multi-responsive supramolecular systems for drug delivery is a challenging task.In this work,a Pd_(2)L_(4) metallacage 1·([BF_(4)]^(−))_(4) with four pyrene units was first designed and synthesized through coordination-driven self-assembly.After the introduction ofγ-CD,a supramolecular amphiphile 1–γ-CD was successfully constructed based on the host–guest molecular recognition betweenγ-CD and the pyrene unit of 1·([BF_(4)]^(−))_(4),which further self-assembled into dual-responsive supramolecular vesicles in aqueous solution.DOX·HCl was used as a model molecule to study the drug encapsulation and release behavior of the supramolecular vesicles.By adjusting the pH of the solution to acidic condition or adding a certain amount ofα-amylase,the vesicle structure was destroyed to achieve rapid and effective release of the drug molecules.This study provides an example for the rational design of efficient dual-responsive supramolecular nanocarriers,which have potential application value in the field of controlled drug delivery.展开更多
A pillar[5]arene prepared from monomer 1 has four constitutional isomers.Although these constitutional iso-mers have the same molecular formula,their other properties that we have investigated are more or less differe...A pillar[5]arene prepared from monomer 1 has four constitutional isomers.Although these constitutional iso-mers have the same molecular formula,their other properties that we have investigated are more or less different.They have different melting points,different NMR spectra and different crystal structures.Furthermore,the corre-sponding four anionic constitutional pillar[5]arene isomers derived from these four constitutional isomers showed different binding abilities with paraquat G in water.The association constants of 3a⊃G,3b⊃G,3c⊃G and 3d⊃G were determined to be(3.33±0.46)×10^(4)L•mol^(−1),(5.00±0.63)×10^(4)L•mol^(−1),(3.33±0.28)×10^(4)L•mol^(−1),and(1.43±0.09)×10^(4)L•mol^(−1),respectively.展开更多
基金financial support of the National Natural Science Foundation of China (No. 21702020)
文摘Artificial light-harvesting systems(LHSs) have drawn increasing research interest in recent times due to the energy crisis worldwide. Concurrently, macrocycle-based host–guest interactions have played an important role in the development of supramolecular chemistry. In recent years, studies towards artificial LHSs driven by macrocycle-based host–guest interactions are gradually being disclosed. In this mini-review, we briefly introduce the burgeoning progress of artificial LHSs driven by host–guest interactions. We believe that an increasing number of reports of artificial LHSs driven by host–guest interactions will appear in the near future and will provide a viable alternative for the future production of renewable energy.
基金Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)Project-ID 433682494-SFB 1459 Intelligent Matter)(T.D.and T.K.)。
文摘The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.
基金supported by the National Basic Research Program of China (No. 2016YFA0200700)the National Natural Science Foundation of China (Nos. 21773041 and 21472029)
文摘Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids is a strong intermolecular force and has directionality and saturation,which plays a very important role in the self-assembly and regulation of aromatic carboxylic acids.In this review,we introduce surface organization formed by aromatic carboxylic acids with the aid of scanning tunneling microscopy(STM).These two-dimensional structures include molecular templates,host-guest systems,and photo-isomerization structures.We also emphasize the thermodynamics and dynamics,which are important research topics of current and future study.
基金This work was supported by the National Natural Science Foundation of China(Nos.21971032,51725204,21771132,51972216).
文摘Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axial chiral lanthanide metal clusters.In the structure,rare four-pointed star coordination mode of oxalic acid is reported by this work.In addition,as a fluorescence sensor,the complex 2 exhibits high enantioselectivity for R-/S-BINOL-TF_(2)(EF=2.87)and other chiral binaphthyl derivatives.
文摘Three-component framework of cucurbit[6]uril, 3-（1-methylimidazolium-3-yl）propane-l-sulfonate and boric acid has been constructed. The crystal structure reveals 1 ： 2 host-guest motif of cucurbit[6]uril and 3-（1-methyl- imidazolium-3-yl）propane-l-sulfonate, demonstrating both cation binding of imidazolium moiety and anion binding of sulfonate moiety for the first time. Incorporation of dimeric boric acid facilitates the formation of metal-free three-dimensional framework.
基金supported by the National Natural Science Foundation of China(21031006)NSFC-DFG joint fund(TRR 61)the National Basic Research 973 Program of China(2011CB932302 and 2012CB932900)
文摘Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.
基金supported by the National Natural Science Foundation of China(22001214,21662031,21661028,22061039)B.S.thanks the Natural Science Foundation of Northwest Normal University(NWNU-LKQN2020-02)for financial support.
文摘The construction of multi-responsive supramolecular systems for drug delivery is a challenging task.In this work,a Pd_(2)L_(4) metallacage 1·([BF_(4)]^(−))_(4) with four pyrene units was first designed and synthesized through coordination-driven self-assembly.After the introduction ofγ-CD,a supramolecular amphiphile 1–γ-CD was successfully constructed based on the host–guest molecular recognition betweenγ-CD and the pyrene unit of 1·([BF_(4)]^(−))_(4),which further self-assembled into dual-responsive supramolecular vesicles in aqueous solution.DOX·HCl was used as a model molecule to study the drug encapsulation and release behavior of the supramolecular vesicles.By adjusting the pH of the solution to acidic condition or adding a certain amount ofα-amylase,the vesicle structure was destroyed to achieve rapid and effective release of the drug molecules.This study provides an example for the rational design of efficient dual-responsive supramolecular nanocarriers,which have potential application value in the field of controlled drug delivery.
基金supported by National Basic Re-search Program(2013CB834502)the National Natural Science Foundation of China(Nos.21125417,21434005)the Fundamental Research Funds for the Central Universities.
文摘A pillar[5]arene prepared from monomer 1 has four constitutional isomers.Although these constitutional iso-mers have the same molecular formula,their other properties that we have investigated are more or less different.They have different melting points,different NMR spectra and different crystal structures.Furthermore,the corre-sponding four anionic constitutional pillar[5]arene isomers derived from these four constitutional isomers showed different binding abilities with paraquat G in water.The association constants of 3a⊃G,3b⊃G,3c⊃G and 3d⊃G were determined to be(3.33±0.46)×10^(4)L•mol^(−1),(5.00±0.63)×10^(4)L•mol^(−1),(3.33±0.28)×10^(4)L•mol^(−1),and(1.43±0.09)×10^(4)L•mol^(−1),respectively.
