Developing dedicated nanomedicines to improve delivery efficacy of anti-inflammatory drugs is still a formidable challenge.In this study,we present an extremely simple yet efficient approach to obtain hybrid nanodrugs...Developing dedicated nanomedicines to improve delivery efficacy of anti-inflammatory drugs is still a formidable challenge.In this study,we present an extremely simple yet efficient approach to obtain hybrid nanodrugs through metal-drug coordination-driven self-assembly for carrier-free drug delivery.The resulting metallo-nanodrugs exhibit well-defined morphology and high drug encapsulation capability,allowing for the combination of magnetic resonance imaging and anti-inflammatory therapy.In the case of osteoarthritis(OA),the metallo-nanodrugs remarkably alleviate synovial inflammation,preventing cartilage destruction and extracellular matrix loss.In addition,it led to significantly improved therapeutic efficacy compared with intra-articular administration of the same dose of free drugs in OA mouse model.This work provides a very simple approach for the development of anti-inflammatory nanoformulations by exploiting coordination-driven self-assembly.展开更多
We report the facile construction of a molecular 8_(18) knot and a molecular Borromean rings assembly through self-assembly directed by Cp^(*)Rh corner units. Two curved ligands of similar size and shape were used in ...We report the facile construction of a molecular 8_(18) knot and a molecular Borromean rings assembly through self-assembly directed by Cp^(*)Rh corner units. Two curved ligands of similar size and shape were used in this study. The slight steric differences between the two ligands induce the formation of distinctly different topologies of the assembled products. The structures were confirmed by single-crystal X-ray analysis and nuclear magnetic resonance spectroscopy.展开更多
A novel 1D copper（II） helical chain is constructed through the connection of tetranuclear copper（ll） units [Cu4（L）（Py）4] （H8L=N,N＇-（BINOL-3,3＇-dicarboxyl）-disalicylhydrazide, where BINOL is 1,l＇-binaphth...A novel 1D copper（II） helical chain is constructed through the connection of tetranuclear copper（ll） units [Cu4（L）（Py）4] （H8L=N,N＇-（BINOL-3,3＇-dicarboxyl）-disalicylhydrazide, where BINOL is 1,l＇-binaphthalenyl-2,2＇- diol, py=pyridine） by weak coordination-driven self-assembly, and characterized by IR, single crystal X-ray dif- fraction, thermogravimetric analysis, and X-ray power diffraction analysis. Interestingly, the helical chains are packed in an alternating left-（M） and right-handed （P） chirality, the orientation of the helices was determined by the axial chirality of the ligand. The complex shows antiferromagnetic interactions between the copper centers.展开更多
The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms...The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures,allowing for precise control over the number and distribution of these components.In this study,we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF_(2)-chelated dipyrromethene(BODIPY)-containing Pt(Ⅱ)metallacycles by varying pre-designed Pt(Ⅱ)acceptors.By utilizing different Pt(Ⅱ)acceptors with varying Pt atom configurations and degrees ofπ-conjugated organic moieties,we observed tunable characteristics in the photosensitization process and singlet oxygen(^(1)O_(2))generation efficiency of these targeted metallacycles.Furthermore,we successfully conducted the visible-light-driven oxidative coupling of various amines to imines,catalyzed by the prepared metallacycle PSs.This study offers a novel approach for fabricating efficient PSs based on SCCs,featuring tunable photosensitization efficiency and excellent photocatalytic reactivity,while providing new insights into the preparation of effective PSs.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 square-shaped metallacycle M,functionalized with carbazole and benzothiadiazole,was synthesized through coordination-driven self-assembly.The discrete metallacyclic architecture endows M with superior optical ...A novel square-shaped metallacycle M,functionalized with carbazole and benzothiadiazole,was synthesized through coordination-driven self-assembly.The discrete metallacyclic architecture endows M with superior optical properties owing to its rigid metallacyclic skeleton and donor-acceptor electronic structure.The femtosecond transient absorption(fs-TA)spectroscopic measurements demonstrated that the macrocyclic skeleton significantly promotes the intramolecular charge transfer efficiency and the rapid formation of triplet states.Furthermore,leveraging M as a photocatalyst enabled to drive the cross-dehydrogenative coupling(CDC)reactions with>90%efficiency,which was facilitated by its persistent charge separation states and long-lived triplet states.This work highlights the critical role of metallacycle engineering in optimizing photophysical dynamics and advancing applications in smart optoelectronics and sustainable photocatalysis.展开更多
The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists.Nevertheless,the achievement on photothermal property enhancement and their applicatio...The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists.Nevertheless,the achievement on photothermal property enhancement and their application in solar-driven water evaporation via structural modulation remain scarce.Here,four organometallic cages 1,2,3 and 4 with different functional sites are synthesized via reasonably selecting different building units E1,E2,E3 and E4 based on a tetradentate pyridyl ligand L1.These complexes are characterized by single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy and ESI-TOF-MS analysis.Notably,they exhibit different near-infrared(NIR)photothermal conversion properties due to variations in their size,conjugated area,and electron-withdrawing characteristic of halogen atoms in building units.Compound 4 shows the optimal photothermal performance among this series,with notably enhanced near-infrared absorption and the highest photothermal conversion efficiency.The radical effect of the building unit plays an important role in photothermal conversion ability,as evidenced by the significant EPR signal changes.Therefore,compound 4 is used to construct new membrane 1',achieving a solar power-induced water steam generation rate of 1.92 kg·m^(-2).h^(−1),demonstrating its suitability for the collection of fresh water through desalination and wastewater treatment.This research provides a new strategy for synthesizing and optimizing photothermal conversion property of half sandwich organometallic cages.展开更多
We designed and constructed a new family of 608 dendritic dipyridyl donors, from which two novel triangular metallodendrimers were successfully prepared via coordination-driven self-assembly.Inspired by the existence ...We designed and constructed a new family of 608 dendritic dipyridyl donors, from which two novel triangular metallodendrimers were successfully prepared via coordination-driven self-assembly.Inspired by the existence of multiple intermolecular interactions（e.g., p–p stacking and CH–p interactions） imposed by the DMIP-functionalized poly（benzyl ether） dendrons, their hierarchical selfassembly behaviors were studied in various mixed solvents by using scanning electron microscopy（SEM）. Interestingly, it was found that the morphologies of the obtained metallodendrimers were highly depended on the dendron generation. For example, the first-generation metallodendrimer was able to hierarchically self-assemble into the spherical nanostructures in various mixed solvents. However, the nanofibers were observed for the second-generation metallodendrimer under the similar conditions.Furthermore, the driven force for the formation of such ordered nanostructures was investigated by using1 H NMR and fluorescence spectroscopy.展开更多
During the past few years, the construction of fluorescent supramolecular metallocycles has attracted extensive attention due to their diverse applications such as sensing, photoelectric devices, and mimicking complic...During the past few years, the construction of fluorescent supramolecular metallocycles has attracted extensive attention due to their diverse applications such as sensing, photoelectric devices, and mimicking complicated natural photo-processes. In this review, we will discuss how we entered the field of fluorescent supramolecular metallacycles and what we investigated in this field. The preparation of various fluorescent supramolecular metallacycles and their applications in monitoring the dynamics of coordination-driven self-assembly, sensing, catalysts, and supramolecular gels will be summarized.展开更多
During the past few years, the construction of BODIPY-based supramolecular fluorescent metallacages through coordination-driven self-assembly has gained increasing interest due to their unique photophysical properties...During the past few years, the construction of BODIPY-based supramolecular fluorescent metallacages through coordination-driven self-assembly has gained increasing interest due to their unique photophysical properties and applications in catalysis, sensing, and bioimaging. In consideration of the rapid development of this field, it is time to summarize recent developments involving BODIPY-based metallacages.In this review, a comprehensive summary of the construction of BODIPY-based metallacages as well as their photophysical properties and applications will be presented.展开更多
Herein,we designed and constructed two metallacycles,1 and 2,to illustrate the conformational effect of isomeric AIE fluoropho res on the platfo rm of supramolecular coordination complexe s(SCCs).Specifically,the dang...Herein,we designed and constructed two metallacycles,1 and 2,to illustrate the conformational effect of isomeric AIE fluoropho res on the platfo rm of supramolecular coordination complexe s(SCCs).Specifically,the dangling phenyl rings in TPE units of the metallacycle 1 align completely outside the main cyclic structure,while in the metallacycle 2,these phenyl rings align half inside and half outside.The experimental results showed that two metallacycles exhibited different behaviors in terms of AIE fluorescence and chemical sensing,which could be attributed to the subtle structural difference of the TPE units.This work repre sents the unification of topics such as self-assembly,AIE,and chemical sensing,and further promotes the understanding for the structure-property relationship of isomeric AIE fluorophores.展开更多
Herein,we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks.Specifically,the tetraphenylethylene-based donor...Herein,we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks.Specifically,the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(Ⅱ)centers were combined via coordination-driven self-assembly.Owing to the differences in the shapes of the assemblies,the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions,while a reversal of fluorescence intensities was observed in the aggregation process.Overall,this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors,which can be controlled precisely at the molecular level.展开更多
Two novel,supramolecular,multiferrocenyl rhomboids 5 and 6 have been successfully constructed from newly designed 60 ferrocenyl donor precursor 1 via coordination-driven self-assembly.The structures of all multiferroc...Two novel,supramolecular,multiferrocenyl rhomboids 5 and 6 have been successfully constructed from newly designed 60 ferrocenyl donor precursor 1 via coordination-driven self-assembly.The structures of all multiferrocenyl rhomboids were characterized by multinuclear NMR（~1H and ^（31）P）,CSI-TOF-MS, and PM6 semi-empirical molecular simulation,and their electrochemical behaviors have been investigated.展开更多
During past few years,the construction of fluorescent metallacycles featuring the fluorescenceresonance energy transfer behavior has attracted extensive attention due to their diverse applications such as real-time mo...During past few years,the construction of fluorescent metallacycles featuring the fluorescenceresonance energy transfer behavior has attracted extensive attention due to their diverse applications such as real-time monitoring the dynamics of coordination-driven self-assembly,photoswitching fluorescence-resonance energy transfer,and light-controlled generation of singlet oxygen for cancer therapy.This review focuses on the recent advances on the design principles,preparation methods,optical properties,and the wide applications of fluorescent metallacycles with the FRET property.展开更多
The supramolecular assemblies of luminescent metallohelicates play a crucial role in ion transport,thanks to their tunable three-dimensional molecular architecture and advantageous fluorescence properties.In this stud...The supramolecular assemblies of luminescent metallohelicates play a crucial role in ion transport,thanks to their tunable three-dimensional molecular architecture and advantageous fluorescence properties.In this study,we synthesized a series of benzo[c][1,2,5]thiadiazole(BTZ)-based metallohelicates specifically designed for ion transport applications.These carefully crafted metallohelicates possess internal cavities and varying lengths of alkyl side chains,which enable modulation of their compatibility with phospholipid membranes and enhance ion transport efficiency.Moreover,their high fluorescence quantum yields allow for characterization via fluorescence microscopy following successful incorporation into the membranes.Importantly,due to their strong affinity for anions and the smaller ionic radius of chloride,these metallohelicates exhibit selective transport activity for chloride ions.展开更多
The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades.Nevertheless,the synthesis of a series of interlocked topologies possess...The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades.Nevertheless,the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge.Herein,we introduce a new dipyridinyl ligand L1 featuring two methoxy groups,which act as electron-donating species and provide electrons to the central benzene ring,resulting in an enhanced electron rich effect.Previous research indicates that this feature significantly contributes to forming π-stacking interactions.Furthermore,four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of[2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect.Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis,NMR spectroscopy,and ESI-TOF-MS.In addition,dynamic structural transformation between[2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect.Photothermal conversion abilities of the isolated complexes were studied and we observed that[2]catenane 3a displayed significant temperature changes(from 25.8℃ to 50.3℃)under laser irradiation of 1.5 W/cm^(2),thereby reaching a photothermal conversion efficiency of 40.42%.Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of[2]catenanes most likely generated photothermal conversion.展开更多
Stacking angles played a decisive role in the coupling strength of the excited state,the overlap of electronic orbitals,and behavior of excitons,which further have ultimately affected the luminescent properties.Howeve...Stacking angles played a decisive role in the coupling strength of the excited state,the overlap of electronic orbitals,and behavior of excitons,which further have ultimately affected the luminescent properties.However,developing effective strategies to precisely tailor molecular stacking anglets of chromophores still remains challenges.In this work,we constructed a series of figureeight supramolecules S1-S3 through the coordination-driven self-assembly of anthracene-based 180◦di-platinum(II)acceptor L and ditopic pyridyl ligands L1-L3,respectively.Variation in ligand length enabled regulation of intramolecular anthracene stacking angles in the assembled structures and photoluminescent properties.Photophysical studies revealed that larger stacking angles significantly enhance fluorescent intensities and photoluminescence quantum yields in both solution and solid states.Femtosecond transient absorption spectroscopy further demonstrated that the excited-state lifetimes of S1-S3 were extended due to suppressed non-radiative decay pathways.Moreover,density functional theory calculations showed that the increasing stacking angles weakened intramolecular anthracene interactions,leading to enhanced radiative transition rates.This study elucidated the relationship of molecular packing and luminescent properties,whichwill pave theway for construction of materialswith excellent luminescent performance.展开更多
The selective construction of sophisticated supramolecular topologies has always attracted the remarkable attention of researchers.Thus;various molecular knots and catenanes have recently been reported and were obtain...The selective construction of sophisticated supramolecular topologies has always attracted the remarkable attention of researchers.Thus;various molecular knots and catenanes have recently been reported and were obtained either accidentally or by following a previously planned synthetic strategy.Herein;we introduce a series of supramolecular topologies including double trefoil knot(1);trefoil knot(2)and[2]catenanes(4,5);which were prepared via an elaborated self-assembly strategy by using half-sandwich units based on a flexible pyridyl linker L1.The formation of all the structures has been confirmed by single crystal X-ray diffraction analysis and NMR spectroscopy;and ESI-MS.Remarkably;the central potassium ion of 1 coordinates six oxygen atoms belonging to six amide groups from two trefoil segments.The double trefoil knot 1 and[2]catenanes 4;5 are stabilized by parallel-displacedπ···πstacking interactions(of interlayer distance 3.34-3.82?)between the pyridyl fraction and phenyl moieties of three ligands L1;and by edge-to-face-type CH···πinteractions(2.64-2.83A)between Bi Bz Im conjugated planes and phenyl hydrocarbon bond.Interestingly;the addition/removal of potassium ions resulted in topological transformation between the double trefoil knot 1 and the trefoil knot 2.In addition;the addition of DMF-d7 to a methanolic solution of the double trefoil knot 1 induced its structural conversion into the metallamacrocycle 3.NIR photothermal studies of 1;4;and 5 showed different photothermal responses in solid and solution states.Thus;the photothermal conversion efficiencies of 4;and 5 were within the limit of 16.8%-45.1%based on different power areas;the number and the fashion ofπ···πstacking interactions can directly affect the photothermal conversion efficiency;and EPR experiments confirmed the recorded results.展开更多
Self-assembly post-modification has proven to be an efficient strategy to build higher-order supramolecular architectures and functional materials. In this study, we successfully realized the construction＇of a new fa...Self-assembly post-modification has proven to be an efficient strategy to build higher-order supramolecular architectures and functional materials. In this study, we successfully realized the construction＇of a new family of neutral supramolecular polymeric films containing well-defined metallacycles as the main scaffolds through combination Of coordination-driven self-assembly with post-electropolymerization. The obtained neutral polymeric materials were fully characterized by the cyclic voltammogram （CV）, SEM, and TEM. The thickness of the films was able to be well regulated by the number of scanning cycles. Moreover, we found that the shape of the metallacycles and the number of triphenylamine moieties played important roles in the formation of the final polymer films. We believe that the introduction of the neutral metallacycles into the final polymer structures not only enriches the library of supramolecular polymeric films but also provides a new platform to study neutral molecule detection, separation, and capture.展开更多
Since the first metallacycle was prepared by Verkade in 1983,various metallacycles and metallacages with controllable nanoscale shapes and sizes have been created by modular design and synthesis,showing unique propert...Since the first metallacycle was prepared by Verkade in 1983,various metallacycles and metallacages with controllable nanoscale shapes and sizes have been created by modular design and synthesis,showing unique properties that enable applications in catalysis,sensors,and biomedicine.Everything from their photophysical properties to their antitumor activities and catalysis was found to be influenced by their suprastructures.Thus,it is necessary and helpful to develop a systematic understanding of the relationships among the micro/nanostructures,the resultant photophysical/chemical properties,and the corresponding applications.In this review,we summarized the latest progress in this area in approximately the past 5 years.展开更多
基金funded by the Beijing Natural Science Foundation(No.JQ20005)Guangxi Science and Technology Major Project(No.GuikeAA19254002).
文摘Developing dedicated nanomedicines to improve delivery efficacy of anti-inflammatory drugs is still a formidable challenge.In this study,we present an extremely simple yet efficient approach to obtain hybrid nanodrugs through metal-drug coordination-driven self-assembly for carrier-free drug delivery.The resulting metallo-nanodrugs exhibit well-defined morphology and high drug encapsulation capability,allowing for the combination of magnetic resonance imaging and anti-inflammatory therapy.In the case of osteoarthritis(OA),the metallo-nanodrugs remarkably alleviate synovial inflammation,preventing cartilage destruction and extracellular matrix loss.In addition,it led to significantly improved therapeutic efficacy compared with intra-articular administration of the same dose of free drugs in OA mouse model.This work provides a very simple approach for the development of anti-inflammatory nanoformulations by exploiting coordination-driven self-assembly.
基金supported by the National Natural Science Foundation of China (22031003, 21720102004)Shanghai Science Technology Committee (19DZ2270100)。
文摘We report the facile construction of a molecular 8_(18) knot and a molecular Borromean rings assembly through self-assembly directed by Cp^(*)Rh corner units. Two curved ligands of similar size and shape were used in this study. The slight steric differences between the two ligands induce the formation of distinctly different topologies of the assembled products. The structures were confirmed by single-crystal X-ray analysis and nuclear magnetic resonance spectroscopy.
基金This work was supported by the National Natural Science Foundation of China （No. 20971029） and Guangxi Natural Science Foundation （Nos. 2010GXNSFD013018,2010GXNSFF013001）
文摘A novel 1D copper（II） helical chain is constructed through the connection of tetranuclear copper（ll） units [Cu4（L）（Py）4] （H8L=N,N＇-（BINOL-3,3＇-dicarboxyl）-disalicylhydrazide, where BINOL is 1,l＇-binaphthalenyl-2,2＇- diol, py=pyridine） by weak coordination-driven self-assembly, and characterized by IR, single crystal X-ray dif- fraction, thermogravimetric analysis, and X-ray power diffraction analysis. Interestingly, the helical chains are packed in an alternating left-（M） and right-handed （P） chirality, the orientation of the helices was determined by the axial chirality of the ligand. The complex shows antiferromagnetic interactions between the copper centers.
基金the financial support by the National Natural Science Foundation of China(Nos.22301081,22301269 and 22401096)China Postdoctoral Science Foundation(No.2023M731095)+4 种基金the Shanghai Frontiers Science Center for Molecular Intelligent Synthesesthe Fundamental Research Funds for the Central UniversitiesYoung Talent Fund of Association for Science and Technology in Shaanxi,China(No.20240628)Scientific Research Program Funded by Education Department of Shaanxi Provincial Government(No.23JK0752)Foundation of Yulin Association for Science and Technology(No.20230512)。
文摘The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures,allowing for precise control over the number and distribution of these components.In this study,we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF_(2)-chelated dipyrromethene(BODIPY)-containing Pt(Ⅱ)metallacycles by varying pre-designed Pt(Ⅱ)acceptors.By utilizing different Pt(Ⅱ)acceptors with varying Pt atom configurations and degrees ofπ-conjugated organic moieties,we observed tunable characteristics in the photosensitization process and singlet oxygen(^(1)O_(2))generation efficiency of these targeted metallacycles.Furthermore,we successfully conducted the visible-light-driven oxidative coupling of various amines to imines,catalyzed by the prepared metallacycle PSs.This study offers a novel approach for fabricating efficient PSs based on SCCs,featuring tunable photosensitization efficiency and excellent photocatalytic reactivity,while providing new insights into the preparation of effective PSs.
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 National Natural Science Foundation of China(Nos.22301079 and 22473002)the University Annual Scientific Research Plan of Anhui Province(No.2022AH010013)Anhui Province Key Laboratory for Control and Application of Optoelectronic Information Materials(No.OIM-2024-09).
文摘A novel square-shaped metallacycle M,functionalized with carbazole and benzothiadiazole,was synthesized through coordination-driven self-assembly.The discrete metallacyclic architecture endows M with superior optical properties owing to its rigid metallacyclic skeleton and donor-acceptor electronic structure.The femtosecond transient absorption(fs-TA)spectroscopic measurements demonstrated that the macrocyclic skeleton significantly promotes the intramolecular charge transfer efficiency and the rapid formation of triplet states.Furthermore,leveraging M as a photocatalyst enabled to drive the cross-dehydrogenative coupling(CDC)reactions with>90%efficiency,which was facilitated by its persistent charge separation states and long-lived triplet states.This work highlights the critical role of metallacycle engineering in optimizing photophysical dynamics and advancing applications in smart optoelectronics and sustainable photocatalysis.
基金the National Natural Science Foundation of China(No.22471113)the Natural Science Foundation for Excellent Young Scholars of Henan Province(No.242300421139)the Sci-ence and Technology Innovation Talent Program of the University in Henan Province(25HASTIT001).
文摘The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists.Nevertheless,the achievement on photothermal property enhancement and their application in solar-driven water evaporation via structural modulation remain scarce.Here,four organometallic cages 1,2,3 and 4 with different functional sites are synthesized via reasonably selecting different building units E1,E2,E3 and E4 based on a tetradentate pyridyl ligand L1.These complexes are characterized by single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy and ESI-TOF-MS analysis.Notably,they exhibit different near-infrared(NIR)photothermal conversion properties due to variations in their size,conjugated area,and electron-withdrawing characteristic of halogen atoms in building units.Compound 4 shows the optimal photothermal performance among this series,with notably enhanced near-infrared absorption and the highest photothermal conversion efficiency.The radical effect of the building unit plays an important role in photothermal conversion ability,as evidenced by the significant EPR signal changes.Therefore,compound 4 is used to construct new membrane 1',achieving a solar power-induced water steam generation rate of 1.92 kg·m^(-2).h^(−1),demonstrating its suitability for the collection of fresh water through desalination and wastewater treatment.This research provides a new strategy for synthesizing and optimizing photothermal conversion property of half sandwich organometallic cages.
基金financial support of the National Natural Science Foundation of China (No. 21302058)the financial support of the Key Basic Research Project of Shanghai Science and Technology Commission (No. 13JC1402200)
文摘We designed and constructed a new family of 608 dendritic dipyridyl donors, from which two novel triangular metallodendrimers were successfully prepared via coordination-driven self-assembly.Inspired by the existence of multiple intermolecular interactions（e.g., p–p stacking and CH–p interactions） imposed by the DMIP-functionalized poly（benzyl ether） dendrons, their hierarchical selfassembly behaviors were studied in various mixed solvents by using scanning electron microscopy（SEM）. Interestingly, it was found that the morphologies of the obtained metallodendrimers were highly depended on the dendron generation. For example, the first-generation metallodendrimer was able to hierarchically self-assemble into the spherical nanostructures in various mixed solvents. However, the nanofibers were observed for the second-generation metallodendrimer under the similar conditions.Furthermore, the driven force for the formation of such ordered nanostructures was investigated by using1 H NMR and fluorescence spectroscopy.
基金the National Natural Science Foundation of China (Nos.21871092 and 21672070)Shanghai Pujiang Program (No.18PJD015)the State Key Laboratory of Fine Chemicals (No.KF1801) for the financial support
文摘During the past few years, the construction of fluorescent supramolecular metallocycles has attracted extensive attention due to their diverse applications such as sensing, photoelectric devices, and mimicking complicated natural photo-processes. In this review, we will discuss how we entered the field of fluorescent supramolecular metallacycles and what we investigated in this field. The preparation of various fluorescent supramolecular metallacycles and their applications in monitoring the dynamics of coordination-driven self-assembly, sensing, catalysts, and supramolecular gels will be summarized.
基金supported by the Program of Shanghai Outstanding Academic Leaders(No.21XD1421200)the Fundamental Research Funds for the Central Universities+1 种基金the financial support sponsored by the National Natural Science Foundation of China(No.22101183)China Postdoctoral Science Foundation(No.2021M702251)。
文摘During the past few years, the construction of BODIPY-based supramolecular fluorescent metallacages through coordination-driven self-assembly has gained increasing interest due to their unique photophysical properties and applications in catalysis, sensing, and bioimaging. In consideration of the rapid development of this field, it is time to summarize recent developments involving BODIPY-based metallacages.In this review, a comprehensive summary of the construction of BODIPY-based metallacages as well as their photophysical properties and applications will be presented.
基金This work was financially supported by the National Natrual Science Foundation of China(Nos.21901161 and 22071152)Natural Science Foundation of Shanghai(No.20ZR1429200)+1 种基金the China Postdoctoral Science Foundation(No.2020M671094)Basic Research Program of Xi'an Jiaotong University(No.XZY022020018).
文摘Herein,we designed and constructed two metallacycles,1 and 2,to illustrate the conformational effect of isomeric AIE fluoropho res on the platfo rm of supramolecular coordination complexe s(SCCs).Specifically,the dangling phenyl rings in TPE units of the metallacycle 1 align completely outside the main cyclic structure,while in the metallacycle 2,these phenyl rings align half inside and half outside.The experimental results showed that two metallacycles exhibited different behaviors in terms of AIE fluorescence and chemical sensing,which could be attributed to the subtle structural difference of the TPE units.This work repre sents the unification of topics such as self-assembly,AIE,and chemical sensing,and further promotes the understanding for the structure-property relationship of isomeric AIE fluorophores.
基金financially supported by Interdisciplinary Program of Shanghai Jiao Tong University(No.YG2019QNA16)Shanghai Sailing Program(No.20YF1422600)+1 种基金Natural Science Foundation of Shanghai(No.22dz1207603)National Natural Science Foundation of China(Nos.32101092 and 21901161).
文摘Herein,we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks.Specifically,the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(Ⅱ)centers were combined via coordination-driven self-assembly.Owing to the differences in the shapes of the assemblies,the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions,while a reversal of fluorescence intensities was observed in the aggregation process.Overall,this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors,which can be controlled precisely at the molecular level.
基金financially supported by NSFC(Nos.21132005 and 91027005)
文摘Two novel,supramolecular,multiferrocenyl rhomboids 5 and 6 have been successfully constructed from newly designed 60 ferrocenyl donor precursor 1 via coordination-driven self-assembly.The structures of all multiferrocenyl rhomboids were characterized by multinuclear NMR（~1H and ^（31）P）,CSI-TOF-MS, and PM6 semi-empirical molecular simulation,and their electrochemical behaviors have been investigated.
基金the National Nature Science Foundation of China(Nos.21922506,21871092,21672070 and31702070)Shanghai Pujiang Program(No.18PJD015)+1 种基金the Fundamental Research Funds for the Central Universities,Shanghai Municipal Natural Science Foundation(No.19ZR1437900)the Opening Projects of Shanghai Key Laboratory of Green Chemistry and Chemical Processes,and State Key Laboratory of Fine Chemicals(No.KF 1801)。
文摘During past few years,the construction of fluorescent metallacycles featuring the fluorescenceresonance energy transfer behavior has attracted extensive attention due to their diverse applications such as real-time monitoring the dynamics of coordination-driven self-assembly,photoswitching fluorescence-resonance energy transfer,and light-controlled generation of singlet oxygen for cancer therapy.This review focuses on the recent advances on the design principles,preparation methods,optical properties,and the wide applications of fluorescent metallacycles with the FRET property.
基金the financial support by the Zhejiang Provincial Natural Science Foundation(No.LQ21B020001)the Wenzhou Science and Technology Association(No.kjfw04)+3 种基金the National Natural Science Foundation of China(Nos.22103062 and 52105479)the Shanghai Pujiang Program(No.22PJ1402800)the Shanghai Frontiers Science Center for Molecular Intelligent Synthesesthe Fundamental Research Funds for the Central Universities。
文摘The supramolecular assemblies of luminescent metallohelicates play a crucial role in ion transport,thanks to their tunable three-dimensional molecular architecture and advantageous fluorescence properties.In this study,we synthesized a series of benzo[c][1,2,5]thiadiazole(BTZ)-based metallohelicates specifically designed for ion transport applications.These carefully crafted metallohelicates possess internal cavities and varying lengths of alkyl side chains,which enable modulation of their compatibility with phospholipid membranes and enhance ion transport efficiency.Moreover,their high fluorescence quantum yields allow for characterization via fluorescence microscopy following successful incorporation into the membranes.Importantly,due to their strong affinity for anions and the smaller ionic radius of chloride,these metallohelicates exhibit selective transport activity for chloride ions.
基金supported by the National Natural Science Foundation of China(Nos.22471113 and 22171123)Natural Science Foundation of Henan Province(Nos.242300421139,232300421232)the Science and Technology Innovation Talent Program of University in Henan Province(No.25HASTIT001)。
文摘The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades.Nevertheless,the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge.Herein,we introduce a new dipyridinyl ligand L1 featuring two methoxy groups,which act as electron-donating species and provide electrons to the central benzene ring,resulting in an enhanced electron rich effect.Previous research indicates that this feature significantly contributes to forming π-stacking interactions.Furthermore,four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of[2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect.Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis,NMR spectroscopy,and ESI-TOF-MS.In addition,dynamic structural transformation between[2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect.Photothermal conversion abilities of the isolated complexes were studied and we observed that[2]catenane 3a displayed significant temperature changes(from 25.8℃ to 50.3℃)under laser irradiation of 1.5 W/cm^(2),thereby reaching a photothermal conversion efficiency of 40.42%.Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of[2]catenanes most likely generated photothermal conversion.
基金support from theNationalNatural Science Foundation of China(22271116 for M.W.and 22401107 for J.S.)the Natural Science Foundation of Jilin Province(20230101027JC for M.W.).
文摘Stacking angles played a decisive role in the coupling strength of the excited state,the overlap of electronic orbitals,and behavior of excitons,which further have ultimately affected the luminescent properties.However,developing effective strategies to precisely tailor molecular stacking anglets of chromophores still remains challenges.In this work,we constructed a series of figureeight supramolecules S1-S3 through the coordination-driven self-assembly of anthracene-based 180◦di-platinum(II)acceptor L and ditopic pyridyl ligands L1-L3,respectively.Variation in ligand length enabled regulation of intramolecular anthracene stacking angles in the assembled structures and photoluminescent properties.Photophysical studies revealed that larger stacking angles significantly enhance fluorescent intensities and photoluminescence quantum yields in both solution and solid states.Femtosecond transient absorption spectroscopy further demonstrated that the excited-state lifetimes of S1-S3 were extended due to suppressed non-radiative decay pathways.Moreover,density functional theory calculations showed that the increasing stacking angles weakened intramolecular anthracene interactions,leading to enhanced radiative transition rates.This study elucidated the relationship of molecular packing and luminescent properties,whichwill pave theway for construction of materialswith excellent luminescent performance.
基金supported by the National Natural Science Foundation of China(22471113,22101108,22171123)the Natural Science Foundation of Henan Province(242300421139,232300421232)the Science and Technology Innovation Talent Program of the University in Henan Province(25HASTIT001).
文摘The selective construction of sophisticated supramolecular topologies has always attracted the remarkable attention of researchers.Thus;various molecular knots and catenanes have recently been reported and were obtained either accidentally or by following a previously planned synthetic strategy.Herein;we introduce a series of supramolecular topologies including double trefoil knot(1);trefoil knot(2)and[2]catenanes(4,5);which were prepared via an elaborated self-assembly strategy by using half-sandwich units based on a flexible pyridyl linker L1.The formation of all the structures has been confirmed by single crystal X-ray diffraction analysis and NMR spectroscopy;and ESI-MS.Remarkably;the central potassium ion of 1 coordinates six oxygen atoms belonging to six amide groups from two trefoil segments.The double trefoil knot 1 and[2]catenanes 4;5 are stabilized by parallel-displacedπ···πstacking interactions(of interlayer distance 3.34-3.82?)between the pyridyl fraction and phenyl moieties of three ligands L1;and by edge-to-face-type CH···πinteractions(2.64-2.83A)between Bi Bz Im conjugated planes and phenyl hydrocarbon bond.Interestingly;the addition/removal of potassium ions resulted in topological transformation between the double trefoil knot 1 and the trefoil knot 2.In addition;the addition of DMF-d7 to a methanolic solution of the double trefoil knot 1 induced its structural conversion into the metallamacrocycle 3.NIR photothermal studies of 1;4;and 5 showed different photothermal responses in solid and solution states.Thus;the photothermal conversion efficiencies of 4;and 5 were within the limit of 16.8%-45.1%based on different power areas;the number and the fashion ofπ···πstacking interactions can directly affect the photothermal conversion efficiency;and EPR experiments confirmed the recorded results.
文摘Self-assembly post-modification has proven to be an efficient strategy to build higher-order supramolecular architectures and functional materials. In this study, we successfully realized the construction＇of a new family of neutral supramolecular polymeric films containing well-defined metallacycles as the main scaffolds through combination Of coordination-driven self-assembly with post-electropolymerization. The obtained neutral polymeric materials were fully characterized by the cyclic voltammogram （CV）, SEM, and TEM. The thickness of the films was able to be well regulated by the number of scanning cycles. Moreover, we found that the shape of the metallacycles and the number of triphenylamine moieties played important roles in the formation of the final polymer films. We believe that the introduction of the neutral metallacycles into the final polymer structures not only enriches the library of supramolecular polymeric films but also provides a new platform to study neutral molecule detection, separation, and capture.
文摘Since the first metallacycle was prepared by Verkade in 1983,various metallacycles and metallacages with controllable nanoscale shapes and sizes have been created by modular design and synthesis,showing unique properties that enable applications in catalysis,sensors,and biomedicine.Everything from their photophysical properties to their antitumor activities and catalysis was found to be influenced by their suprastructures.Thus,it is necessary and helpful to develop a systematic understanding of the relationships among the micro/nanostructures,the resultant photophysical/chemical properties,and the corresponding applications.In this review,we summarized the latest progress in this area in approximately the past 5 years.
