Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which ...Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which concerns the synthesis, structure, reactivity and catalytic activity of surface-supported organometallfc compounds is a new展开更多
Although driven by different research interests,single-site catalysts and single-atom catalysts are both believed to be model systems bridging homogeneous and heterogeneous catalysis.The two concepts are similar but d...Although driven by different research interests,single-site catalysts and single-atom catalysts are both believed to be model systems bridging homogeneous and heterogeneous catalysis.The two concepts are similar but different.In this review,we will first explain the difference between single-atom catalysis and single-site catalysis,in terms of their goals,synthetic methods and coordination structures of corresponding catalysts.Then,we will introduce the surface organometallic chemistry method,a method traditionally used for synthesizing single-site catalyst.We will explain why it might benefit the single-atom catalysis community.At last,the choice of support to accommodate the method for synthesizing single-atom catalysts will be discussed.展开更多
The controllable construction of light-emitting organometallic supramolecular materials integrating stimulus responses and biological applications is still a major challenge today.In this work,emissive organometallic ...The controllable construction of light-emitting organometallic supramolecular materials integrating stimulus responses and biological applications is still a major challenge today.In this work,emissive organometallic assemblies based on AgI/AuI and mesoionic carbene-decorated tetraphenylethene(MIC-TPE)ligands have been synthesized and characterized.Photophysical studies showed that these organometallic assemblies[M_(4)(2)_(2)](OTf)_(4) not only fluoresce in various dilute solutions,resulting from the rigidification of MIC-TPE ligands upon complexation,but also show tunable fluorescence wavelengths and intensity behaviors in mixed solvent systems and at varying temperatures while in solution,and mechanical pressure stimulus-responsive fluorescent features in the solid state.Furthermore,the organometallic cages[M_(4)(2)_(2)](OTf)_(4)(M=Ag and Au)were successfully employed for cell imaging and showed the potential of anticancer activity,making them promising candidates for cancer theranostics.This work provides a simple and efficient method to prepare highly emissive and stimulus-responsive organometallic materials and paves the way for related biological applications such as cancer cell imaging and targeted therapy.展开更多
The field of supramolecular assemblies has developed rapidly in the last few decades,thanks in a large part to their diverse applications.These assemblies have been mostly based on Werner-type coordination motifs in w...The field of supramolecular assemblies has developed rapidly in the last few decades,thanks in a large part to their diverse applications.These assemblies have been mostly based on Werner-type coordination motifs in which metal centres are coordinated by nitrogen or oxygen donors.Recently,N-heterocyclic carbene(NHC)ligands have been employed as carbon donors not only because of their appealing structures but also due to the extensive applications in catalysis,biomedicine and material science of the resulting assemblies.During the last decade,NHC-based supramolecular assemblies have witnessed rapid growth and extensive application in molecular recognition,luminescent materials and catalysis.For different topological systems,a diverse selection of poly-NHC precursors and synthetic strategies is crucial to precisely control the synthesis of supramolecular architectures.Several synthetic strategies have been developed to synthesise two-dimensional(2D)molecular metallacycles and three-dimensional(3D)metallacages from a wide range of poly-NHC precursors,including a straightforward one-pot strategy,supramolecular transmetalation,stepwise synthesis,an improved one-pot strategy involving self-sorting behaviour of 3D metallacages and a subtle variation strategy of poly-NHC ligand precursors.This review offers a summary of the synthetic strategies applied for the construction of different poly-NHC-based supramolecular assemblies,particularly emphasizes recent progress in the synthesis of large and complex supramolecular assemblies from poly-NHC precursors,and further attention is given to their application in postsynthetic modifications(PSMs),host-guest chemistry,luminescent properties and biomedical applications.展开更多
The cycloaddition of CO_(2) to epoxides to afford cyclic organic carbonates is an increasingly relevant non-reductive strategy to convert CO_(2) to useful products able to serve as high-boiling solvents,chemical inter...The cycloaddition of CO_(2) to epoxides to afford cyclic organic carbonates is an increasingly relevant non-reductive strategy to convert CO_(2) to useful products able to serve as high-boiling solvents,chemical intermediates,and monomers for the preparation of more sustainable polymers.The development of efficient and robust hetero-geneous catalysts for such transformation is,therefore,crucial and can be carried out by several strategies that often require the preparation of sophisticated and/or expensive organic networks,linkers,or compounds.A different approach to the preparation of heterogeneous catalysts for CO_(2)-epoxide coupling is by applying surface science methodologies to graft molecular fragments or single atoms on various supports leading to well-defined active sites.In this context,surface organometallic chemistry(SOMC),along with comparable methodologies,is a valuable approach for the preparation of efficient,single-site Lewis acids and catalysts for the target cycloaddition reaction on metal oxides,whereas,other grafting methodologies,can be applied to prepare analogous catalysts on different kinds of surfaces.Finally,we discuss very recent advances in the application of surface methodologies for the preparation of single atom catalysts as an increasingly relevant approach towards highly active Lewis acids for the cycloaddition of CO_(2) to epoxides.Overall,we show that Lewis acids and catalysts prepared by facile surface methodologies hold significant potential for future application is the synthesis of cyclic carbonates from CO_(2).展开更多
文摘Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which concerns the synthesis, structure, reactivity and catalytic activity of surface-supported organometallfc compounds is a new
基金ShanghaiTech University Start-up Funding and the Shanghai Pujiang Talent Program,China(No.21PJ1410400).
文摘Although driven by different research interests,single-site catalysts and single-atom catalysts are both believed to be model systems bridging homogeneous and heterogeneous catalysis.The two concepts are similar but different.In this review,we will first explain the difference between single-atom catalysis and single-site catalysis,in terms of their goals,synthetic methods and coordination structures of corresponding catalysts.Then,we will introduce the surface organometallic chemistry method,a method traditionally used for synthesizing single-site catalyst.We will explain why it might benefit the single-atom catalysis community.At last,the choice of support to accommodate the method for synthesizing single-atom catalysts will be discussed.
基金The authors gratefully acknowledge financial support from the National Natural Science Foundation(NSFC)(grant nos.22025107,21722105,and 21771146)the National Youth Top-notch Talent Support Program of China,the Key Science and Technology Innovation Team of Shaanxi Province(nos.2019TD-007 and 2019JLZ-02)the FM&EM International Joint Laboratory of Northwest University.
文摘The controllable construction of light-emitting organometallic supramolecular materials integrating stimulus responses and biological applications is still a major challenge today.In this work,emissive organometallic assemblies based on AgI/AuI and mesoionic carbene-decorated tetraphenylethene(MIC-TPE)ligands have been synthesized and characterized.Photophysical studies showed that these organometallic assemblies[M_(4)(2)_(2)](OTf)_(4) not only fluoresce in various dilute solutions,resulting from the rigidification of MIC-TPE ligands upon complexation,but also show tunable fluorescence wavelengths and intensity behaviors in mixed solvent systems and at varying temperatures while in solution,and mechanical pressure stimulus-responsive fluorescent features in the solid state.Furthermore,the organometallic cages[M_(4)(2)_(2)](OTf)_(4)(M=Ag and Au)were successfully employed for cell imaging and showed the potential of anticancer activity,making them promising candidates for cancer theranostics.This work provides a simple and efficient method to prepare highly emissive and stimulus-responsive organometallic materials and paves the way for related biological applications such as cancer cell imaging and targeted therapy.
基金This work was supported by the National Natural Science Foundation of China(22025107,21722105,21771146)the National Youth Top-notch Talent Support Program of China,the Key Science and Technology Innovation Team of Shaanxi Province(2019TD-007,2019JLZ-02)the FM&EM International Joint Laboratory of Northwest University.
文摘The field of supramolecular assemblies has developed rapidly in the last few decades,thanks in a large part to their diverse applications.These assemblies have been mostly based on Werner-type coordination motifs in which metal centres are coordinated by nitrogen or oxygen donors.Recently,N-heterocyclic carbene(NHC)ligands have been employed as carbon donors not only because of their appealing structures but also due to the extensive applications in catalysis,biomedicine and material science of the resulting assemblies.During the last decade,NHC-based supramolecular assemblies have witnessed rapid growth and extensive application in molecular recognition,luminescent materials and catalysis.For different topological systems,a diverse selection of poly-NHC precursors and synthetic strategies is crucial to precisely control the synthesis of supramolecular architectures.Several synthetic strategies have been developed to synthesise two-dimensional(2D)molecular metallacycles and three-dimensional(3D)metallacages from a wide range of poly-NHC precursors,including a straightforward one-pot strategy,supramolecular transmetalation,stepwise synthesis,an improved one-pot strategy involving self-sorting behaviour of 3D metallacages and a subtle variation strategy of poly-NHC ligand precursors.This review offers a summary of the synthetic strategies applied for the construction of different poly-NHC-based supramolecular assemblies,particularly emphasizes recent progress in the synthesis of large and complex supramolecular assemblies from poly-NHC precursors,and further attention is given to their application in postsynthetic modifications(PSMs),host-guest chemistry,luminescent properties and biomedical applications.
基金V.D.E.thanks the National Research Council of Thailand(NRCT)(grants Nos.N41A640170 and N42A650196)for funding this work.A.W.K.is grateful to Cerca program/Generalitat de Catalunya,ICREA,Ministerio de Ciencia e Innovacion(PID2020-112684GB-100Severo Ochoa Excellence Accreditation 2020-2023 CEX2019-000925-S).
文摘The cycloaddition of CO_(2) to epoxides to afford cyclic organic carbonates is an increasingly relevant non-reductive strategy to convert CO_(2) to useful products able to serve as high-boiling solvents,chemical intermediates,and monomers for the preparation of more sustainable polymers.The development of efficient and robust hetero-geneous catalysts for such transformation is,therefore,crucial and can be carried out by several strategies that often require the preparation of sophisticated and/or expensive organic networks,linkers,or compounds.A different approach to the preparation of heterogeneous catalysts for CO_(2)-epoxide coupling is by applying surface science methodologies to graft molecular fragments or single atoms on various supports leading to well-defined active sites.In this context,surface organometallic chemistry(SOMC),along with comparable methodologies,is a valuable approach for the preparation of efficient,single-site Lewis acids and catalysts for the target cycloaddition reaction on metal oxides,whereas,other grafting methodologies,can be applied to prepare analogous catalysts on different kinds of surfaces.Finally,we discuss very recent advances in the application of surface methodologies for the preparation of single atom catalysts as an increasingly relevant approach towards highly active Lewis acids for the cycloaddition of CO_(2) to epoxides.Overall,we show that Lewis acids and catalysts prepared by facile surface methodologies hold significant potential for future application is the synthesis of cyclic carbonates from CO_(2).
基金financially supported by PRIN 2015(20154X9ATP_004)University of Perugia and MIUR(AMIS,“Dipartimenti di Eccellenza–2018–2022”Program)+1 种基金INSTM and CIRCC for a post-doctoral grantUniversity of Perugia for hospitality and the Erasmus Programme for financial support。
