Surface Organometallic Chemistry——Surface Supported Triruthenium Ketenylidene Clusters and Their Performance in ^(13)CO Isotopic Exchange and Alkylation Reactions

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

Surface Organometallic Chemistry for Single-site Catalysis and Single-atom Catalysis

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.

The Search for New Methods of Synthesis Possible of Organometallic Compounds of P, As, Sb, Bi

The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N （nitrogen） atoms have been replaced on atoms of P （phosphorus）, As （arsenic）, Sb （antimony） and Bi （bismuth）. The authors have proposed a new mechanism for the possible reactions.

Magnetic Properties of the Phosphorous and Carbon with a Four and Five Bonds

The authors discovered a new magnetic properties of the phosphorous and carbon with a four and five bond, and stibine, bismuthine in organometallic chemistry. This allows to modify many of classical reactions by replacing with the nitrogen atoms to atoms of phosphorus, arsenic, antimony and bismuth. The authors have proposed a new mechanism for the possible reactions.

Multistimuli-Responsive Fluorescent Organometallic Assemblies Based on Mesoionic Carbene-Decorated Tetraphenylethene Ligands and Their Applications in Cell Imaging

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.

Strategies for the construction of supramolecular assemblies from poly-NHC ligand precursors

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.

Surface science approach to the heterogeneous cycloaddition of CO_(2) to epoxides catalyzed by site-isolated metal complexes and single atoms: a review

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).

Molecular and heterogenized dinuclear Ir-Cp^* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands

The development of efficient water oxidation catalysts(WOCs)is of key importance in order to drive sustainable reductive processes aimed at producing renewable fuels.Herein,two novel dinuclear complexes,[(Cp^*Ir)2(μ-κ^3-O,N,O-H4-EDTMP)](Ir-H4-EDTMP,H4-EDTMP^4-=ethylenediamine tetra(methylene phosphonate))and[(Cp^*Ir)2(μ-κ^3-O,N,O-EDTA)](Ir-EDTA,EDTA^4-=ethylenediaminetetraacetate),were synthesized and completely characterized in solution,by multinuclear and multidimensional NMR spectroscopy,and in the solid state,by single crystal X-Ray diffraction.They were supported onto rutile TiO2 nanocrystals obtaining Ir-H4-EDTMP@TiO2 and Ir-EDTA@TiO2 hybrid materials.Both molecular complexes and hybrid materials were found to be efficient catalysts for WO driven by NaIO4,providing almost quantitative yields,and TON values only limited by the amount of NaIO4 used.As for the molecular catalysts,Ir-H4-EDTMP(TOF up to 184 min^-1)exhibited much higher activity than Ir-EDTA(TOF up to 19 min^-1),likely owing to the higher propensity of the former to generate a coordination vacancy through the dissociation of a Ir–OP bond(2.123A,significantly longer than Ir–OC,2.0913A),which is a necessary step to activate these saturated complexes.Ir-H4-EDTMP@TiO2(up to 33 min^-1)and IrEDTA@TiO2(up to 41 min^-1)hybrid materials showed similar activity that was only marginally reduced in the second and third catalytic runs carried out after having separated the supernatant,which did not show any sign of activity,instead.The observed TOF values for hybrid materials are higher than those reported for analogous systems deriving from heterogenized mononuclear complexes.This suggests that supporting dinuclear molecular precursors could be a successful strategy to obtain efficient heterogenized water oxidation catalysts.