Syntheses And Properties Of Metal–Organic Complexes Constructed From The Derivatives Of Resorcin[4]arene

In this paper,a series of novel complexes were constructed by metal ions and2-mercaptopyridine N-oxide groups modified resorcin[4]arene（TMR4A）or4-（4′-pyridinyl）thiazole-2-thiol functionalized resorcin[4]arene（TPTR4A-II）under solvothermal conditions.Their structures were confirmed by the single crystal X-ray diffraction.Elemental analyses,thermogravimetric analyses（TGA）,infrared spectra（IR）and powder X-ray diffraction spectra（PXRD）were applied for characterization.Importantly,the catalytic performances of compounds 1-6 for the catalytic oxidation of thioether and2-chloroethyl ethyl sulfide（CEES）were investigated with polyoxometalates（POMs）as main catalytic species.Further,we explored the electrochemical behaviors of compounds 7-9 as anode materials in lithium-ion batteries（LIBs）owing to the reversible electrochemical redox behaviors and electron storage functions for POMs.Additionally,in light of the characteristics of the frameworks for compound 10,its property about the electrochemical detection for nitrophenol isomers was studied.1.TwometalcomplexesofTMR4A,namely,[Ni₂Cl（TMR4A）₂（CH₃CN）₂]·[PMo₁₂O₄₀]·4CH₃CN（1）and[Co₂Cl（TMR4A）₂（CH₃CN）₂]·[PMo₁₂O₄₀]·4CH₃CN（2）were successfully assembled by TMR4A with[PMo₁₂O₄₀]^3-and metal ions.Single-crystal X-ray diffraction reveals that compounds 1 and 2 are isostructural,and both of them display a dimeric structure.Remarkably,1 and 2 are highly stable,and exhibit excellent catalytic oxidation performances as heterogeneous recyclable catalysts.2.A family of isopolymolybdate-based inorganic–organic hybrid materials,namely,[Mn（TMR4A）（H₂O）₄]·[Mo₆O₁₉]·0.5CH₃CH₂OH·H₂O（3）,[Ni（TMR4A）（H₂O）₄]·[Mo₆O₁₉]·0.5CH₃CH₂OH·H₂O（4）,[Zn（TMR4A）（H₂O）₄]·[Mo₆O₁₉]·0.5CH₃CH₂OH·H₂O（5）and[Co₂（TMR4A）₂（H₂O）₄(β-Mo₈O₂₆)]·CH₃CN·12H₂O（6）,were synthesized via the self-assembly of ligand TMR4A with isopolymolybdate and metal ions.To some extent,the different solvents influence the crystallinities of compounds 3-6 and the types of isopolymolybdates in 3-6.Single-crystal X-ray diffraction reveals that compounds 3-5 are isostructural,and they are discrete structures with uncoordinating[Mo₆O₁₉]^2-.Additionally,the[Mo₈O₂₆]^4-anions were transformed into the free[Mo₆O₁₉]^2-anions in 3-5.Differently,[β-Mo₈O₂₆]^4-in compound 6 coordinates to cobalt ion to form an unique dimer.Markedly,3-6possess good chemical stability,and they show efficient catalytic oxidative desulfurization activity toward thioethers as recyclable heterogeneous catalysts.More importantly,compound3 exhibits the effective and selective catalytic oxidation of CEES.3.Aseriesofinorganic–organichybridmaterials,namely,[Co₂（TMR4A）₂（H₂O）₁₀][Si W₁₂O₄₀]·2Et OH·4.5H₂O（7）,[Ni₂（TMR4A）₂（H₂O）₁₀][Si W₁₂O₄₀]·4Et OH·13H₂O（8）and[Zn₂（TMR4A）₂（H₂O）₁₀][Si W₁₂O₄₀]·2Et OH·2H₂O（9）,have been synthesized by assembly of TMR4A with[Si W₁₂O₄₀]^4-and different metal ions.Single-crystal X-ray diffraction reveals that compounds 7-9 are isostructural,and they are discrete structures with uncoordinating[Si W₁₂O₄₀]^4-ions.Compounds 7-9 are expected to be anode materials for LIBs due to the electron storage functions of POMs.However,these compounds possess poor conductivity.So,they are immobilized on reduced graphene oxide（RGO）through the strategy of ball-milling to generate the composites 7@RGO-9@RGO.Further,the electrochemical properties of these materials were explored in detail.Compared with compounds 7-9,7@RGO-9@RGO exhibited superior discharge capacity and cycling stability.In addition,we investigated the electrochemical mechanism of 7@RGO-9@RGO and the effects of different metal ions on the electrochemical performance.4.Under solvothermal condition,a novel microporous MOF,[Mn₄（TPTR4A-II）_0.5（bpdc）₄（H₂O）]·2DMF（10）was successfully obtained through assembly of TPTR4A-II,biphenyl-4,4′-dicarboxylic acid（H₂bpdc）and Mn（II）ions.Interestingly,10possesses 1D nanotubular channels with a size of approximately 12.6×12.6?.Through the strategy of mechanical grinding,the new composite 10@GO was obtained,which changed into 10@RGO at a high negative potential during the electrochemical experiments.It is worth noting that the glassy carbon electrode（GCE）modified by 10@RGO（10@RGO/GCE）exhibited excellent electrocatalytic activity for the individual detection of three nitrophenol isomers.