多酸导向的间苯二酚杯4芳烃Co8配位笼的组装及电化学性质.pdf
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1、基于多金属氧酸盐(POM)的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM杯芳烃的大型Co8配位笼Co8(MTR4A)6Cl8(SiW12O40)230DMF74EtOH(cage1),该配位笼由6个碗状间苯二酚杯4芳烃(MTR4A)分子、8个Co阳离子、2个SiW12O404-抗衡阴离子和8个Cl-阴离子组装而成。值得注意的是,SiW12O404-阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage1表现出良好的锂离子存储能力。cage1也能够实现对亚硝酸盐(NO2-)的还原和抗坏血酸(AA
2、)的氧化,是一种具有高活性的双功能催化剂。关键词:配位笼;间苯二酚杯4芳烃;多酸;电化学性质中图分类号:O614.81+2;O614.61+3文献标识码:A文章编号:10014861(2023)09179109DOI:10.11862/CJIC.2023.143Polyoxometalatedirecting calix4resorcinarenebased giant Co8 coordination cage:Selfassembly and electrochemical performanceGUO TingTingAN YanYanZHAO DanYAN JuanZhi(Depart
3、ment of Materials Science and Chemical Engineering,Taiyuan University,Taiyuan 030032,China)Abstract:Polyoxometalate(POM)based supramolecular coordination cages have aroused wide interest in terms oftheir design and fabrication,however,it still be challenging.Herein,we report a POMcalixarenebased gia
4、nt Co8coordination cage,Co8(MTR4A)6Cl8(SiW12O40)230DMF74EtOH(cage1),assembled with six bowlshaped calix4resorcinarene(MTR4A)molecules,eight Co cations,two SiW12O404-counter anions,and eight Cl-anions.Remarkably,SiW12O404-anions were sandwiched between layers via hydrogenbonded to form a 3D supramole
5、cular architecture.Moreover,cage1 showed a good lithiumion storage capacity as an anode material in lithiumionbatteries(LIBs).Furthermore,it was shown to be a highly active bifunctional electrocatalytic performance for reducing nitrite(NO2-)and oxidizing ascorbic acid(AA).CCDC:2248724.Keywords:coord
6、ination cages;calix4resorcinarene;polyoxometalate;electrocatalytic property0IntroductionSelfassembled supramolecular coordination cages have attracted considerable interest because of theirprominent applications in gas storage,catalysis,andelectrochemical sensing16.The coordination cagescould be rat
7、ionally assembled with directional bridgingorganic ligands and different types of metal ions79.Fromthisperspective,calix4resorcinarenebasedderivatives,possessing large inner cavities and controllablecavityenvironments,havebeenextensivelyutilized as building blocks for supramolecular self无机化学学报第39卷as
8、sembly1013.For instance,Pei et al.synthesized agiant coordination cage that was formed by the selfassembly of calix4resorcinarene,Zn(NO3)26H2O and3,3,5,5azobenzene tetracarboxylic acid14.He et al.reported a huge cubic supramolecular nanocapsulebearing six calix4resorcinarene subunits15.The functiona
9、lized calix4resorcinarene cavitand is an essentialbuilding block for the controllable assembly of giantcoordination cages1619.Polyoxometalates(POMs),one fascinating class ofmetaloxo clusters,feature highvalent metal ions(e.g.,V,Mo,W)and abundant redox active sites,which havebeen proven to be candida
10、te anode materials used inlithium ion batteries(LIBs)2023.Nonetheless,POMsare easily soluble in electrolytes,limiting their wideapplication24.Therefore,the selfassembly of supramolecular coordination cages and POMs is a syntheticapproach to take advantage of their structure features25.The POMs could
11、 act as inorganic buildingblocks and guest counter ions in the construction ofinorganicorganic hybrid complexes2634.Nevertheless,to our knowledge,POMcalixarenebased coordinationcages have been rarely reported,since giant coordination cage selfassembly and the strategy of introducingPOMs are still su
12、bstantially challenging for crystalengineering in supramolecular chemistry35.Based on the above consideration,we designedanewPOMcalixarenebasedCo8coordinationcages,namely Co8(MTR4A)6Cl8(SiW12O40)230DMF74EtOH(cage1),synthesized with a methyl imidazolefunctionalized resorcin4arenebased ligand(MTR4A),H
13、4SiO4(W3O9)4 and Co cations under solvothermalconditions(Scheme 1)36.Notably,cage1 is a uniqueexample of hexameric Co8 cationic coordination cagessurrounded by six MTR4A molecules with POMs counter anions.Importantly,cage 1 featured a satisfiedlithiumion storage capacity and stability.Moreover,cage1
14、showedgoodelectrochemicalfunctionsinreducing nitrite(NO2-)and oxidizing ascorbic acid(AA).Scheme 1Synthetic procedure for cage11Experimental1.1Materials and physical measurementAll materials were provided by pharmaceuticalcompanies.FTIR spectroscopy was characterized usinga Nicolet Magna 560 Fourier
15、 transform IR spectrometer in 4 000400 cm-1.The VarioEL ElementalAnalyzer was employed to collect elemental results oncarbon,nitrogen,and hydrogen.The Rigaku SmartLabXray diffractometer was utilized to obtain powderXray diffraction(PXRD)patterns,under the graphitemonochromatized Cu K radiation(=0.15
16、4 nm,U=45kV,I=40 mA,2=230).An electrochemical workstation CHI660E was employed to record electrochemicalbehaviors.The LAND test system(LANHE CT2001A)was adopted for measuring the galvanostatic charge1792第9期discharge curves at 100 mAg-1and the potential of0.013 V(vs Li/Li+).1.2Synthesis of cage1Purpl
17、e crystals of cage1(24 mg,80%based onMTR4A)were achieved from the solvothermal reactionof MTR4A(11 mg,10 mmol),CoCl26H2O(10 mg,40mmol)and H4SiO4(W3O9)4(14 mg,5 mmol)in DMF/EtOH(8 mL,1 1,V/V)at 80 for 3 d.Anal.Calcd.for Co8C574H990N78O232S24Cl8Si2W24(%):C,36.85;H,5.30;N,5.84.Found(%):C,37.22;H,5.12;N
18、,5.78.IR data(KBr,cm-1):3 121(w),2 937(w),1 666(s),1 530(w),1 467(m),1 386(m),1 337(w),1 285(w),1 251(m),1 147(m),1 095(m),1 055(w),1 013(m),971(s),922(s),804(s),691(w),662(w),584(w),534(w).1.3Xray crystallographyThe Bruker D8 VENTURE Xray diffractometerwas used to record crystallographic data under
19、 theCu K radiation(=0.154 178 nm)for cage1 at 173K.The structure was improved onto F2using the fullmatrix leastsquares by adopting SHELXTL2018/3 inWINGX3739.All hydrogen atoms were placed geometrically.The highly disordered solvents were removed bythe SQUEEZE routine in PLATON40.Table S1 andTable S2
20、(Supporting information)list structure refinement parameters and crystallographic results.CCDC:2248724.2Results and discussion2.1Crystal structure of cage1Thecalix4resorcinarenebasedCo8cationiccoordination cage was achieved by self assembly ofMTR4A,H4SiO4(W3O9)4 and CoCl26H2O under solvothermal cond
21、itions.Single crystal X ray diffractionreveals that cage1 crystallizes in space group P1 within a triclinic system.As shown in Fig.1a,cage1 iscomposed of six calix4resorciarene molecules,eightFig.1(a)Structure of cage1;(b)SiW12O404-cation with three cages from one direction by hydrogen bonding;(c)Si
22、W12O404-cation with three cages from different directions by hydrogen bonding;(d)Hydrogenbondingsupramolecular structure of cage1郭婷婷等:多酸导向的间苯二酚杯4芳烃Co8配位笼的组装及电化学性质1793无机化学学报第39卷Co cations,two SiW12O404-counter anions,andeight Cl-anions.Each Co center adopts the fourcoordinated mode by three nitrogen
23、atoms from thethree adjacent ligands,with CoN distances of 0.197 50.205 5 nm,and one chlorine atom,with CoCl distances of 0.205 5 0.22 51 nm,featuring an elegantnanosizedCo8coordinationcage.ThetwofreeSiW12O404-anions act as counter ions to balance thenegative charge.Noticeably,the SiW12O404-anionsre
24、veal two different connected modes through weak CHOhydrogenbondinginteractions.Therelatedhydrogen bond data are listed in Table 1.They both aresurrounded by three MTR4A ligands,the difference isthat one SiW12O404-anion is surrounded by three cages from one direction,while the other from differentdir
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