| Metal nanoclusters are nanoscale ultrafine particles whose properties are completely different from those of macroscopic metals.In recent years,metal nanoclusters have attracted more and more attention in the fields of synthesis,materials,catalysis,biochemistry and theoretical chemistry.Among the Group 11 metals(copper,silver,and gold),silver nanoclusters protected by ligands are valued due to their structural diversity and potential application value.At present,in addition to the common thiol ligands,alkynyl ligand and organophosphorus ligands,calixarenes and their derivatives have also been widely used in coordination chemistry.In this paper,we mainly use tert-butyl acetylene silver as the precursor,p-tert-butylthiacalix[4]arene as the main ligand,by changing the soluble silver salt and synthesis conditions,we obtained some novel p-tert-butylthiacalix[4]arene modified silver nanoclusters by conventional synthesis and solvothermal methods.The structures of these compounds were characterized by single crystal X-ray diffraction,PXRD,infrared spectroscopy and thermogravimetric analysis,and their electrochemical,photoelectric and luminescent properties were studied.The main work contents of this paper are as follows:1.Under solvo-thermal conditions,a case of a thiacalix[4]arene modified[Na2Ag9(TC4A)(tBu C?C)4(CH3OH)2(Sb F6)0.5(BH4)2.5]·6H2O(1,abbreviated as Ag9)was synthesized by using[tBuC?CAg]n and H4TC4A as the reactant,Ag Sb F6 as soluble silver salt,methanol,trichloromethane and toluene as solvents.Also,without changing the[tBu C?CAg]n and H4TC4A,after replacing the soluble silver salt AgSbF6 with CF3COOAg,we obtained a case of compound[Ag9(TC4A)(tBu C?C)4(CF3COO)]2·2H2O(2,abbreviated as Ag18).The structure of the two compounds was characterized by single crystal X-ray diffraction,and the results showed that the asymmetric structural unit of Ag18 was extremely similar to Ag9,and they both contain the same[Ag9(TC4A)(tBuC?C)4]+structural units.therefore,the main skeleton of Ag18 could be regarded as the dimer form of the main skeleton of Ag9.These both compounds have certain thermal stability and solution stability.The luminescence performance,photocurrent responses and electrochemical properties of compound 1 and2 were also studied.2.Using H4TC4A,[tBuC?CAg]n,KMnO4 and glutaric acid as reactants,two novel silver nanoclusters{[Ag(TC4A)·DMF]}2(3,abbreviation Ag2)and[Ag10Mn2(TC4A)2(C?CtBu)4(C?C)2(DMF)2]·H2O(4,abbreviation Ag10)were synthesized by changing the molar ratio of the reactants under conventional synthesis method.Compound 3 is a binuclear cluster with a partial cone conformation of p-tert-butythiacalix[4]arene in its structure.Due to the harsh crystal growth conditions and low yield of compound 3,its characterization and properties still need to be further explored.The compound 4 is a deconuclear cluster consisting of ten silver atoms,two manganese atoms and two thiacalix[4]arenes,which has been shown to be a potential semiconductor luminescent material. |
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