| High nuclear silver clusters are becoming hotspots of research because of their structural diversities and various potential applications.Group 11 elements(Cu,Ag and Au)with dio electron configuration are frequently employed in the syntheses of novel cluster complexes due to their enhanced metallophilic interaction that overcomes repulsion between cationic metal centers.Anion template method is a simple and effective pattern in synthesis silver clusters.However,it is still in the primary stage to study the control of the structure of silver clusters by using anionic templates.On the other hand,nobel metal(gold,silver and gold-silver alloy)nanoclusters of atomic precision have attracted increasing attention owing to their applications in catalysis,sensing,electronchemistry,luminescence or in biomedical fileds.Hitherto,many important advances have been made for gold nanoclusters due to their high stability and easy preparation characteristics,silver nanoclusters are still not as well understood as those of their Au cousins predominantly due to their instability and synthesis bottlenecks.Alloy nanoclusters usually demonstrate interesting characteristics that can be superior to their monometallic analogues.However,the greater difficulties from determining the distribution of both metals in such alloy nanoclusters hindered progress in this area.In general,the development of high-nuclearity silver cluster based on Ag(I)and nanoclusters constructed by partially reduced zerovalent and monovalent Ag continue to be meaningful.The thesis consists of three sections:I:The reaction of iPrSH with AgNO3 was used to produce insoluble(iPrSAg)n precusor,and then silver nitrate was added to depolymerize the precursor,two anionic template silver cluster Metal-Organic-Frameworks(MOFs)were obtained in different solvents,namely,[CO3@Ag20(iPrS)10(NO3)8(DMF)2]n(1);[SO4@Ag22(iPrS)12(NO3)6·2NO3]n(2).The CO32-is from carbon dioxide in air,whereas SO42-is from the oxidation of S2' under solvothermal conditions.To the best of our knowledge,complex 2 is the first example of a silver cluster based interpenetrated 3D framework.We found that the kind of solvent has a direct effect on the structure of the product.The photoluminescent and electrochemical properties of 2 are discussed in detail.II:we first extended the scope of the anion-template to mixed thiolate and diphosphine co-protected silver clusters,and we used Ag-S precursor,anion template,diphosphine ligand and silver salt synthesized six novel high-nuclear silver clusters with the nuclearities ranging from 18 and 24,to 46.namely,[S@Ag18(tBuC6H4S)16(dppp)4]·DMF·5CH3CN-3CH3OH(3),[MoO4@Ag24(MeC6H4S)12(dppm)6(MoO4)4]·2BF4·C2H5NO(4),[MoO4@Ag24(MeC6H4S)12(dppm)6(MoO4)4]·2CF3SO3(5),[MoO4@Ag24(MeC6H4S)12(dppf)6(MoO4)4]·2CF3SO3(6),[MoO4@Ag24(MeC6H4S)12(dppb)6(MoO4)4]·2CF3SO3(7)and[Mo6O22@Ag46(tBuC6H4S)32(dppm)4(CH3CN)8]·6CF3SO3(8),The S2-ion should originate from the C-S bond cleavage of tBuC6H4S-ligand under solvothermal conditions in complex 3;Mo6O228-template in complex 8 should be in situ generated from(Bu4N)2Mo6O19,the lindqvist-type isopolyanion;High-resolution electrospray mass spectrometry(HR-ESI-MS)analyses of 6 indicate its exceptionally high stability in acetonitrile;The dual-emissive and thermochromism of photoluminescent properties of complex 3 are discussed in detail.?:We use Au(PPh2Py)Cl and AgNO3 as Au and Ag resources,respectively,PhCH2SH as monodentate ligand to react with NaBH4,the Au doped Ag alloy nanocluster 9[Au3Ag38(SCH2Ph)24X5]2-(X= Cl or Br)was obtained under the reduction of NaBH4.The cluster 9 features an all-metallic face-fused biicosahedral Au2@AuAg20 rod-like kernel enwrapped by the outermost Ag18(SCH2Ph)24X3 shell,with comprised of two Ag6S6 cycles and one Ag6S2X3 arc,different from the underlying S-Au(Ag)-S staple;the cluster can be viewed as a 14e system and the electrochemical and photoluminescent properties was discussed in detail. |
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