| The monocarba-closo-dodecaborate anion[CB11H12]-is significantly different from traditional organic molecules due to its unique stereochemistry and inner negative charge properties.Its molecular orbitals are formed by the overlap of pure σ and,π orbitals,resulting in a big HOMO/LUMO gaps.Compared to the neutral[C2B10H12],[CB11H12]-is more pronouncing due to the inner anionic charge.The carborane anion[CB11H12]-is inherently weakly coordinated because the charge of the cluster is delocalized throughout the three-dimensional aromatic core.This thesis is devoted to the synthesis of active intermediates C-Li and C-Cu based on carborane anion[CB11H12]-.A carborane carbon lithium complex could be used as a reactive intermediate for Pd-catalyzed carbon-carbon bond formation at the 1 position of carborane anion;mono-carborane Cu(Ⅰ)acetylides could be converted into novel complexes by adding auxiliary phosphine and pyridine ligands,which exhibit a surprising variety of structural complexity.X-ray crystallography revealed cores with two to ten Cu(Ⅰ)centers.In the solid state,the compounds featured room-temperature phosphorescence across the visible spectrum in colors from blue to deep red.Lifetimes at room temperature are in the microsecond regime,and quantum yields of up to 0=0.99 were observed.At the same time,this kind of compound had high reactivity in organic synthesis,transmetalation occurred efficiently and quickly,and play ed a vital role in the formation of C-C and C-N bonds.At the same time,the isolated speci’fic alkyne copper complex is applied in the Glaser reaction and the CuAAC reaction,and we can obtain more novel carborane derivatives.1.Crystal structure of a carborane endo/exo-dianion and its use in the synthesis of ditopic ligands for supramolecular frameworks.It was found that lithium 2,2,6,6-tetramethylpiperidin-l-ide(LiTMP)could be used as a novel lithiation reagent at the 1-position of mono-carborane,and a deprotonated carborane dianion derivative is obtained at this position.So far,this is the first single crystal structure for carborane dianion with the structural composition of[Li(THF)3]2-[CB11H10-12-CN].The transmetalation of monovalent copper is completed by using this as a starting material,and then a series of ditopic ligands were formed under the condition of Pd catalysis.The resulting ditopic ligands were used to synthesize the novel metal-organic frameworks.A one-dimensional metal-organic framework with the composition of[((MeCN)2Cu)-1-pyridyl-CB11H10-12-CN]n was obtained2.Mono-Copper(Ⅰ)Complexes Stabilized by Monocarba-closo-dodecaborane Anion[CB11H11-12-C≡CH]-and Auxiliary Ligands.The weakly coordinating anion[CB11H12]-was successfully introduced as a component of copper acetylides.We could obtain different monocarborane copper acetylides after treatment of[Cs][CB11H11-12-C≡CH]with different equivalents of CuI.[(CB11H11-12-C≡CH)Cu(NH3)2]was obtained after treatment with 1.0 equiv of cuprous iodide and concentrated aqueous ammonia at low temperature.Optionally,[(CB11H11-12-C≡CH)Cu(NH3)2]was transferred into a series of novel monocarborane copper acetylides with the addition of different sterically hindered phosphine and pyridine ligands.The results show that the addition of pyridine ligands afforded structurally similar complexes with the composition of[(CB11H11-12-C≡CH)Cu(pyridyl)2],in which the Cu(Ⅰ)atom interacted with the terminal-C≡CH in π-bond;when different sterically hindered phosphine ligands were added,the Cu(Ⅰ)atom became a free counter cation in the product,no longer coordinated to the terminal alkyne-C≡CH.Under the room temperature conditions,{(CB11H11-12-C≡C)2Cu4(NH3)3}n was obtained after treatment of[Cs][CB11H11-12-C≡CH]with 2.2 equiv of cuprous iodide and concentrated aqueous ammonia3.Well-Defined Monocarborane Copper(Ⅰ)Acetylides with Structural and Luminescence Properties Controlled by Ligand Sterics.The weakly coordinating anion[CB11H12]-was successfully introduced into the copper acetylides,and[Cs][CB11H11-12-C≡CH]was treated with 2.2 equiv of cuprous iodide and aquous ammonia to give {(CB11H11-12-C≡C)2Cu4(NH3)3}n.{(CB11H11-12-C≡C)2Cu4(NH3)3}n was transferrred into a series of novel monocarborane copper acetylides with the addition of different sterically hindered phosphine and pyridine ligands.The structure of the resulting novel complexes were complicated and diverse.The single crystal structures revealed that the series of monocarborane copper acetylides had two to ten Cu(Ⅰ)atoms as the central motif.In the solid state,the compounds featured room-temperature phosphorescence across the visible spectrum in colors from blue to deep red.Lifetimes at room temperature are in the microsecond regime,and quantum yields of up to Φ＝0.99 were observed.The resulting copper acetylides of the certain structures were used for the study of the CuAAC reaction,and the target product was obtained in a very high yield and in a short time. |
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