The Solvothermal Syntheses, Structures Of Copper(Ⅰ) Halide/Pseudohalide Complexes Containing Terpyridine-like/Terpyridine Ligands

This work mainly paid on the solvothermal syntheses and characterization of new copper(I) halides/pseudohalides complexes containing terpyridine-like ligands. During the syntheses of the novel complexes, interesting in situ reactions, such as hydrolysis, sulfur transformations, have been founded and examined. On the other hand, the template syntheses of some interesting anionic copper(I) pseudohailides infinite networks with bis-terpyridine metal complex cationsare also explored. The thesis is divided into four chapters.In Chapter 1, the study background of this work is concisely introduced with the emphasis on the current survey of in situ syntheses of metal complexes under hydro(solvo)thermal condtions and the copper(I) halides/pseudohalides coordination polymers of N-Containing heterocyclic ligands. The meaning and the progress of this work also have been outlined.In Chapter 2, the reactions of 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tpt) with copper(I) halides under solvothermal or traditional conditions have been carried out and examined. During the progress, two polymeric Cu(I) complexes [Cu₂I₂(tpt)]_n (1) and [Cu₃I₃(tpt)]_n (2), one mixed-valence Cu(I)-Cu(II) complex [Cu₄Cl₂I₄(tpt)₂] (3), and two Cu(II) complexes [CuBr(bpca)] (4) and [Cul(bpca)] (5) [bpca = bis(2-pyridylcarbonyl)amine], were yielded. Complex 1 is a zig-zag chain with tpt in a bis-bipyridine-like coordination mode, while complex 2 with tpt chelating three Cu(I) cations is a ladder-like coordination polymer. Complex 3 is mixed-valence with Cu(I) in a distorted tetrahedral geometry and Cu(II) in a distorted square pyramidal geometry, forming a ladder-like supramolecular chain. Complexes 4 and 5 are the products of in situ hydrolysis of tpt involving the oxidation of Cu(I). The syntheses and characterizations of complex 1, 2, and 5 indicated that Cu(I) can not promote the hydrolysis of tpt. Theoretical study shows that the main effect for hydrolysis of tpt is electron-withdrawing of metal ions rather than metal ions inducing angular strain.In Chapter 3, the reactions of tpt ligand with copper(I) pseudohalides under solvothermal conditions have been carried out and examined. The solvothermal reaction of CuSCN with l,2-bis(diphenylphosphino)ethane (dppe) yielded a coordination polymer, which was characterized to be a complex of CuCN and l,2-bis(diphenylthiophosphinyl)ethane(dppsS₂):...