Synthesis, Crystal Structures And Luminescence Of Cu (Ⅰ)/Cd(Ⅱ) Complexes Based On Pyridyl-conjugated Aminotriazoles

Up to now,triazole derivation ligands have built coordination polymers with all kinds of novel structures, and the diverse and favorable applications of coordination polymers (CPs) based triazole and its ramification in making optically, electrically and magnetically responsive devices and in absorption, separation, catalysis and molecular recognition,moreover, Because of its ramofications and the second ligands'diversity and different coordination modes, their design and solvothermal fabrication have attracted considerable attention of contemporary coordination chemistry and crystal engineering.In quest for the CPs with different structures and functionalities, we designed and prepared three pyridyl-midified aminotriazole ligands, namely 3,5-(pyrid-2-yl)-4-amino-1,2,4-triazole (2-bpat), 3,5-(pyrid-3-yl),4-amino-1,2,4-triazole (3-bpat) and 3,5-(pyrid-4-yl)-4-amino-1,2,4- triazole (4-bpat), then from which we synthesized 15 complexes of Cd(II) and Cu(I). The products were structurally determined by X-ray diffraction and their responses to heat and light were studied. Based on the outcomes we explored the expression of secondary building blocks in construction of metal-organic frameworks (MOFs) and the influence of position-isomeric ligands and (pseudo)halides, as auxiliary ligands, on the stuctures and properties of CPs. Herein we summarize the outcomes of lab research into this dissertation.Chapter one mainly introduces the background and current progress of coordination polymer research and elucidates the principle of predesigning CPs and enumerates the factors influencing the structures of CPs. In addition, it also introduces the concept and application of secondary building blocks in constructing MOFs and the coordination chemistry of pyridyl-conjugated aminotriazole, meanwhile, elucidates the luminescence basic principle of d10 metal complexes and finally the aim and meaning of this study.The second chapter reports the synthesis of 2-bpat, 3-bpat and 4-bpat and the crystal structures and properties of 9 complexes with the bptas as primary ligands and (pseudo)halid as second ligands. The complexes include [Cu₂I₂(3-bpat)₂]_n (1), [Cu₃I₃(3-bpat)]_n (2), [Cu₄I₄(3-bpat)₂]_n (3), [Cu₂(CN)₂(3-bpat)]_n (4), [Cu_2.5(SCN)(CN)_1.5(3-bpat)]_n (5), [Cu₃(SCN)₃(3-bpat)]_n (6), [Cu₃(CN)₃(4-bpat)₂]_n (7), [Cu₂Cl(CN)(4-bpat)]_n (8), [CuS(4-bpat)]_n (9), of which complex 4 is unique being one-dimensional (1D), 1, 2, 3, 6 and 9 are 2D and 5, 7 and 8 are 3D. 1 and 3 can be isolated concomitantly in one pot, but, at specified temperature, 1 can be resulted as only product. 3 can also be obtained as a concomitant of 2, but in a low yield. The facts implicate that temperature is influential on the self-assenbly of CPs. 4 is a twist-drill shaped chain, in which the 3-bpat adopts a convergent coordination manner. If keep the reaction conditions all the same but time, the reaction gives 5 as product, which means that 5 is thermodynamically favored product, but 4 is kinetically favored. The structures of complexes 6-9 reveals an effect of second ligand on construction of CPs. 6 is a 2D poltmer containing SCN-Cu network, 7 is 3D containing 1D CN-Cu chain, 8 is 3D containing 1D CN-Cu chain and coordinating Cl, while 9 is 2D containging S-CN chain. Apparently the results included in this chapter provide a new sight into the design of CPs.Chapter three describes the synthesis, structures and luminescence of six Cd(II) complexes with 2-bpat and 3-bpat as ligands. Among these [Cd(2-abpt)₂Cl₂]_n (10) is mononuclear, while the [Cd₂(2-abpt)₂Cl₄] (11) and [Cd₂(2-abpt)₂Cl₄]·CH₃CN (12) are the binuclear pseudoisomers discrinated by solvent. Comparing the isolations of 11 and 12 suggest strongly a directing effect of solvent on assembly of complexes. Complexes [Cd₃(2-abpt)Cl₆]_n (13) and [Cd₂(2-bpt)(CN)₂(SCN)]_n (14) are both 2D, whose preparations are analogous, but that of 14 was added CuCl₂ as second metal source. Their structural diversity indicates that the presence of non-coordinative metal ion affects the CPs'structures. More than that, the structure of 14 suggests a reduction of aminotriazole and an oxidation of SCN-, with which confirms the influence of reaction condition on structures of CPs through enhancing the reactivity of reagents. [Cd₂(3-abpt)Cl₄]_n(15) is 3D, as a comparison of 13, embodying the effect of ligand geometry on structures of CPs. These CPs, except for 14, all showing an emission band around 433nm that can be attributed to ligand-based excitations since their locations are near to those of ligands.Chapter four sum up the work according to the structures and property'research of complexes 1-15.