Synthesis, Structures And Properties Of Supramolecular Compounds Based On Bipyrazole

Recently, supramolecular compounds have attracted much attention because of their application in luminescence, magnetism, gas storage and so on. In this thesis, we choose 3,3’,5,5’-tetramethyl-4,4’-bipyrazole (bpz) as the primary ligand, together with dicarboxylic acid as secondary ligand, to react with different ions and obtained twenty two compounds. What’s more, all compounds have been determined by single-crystal X-ray crystallography, elemental analysis, powder X-ray diffraction, thermal analysis, flurescence spectroscopy and UV-Vis spectra. The text is divided into five chapters, each chapter is as follows:In the first preface chapter, the basic concepts of supramolecular chemistry, coordination chemistry, synthetic technology and factors of self-assembly process were introduced. And we highlight the research status of pyrazole chemistry.In the second chapter, using bpz ligand and dicarboxylates with varied carbon chain length and Ag(I) ion, seven compounds were obtained, namely, [Ag2(bpz)4(mal)·8H2O]n (1L and 1R), [Ag2(bpz)3(suc)]n (2),[Ag4(bpz)5(glu)2]n (3), [Ag4(bpz)5(adip)2]n (4),[Ag4(bpz)7(pim)2·12H2O]n (5), [Ag2(bpz)4(sub)·7H2O]n (6), and [Ag2(bpz)3(aze)·4H2O]n (7). Because of the effect of dicarboxylates, these seven compounds range from 2D hcb and fes layers to 3D chiral SrSi2, a chiral dia-f, and 3,4T1 networks.In the third chapter, using bpz ligand and different dicarboxylates and Cu(II) ion, seven compounds were obtained, namely, [Cu(bpz)o.s(adip)]n (8), [Cu2(bpz)4(sub)2]n (9), [Cu4(bpz)1.5(aze)-H2O]n (10), [Cu2(bpz)(pta)2(H2O)·H2O]n(11), [Cu2(bpz)(ipa)]n (12),[Cu2(bpz)(o-pda)2·H2O]n(13), [Cu2(μ3-OH)(bpz)(p-pda)1.5·H2O]n(14). Depending on different dicarboxylates, we obtained 1D tape built from bpz serged 1D helical Cu2(ipa) chain (12),2D 44-sqI networks (9 and 11),3D pcu networks (8 and 13), rare 3D 5-connected hxg-d-5-C2/c (10) and 3D 8-connected hex (14) network.In the fourth chapter, using bpz ligand and different dicarboxylates and Zn(II) ion, six compounds were obtained, namely, [Zn(bpz)2(H2O)3·2Hpta]n(15), [Zn(bpz)(pta)]n(16), [Zn(bpz)(tpa)·(H2O)]n(17), [Zn(bpz)(tpa)·4H2O](18), [Zn(bpz)(npa)·H2O]n(19),[Zn(bpz)(npa)·H2O]n(20). And the control of solvent on structure of compounds was studied in detail. Interestingly, discrete 15 can irreversibly transform from OD discrete molecule to an infinite 3D structure (16) by heating it in CH3OH-H2O solvent, indicating a solvent-induced structural transformation.In the fifth chapter, using bpz ligand and different dicarboxylates, two compounds were obtained, namely, [(bpz)2-H2sub]n (21) and [(bpz)2·H2seb]n(22). Because of dicarboxylates with varied carbon chain length, these two compounds showing varying degrees of interpenetration. At the same time, the "green" mechanochemical reaction route was also proven to be efficient in this chapter.