Syntheses And Structures Of Sulfur-Rich Compounds With Carboxylate And Imine Groups

Tetrathiafulvalene (TTF) derivatives have been one kind of extensively studied functional molecules due to their applications in the field of material chemistry and supramolecular chemistry. On the other hand, carboxylates have been used in analysis chemistry, chemical catalysis, bionics chemistry, and material chemistry. In this thesis, we pay attention to the study of coordination chemistry and molecular assembly of TTF-carboxylate derivatives. The major contents we researched were as follows:1,In introduction, the important achievements of TTF derivatives are reviewed briefly, and then the latest progresses of TTF derivatives in optical, electrical and magnetical properties are illustrated. On the other hand, the different coordination modes of carboxyl groups are summarized and the recent researches on TTF–carboxylates are also described.2,TTF-tetracarboxylate salts (C10O8S4Na4) and their metal complexes with Mn(II) and Cu(II) were synthesized. [Mn(L)_0.5(phen)(H₂O)₂]n·nH₂O (1), [Mn(L)_0.5(bpy)]n·nH₂O (2), [Mn(L)_0.5(bpy)(CH₃OH)]n·2nH₂O (3), [Cu(L)_0.5(bpy)(DMF)]n·n(DMF) (4). Structures of the complexes were determined by single crystal X-ray diffraction. Antiferromagnetic and electrochemical properties of these complexes have been studied.3,Polymeric transition metal complexes with Co(II) and Cd(II) of TTF-tetracarboxylate ligand were synthesized under room temperature and solvothermal conditions. [Co(L)_0.5(phen)(H₂O)₂]n·nH₂O (5), [Co(L)_0.5(phen)(H₂O)₂]n·nH₂O (6), [Co(L)_0.5(4,4-bipy)(CH₃OH)]n·nH₂O (7), [Cd(L)_0.5(bpy)(H₂O)₂]n·3nH₂O (8), [Cd(L)_0.5(phen)(H₂O)₂]n·nH₂O·nCH₃OH (9), [Cd(L)_0.5(bpy)(C2H5OH)(H₂O)]n·nH₂O·nCH₃OH (10). The structures of these complexes were determined by single crystal X-ray diffraction. There are different coordination abilities and different coordination modes of carboxyl groups under different conditions, and the auxillary ligand has an important influence on the structures of the complexes. Except acting as a rigid spacer, the TTF moiety is also a redox switchable building block that can build polymeric metal complexes and metal-organic framework with redox activities.