| Tetrathiafulvalene (TTF) and its derivatives have stimulated great interest for a long time, due to their unique donor and redox properties. They have been used as organic conductors or semi-conductors, molecular sensors. In recent decades, one of the hotspots in this field is to design bi-functional TTF derivatives with redox and coordinating/hydrogen bonding functions, such as TTF -Py, TTF-crown or TTF-amide. The amide group can form rich hydrogen-bonds, which makes them have good application in molecular assembling and responding. Although some TTF-amide derivatives have been reported, this field needs to be further studied. In this thesis, some new TTF-amide derivatives and their metal complexes have been synthesized; their solid-state chemistry and solution chemistry have also been studied. The major contents are as follows:1. Three charge-transfer compounds [L12Cu2Cl6] (1), [L12Cu2Br6] (2) and L12Cu2Br4 (3) were obtained by reacting of DMT-TTF-(CONH2)2 (L1) with CuX2 (X=Cl, Br). Copper ions in 1 were directly coordinated to oxygen atoms of amides. It is the first example of TTF-amide which was oxidized and coordinated with metal ions. Compound 3 is a charge-transfer salt with a Cu2Br42– anion and a [DMT-TTF-(CONH2)2]+ cation. Hydrogen bonds and S···S short contacts play an important role in the assembly of compounds 1 and 3.2. Four charge-transfer compounds L22CuBr4 (4), L22CuCl4 (5), L2·ClO4 (6) and L2·Br (7) were obtained by reacting DMT-TTF-(CONHMe)2 (L2) with copper (II) salts. Comparing with the structures of compounds 4, 6 and 7, we draw a conclusion that C···C contacts play the main role in the properties of these compounds, when the S···S contacts are equivalent. Reaction of DMT-TTF-CONHMe (L3) with CuX2 (X=Cl, Br) afforded three charge-transfer compounds L32CuBr3·2THF (8), L32CuCl3 (9) and L3·Br (10). Redox recognitions of L2 to H2PO4– and other anions were investigated by 1HNMR and electrochemistry. The results indicate that L2 presents different recognitions to different anions and the strongest interaction occurs between L2 and H2PO4– anion.3. Four complexes [Cu2I2L42]·THF·CH3CN (11), [AgL42]·ClO4·H2O (12), [MnCl2L42]·CH3CH2OH (13) and [Ni(acac)2L4]·2CH3OH (14) were obtained by reacting of DMT-TTF-(CONHCH2Py)2 (L4) with CuI, AgClO4, MnCl2, Ni(acac)2. The results indicate that complex 11 is a one-dimensional compound; the metal in complex 12 adopts liner arrangement, and forms quasi-metal line through the disorderly vibration of Ag···Ag interactions; complex 13 is the first example of the two-dimensional polymer in TTF-Py system; while complex 14 is a simple mono-nuclear complex. Their electrochemistry and spectrum properties were also studied.4. A new TTF-amide derivative DMT-TTF-(CONHCH2CH2NH2)2 (L5) was synthesized. Reactions of L5 with Cu(ClO4)2, Ni(OAC)2, HClO4 afforded two complexes [NiL5]·1.5CH3OH (15), [CuL5(CH3OH)]·H2O (16) and a protonated salt [L5H2]·2ClO4 (17). The structures of complexes 15 and 16 are similar, the metal ions form coordinated bonds with the free amines and covalent bonds with amides.We chose TTF-amides as the precursors, discussed the interactions between precursors and metal ions, and explored their redox and magnetic properties. The fundamental properties of these TTF-amide derivates were released in theory and structure, their supermolecular structure and coordinated assembly were discussed. Our work is important for the exploitation of molecular materials.
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