Synthesis And Properties Of Functional Complexes Based On Conjugated Tetrathiafulvalene Ligands

Tetrathiafulvalene (TTF) and its derivatives have been widely used as versatile building blocks in the fields of supramolecular and material chemistry due to its high π-electron donor ability and multiple and reversible redox processes. One of the research trends in novel functional materials is to search for molecules with more π-extended systems. Intensive studies have shown that the extension of TTF units not only leads to stabilize oxidized states but also can enhance the dimensionality of materials by increased π…π or S…S interactions between planes. In this dissertation, we report the synthesis of four new polymeric metal compounds based on the tetrathiafulvalene-tetrabenzoate ligand and a dinuclear ruthuium complex based on bis-(1,10-phenanthroline)tetrathiafulvalene ligand. Moreover, the photophysical and electrochemical properties of these compounds are systematically studied.1. Synthesis and properties of electroactive coordination polymers based on the tetrathiafulvalene-tetrabenzoate ligandFour new coordination polymers (1-4) based on tetrathiafulvalene-tetrabenzolate ligand (H4L1) were synthesized and structurally characterized. The versatile carboxylate ligand coordination modes and different metal ions used as the variable metal nodes eventually gave rise to these (3,4), (3,8), (4,8)-connected topological networks. The redox properties of the coordination polymers 3 and 4 were investigated and two reversible oxidation processes were observed. Gas adsorption measurements indicated adsorption selectivity for CO2 over N2 due to the large π-electron clouds of TTF ligands in MOFs. These results suggest that the incorporation of redox-active ligands into coordination frameworks is an effective strategy to engineer porosity and redox activity into framework systems leading to potential applications in electrical swing adsorption for gas separations.2. Synthesis and properties of a ruthuium complex based on the bis-(1,10-phenanthroline)tetrathiafulvalene ligandThe bis-(1,10-phenanthroline)tetrathiafulvalene ligand (L2) was synthesized via self-coupling reaction for the first time. Microwace-assistant synthesis of its ruthenium complex (5) offers an effective strategy to incorporate insoluble rigid and nearly planar TTF ligands into molecule-based materials. To the best of our knowledge, the crystal structure of 5 unambiguously displays the formation of crossly stacked dimer due to gigantic steric hindrances, a rare phenomenon. Besides, the dinuclear ruthenium exhibits rich electrochemical property with multiple redox process and can be investigated through theoretical calculations to interpret the electrochemical and optical properties. The electron paramagnetic resonance measurement confirms that there are some charge-transfer-induced partial electron transfer processes both in the ligand and metal complex.