Investigation Of Optic-magnetic MOFs And Self-assembly Of Ru(â…¡) Nanosphere Based On Heterocyclic Ligand Containing Nitrogen

Metal-organic frameworks (MOFs) and supramolecular coordination complexes (SCCs) are two new branches of coordination chemistry. Here, we contributed to these fields with some new MOFs and novel SCCs. Firstly, forty-five MOFs have been synthesized from the ligand (H3ctia) and the selective metal centers under the hydrothermal condtions. The structure of these complexes was determined by single crystal X-ray diffraction, IR and elemental analysis. At the same time, the magnetic and luminescent properties of these complexes were studied in detail. Secondly, a series of novel tridentate terpyridinyl ligands with three arms have been designed, synthesized and characterized by NMR and MALDI-ToF MS. With these ligands, we firstly synthesized and isolated a series of terpyridine-based, spherical supramoleculars. The structure of the complexes was characterized by1D and2D NMR, ESI-MS, gMS2, ESI-TWIM-MS and molecular modeling. The stability of these complexes was also studied. The main contributions are as follows.(1) Twenty3d-4f heterometallic complexes were constructed from H3ctia ligand. The analysis of single crystal X-ray diffraction shows complexes1-19are isomorphous and displays novel3D frameworks based on the parallel arrangement3d coordination chains and4f coordination layers. The out-of-phase signals of ac susceptibility observed for9and18suggest the slow-relaxation process, which are not common in3D coordination polymers, especially in3D heterometallic coordination polymers. The emission spectra in visible and near infrared region and the luminescence lifetime were aquired.(2) Fourteen4f metal complexes have been constructed from H3ctia and (NH4)2C2O4The results of single crystal X-ray diffraction display dihelical-chains were observed in compound21-27, which formed from dinuclear lantern SBUs linked by C2O42-. The magnetic and luminescent properties of these complexes were studied. The emission spectra in visible and near infrared region, the luminescence lifetime and the quantum efficiency of these complexes were acquired.(3) Eleven3d metal complexes have synthesized with H3ctia by adjusting the pH value, reaction temperature and reaction time under the hydrothermal conditions. The structure of these complexes was determined by single crystal X-ray diffraction, IR, etc. The magnetic and luminescent properties of these complexes were studied. The results indicate the presence of antiferromagnetic couplings among metal centers. Complex40is a spin-glass. Complex41is an antiferromagnetism wth TN=4.5K.(4) Four novel tridentate terpyridinyl ligands with three arms have been designed and synthesized. The structure of these ligands was characterized by1H NMR,2D COSY,2D NOESY and MALDI-ToF-MS.(5) With these ligands, we firstly synthesized and isolated a series of terpyridine-based, spherical supramolecular through the combination of novel tridentate terpyridinyl ligands with inert Ru(II) ions in a one-step reaction. Unequivocal characterization was accomplished by1D and2D NMR experiments, ESI-MS, gMS2, ESI-TWIM-MS spectroscopies and molecular modeling. These complexes show good stability under thermal, acidic or basic conditions. We obtained the first single crystal structure of3D terpyridine-based coordination supramolecular.(6) Three Dimer and two Dendrimer core units have been synthesized and characterized by1H NMR and ESI-MS。...