| In this dissertation, a series of novel supermolecular architecture have been designed inthe principle of crystal engineering by means of solution evaporation and hydrothermalconditions. The structures and characters of these compounds were measured and expressedby single-crystal X-ray diffraction, X-ray powder diffraction, IR spectrum and elementalanalyses, and thermal gravimetric analyses, fluorescent properties are also discussed.1.11 new supramolecular complexes were designed and synthesized:[Ni(phen-dione)·4(H2O)2]·SO4·H2O 1,[Co(phen-dione)·4(H2O)]·SO4·H2O 2,[Zn(phen-dione)·4(H2O)]·SO4·H2O 3,Ag(phen-dione)·NO3 4,[Cu(phen-dione)(SIP)(H2O)2]·H2O 5,[Cu(dafo)2(H2O)2]·H2SIP·2H2O 6,[Ag(phen-dione)2]·H2SIP·H2O 7,[Mn(phen)2(H2O)2]·2HSIP·2H 8,[Co(phen)2(H2O)2]·HSIP·3H2O 9,Pb3(phen)2(SIP)2(H2O)3 10,[Pb4(μ4-O)(SIP)2(CH3OH)] 11,2. Complexes 1, 2, 3, 5, 6, 7, 8 and 9 are all zero-dimensional structures. Complexes 1, 2and 3 are all adopted octahedral geometry, and be expanded into 3D supramolecularstructures by hydrogen bonds. Complex 5 is the first example of mixed ligands, includingphen-dione and SIP ligands, and further connected into 1D ladder-like supramolecular chainby hydrogen bond interactions. In the structure of 6, 7, 8 and 9, the ligands SIP are all notcoordinated with metal ions, engaging in the formation of hydrogen bond. Complexes 4 and10 are one-dimensional chain structures, and further assembled together through hydrogenbonding andπ-πstacking interactions into the 3D supramolecular frameworks. Complex 11 is2D layer structure with tetranuclear secondary building unit [Pb4(μ4-O)]. The fullydeprotonated SIP in 11 performs six complicated coordination modes, which have not beenreported up to the present. Pb-Pb,hydrogen bond andπ-πstacking interactions constructed1D into 2D or 3D supramolecular structure.3. Thermalgravimetric analyses exhibit that the organic framework of 1-11 do notcollapse until the temperature rising up to 420°C for 1, 2 and 3, 450°C for 5, 6, 7 and 9, 350°C for 4, 8, 10, showing the high thermal stability.4. The electrochemical properties of 5 and 6 were measured in DMSO solution by cyclicvoltammetry. The test results showed an irreversibile, one-electron wave for 1, correspondingthe Cu(II)/Cu(I) couple (Epa = 0.333 V, Epc = 0.026 V,ΔE = 0.3 V, Ip,c/Ip,a = 1.7). Complex6 has two pairs of irreversibile redox peaks, Epa1 = 0.05 V,Epc1 = -0.45 V,Epa2 = 1.1 V,Epc2= 0.82 V, corresponding to the redox process of ligand and Cu(II)/Cu(I) couple, respectively.5. In the solid state, the title compounds exhibit intense fluorescence (λmax = 435 nmand 492 nm for 1, 430 nm and 467 nm for 2, 424 nm and 488 nm for 3, 420 nm and 487 nmfor 4, 456 nm for 5, 491 nm for 6, 456 nm and 492 nm for 7, 425 nm for 8, 390 nm for 9, 380nm and 484 nm for 10 and 446 nm for 11). The emission bands are assigned to be intraligandcharge transfer of phen-dione ligand for 1-5 and 7, phen for 8-10, and ligand-to-metal ormetal-to-ligand charge transfer of SIP for 11. 6. The electronic spectra of 5 and 6 are recorded in DMSO solution in the wavelengthrange 250-600 nm. Results show that complexes have quite similar absorption peaks withthese ligand. The characteristic K-band (the band region of ca. 266-310 nm), B-band (theband region of ca. 324-345 nm) and R-band (the band region of ca. 353-370 nm) are stilltypical in the absorption spectra. The R-band remains the same in energy, corresponding theintraligand n–π* transitions, whereas the B-band and K-band shift toward lower energy due tothe coordination of Cu2+ ion with ligands. Moreover, in complexes 5, Density functionaltheory (DFT) calculations (GAUSSIAN 03) were performed to provide information ofabsorption spectra. Results show that the experimental values are basically consistent with thetheoretical values. |
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