Synthesis, Characterization, Self-assemblies And Spectroscopic Properties Of Meso-tetrakis (4-hydroxyphenyl) Metalloporphyrins

This thesis introduces the synthesis of meso-tetrakis(4-hydroxyphenyl) porphyrin (H₂THPP) andits metalloporphyrins, also the self-assemblies of meso-tetra(4-hydroxyphenyl) porphyrinmanganese(â…¢) chloride. Based on that, we discussed spectroscopic property of differentmetalloporphyrins after axial coordination, which could provide some new methods and thoughts inthe controlled design of functional metalloporphyrin compounds. In addition, we found a simple insitu redox way to synthesize and separate triiron(â…¢) and dicopper(â…¡) clusters with PhCOO^--bridged. The thesis includes four chapters.In chapter 1, the research background is concisely introduced, which focuses on the currentsyntheses, applications, catalysis, and self-assemblies of metalloporphyrin complexes. What ismore, the significance of this work was also described.In chapter 2, H₂THPP and its metalloporphyrins are prepared and characterized by elementalanalyses (EA), infrared spectra (IR) and UV-vis spectroscopic analyses. Besides, two new structuresof meso-tetrakis(4-hydroxyphenyl) porphyfinato manganese (â…¢) chloride [MnTHPPCl] areassembled in solutions. Their crystal structures are determined by single-crystal X-ray diffractionand AFM. One is packed typically layer by layer, and the other shows a novel 1D helical chainsalong a axis, which is firstly self-assembled by achiral MnTHPPCl via the axial Mn-O coordinateinteractions. This successful assembling of the right-handed helical supermolecule of MnTHPPH₂Osproves the correctness of the quantum calculation results about the N-protonated porphyrins toaggregate with DNA helix selectivity. The AFM images also demonstrate the accordant evidencebetween microstructure and macrostructure.In chapter 3, the effect on the change of spectroscopic properties are discussed before and afterthe axial coordination to metalloporphyrins(Co, Cd, Sn) by axial ligand (Hmt and His). Thephotoluminescence, especially the effect of the coordination and supramolecular interactions on thephotoluminescence of metalloporphyrins are worthy to be further studied. And the SEM imagesshow the facial structural differences between before and after the axial coordination tometalloporphyrins.In chapter 4 is another research aspect. Two types of cluster of triiron(â…¢) and dicopper(â…¡) with PhCOO^--bridged are obtained by an easy in situ redox way, and structurally characterized byelemental analyses (EA), spectroscopic analyses(IR, UV-vis) and single-crystal X-ray diffraction.X-ray crystallography analysis results show that the asymmetry triiron(â…¢) clusters form 1D zigzagchains with intramolecular hydrogen-bonding interactions. The magnetic property was alsocharacterized, and triiron(â…¢) clusters was expected to be a good paramagnetic materials. Contrarily,among the symmetrical dicopper(â…¡) cluster, there is no hydrogen-bonding interactions.