Sharif Digital Repository

In this project, M2 macrocyclic ligand, bearing three pyridine side arms (3p) was synthesized and characterized by employing elemental analysis and 1H NMR, 13C NMR and IR methods. The interaction of 3p with zinc tetraphenylporphyrin was investigated, using fluorescence and UV-vis spectroscopy in solution phase. The observed quenching in the fluorescence spectrum alongside Q band shift in UV-vis spectrum indicate on the interaction of 3p with ZnTPP. The formation constant for these interactions in 1:1 ratio was calculated 10100 M-1, employing fluorescence method. The formation constant was calculated 630 M-1 for 1:2 ratio for 3p:ZnTPP. Having 1:2 ratio 3pZnTPP was also synthesized and... 

Epoxidation of alkenes by Mn(III)meso-tetra(4-sulfonatophenyl)porphyrin chloride (MnTPPS4Cl) in the various homogeneous and heterogeneous catalytic systems was investigated. In the case of homogeneous catalysis, epoxidation of cyclooctene in CH2Cl2/MeOH mixture using urea hydrogen peroxide (UHP) as an oxidant and imidazole as a co-catalyst results in the formation of cycloocetene oxide in 87% yield. Using this catalytic system various alkenes successfully oxidized to their corresponding epoxide in high conversions and selectivity. Cyclic alkenes oxidized more easily than linear alkenes. In addition, epoxidation of alkenes was investigated in the heterogeneous catalytic systems. For this... 

Self-Assembled Monolayer (SAM) is the first step in all surface engineering and assembly processes. It is used in sensor fabrication, memories and molecular recognition and optoelectronic devises as an active surface for patterning and chemical architecting of solid substrates. Tetraphenyl porphyrins because of their high stability and uniqe electronic and optic properties, that comes from their conjugate π electrons, easily can be used in these monolayers. Moreover they have a wide application because of their ability for coordination with metals and accepting substituents with electron donating and withdrawing properties. Electron transport through these layars which attach to the surface... 

In the present research, a series of bimacrocyclic tweezer anchored through azobenzene moiety were synthesized and characterized by applying IR spectroscopy, 1H and 13C{1H} NMR, fluorescence spectroscopy, UV-visible spectroscopy, mass spectrometry and elemental analysis and in some cases by X-ray crystallography. Firstly, UV-visible spectroscopy established that the irradiation of the tweezers with UV light promoted the trans to cis isomerization. On the other hand, thermal cis-trans isomerization behavior of the azobenzene moiety in tweezers was surveyed in which the cis isomers were formed of the heating at 50 oC for 5 minutes. Where the -OH group was replaced with 4-toluenesulfonyl... 

The goal of this study is to synthesise and study the catalytic properties of a Mn-Porphyrin complex fixed on a magnetic nanoparticle bed. This nanocatalyst was used in oxidation of sulfides and epoxylation of olefin. In the multistage synthesis of this catalyst, iron oxide magnetic nanoparticles were first prepared, then, by silanizing these nanoparticles, and then using the 3-chloropropyltrimethoxy methanol reactor, Immobilzation the material on the substrate and immediately react in reaction Substitution of the nucleus of friendship and using a sodium azide reaction, bromide is replaced by azide. Subsequently, by synthesising 4-hydroxy porphyrin and replacing one of its positions with... 

In this thesis, functionalized Fe3O4 nanoparticles have been utilized as a support for immobilization of homogeneous catalysts. The catalytic activity of the supported heterogeneous nanocatalysts was investigated in hydrocarbon and sulfide oxidation reactions. In the first part of this research, imidazole functionalized Fe3O4 nanoparticles (Fe3O4@SiO2-Im) were used as a support to anchor manganese porphyrin complex, [MnT(4-OMeP)P]OAc; via axial ligation. Catalytic application of the immobilized manganese porphyrin was studied in oxidation of alkenes and sulfides. To find suitable reaction conditions, the effect of different parameters such as solvent and temperature on immobilization process... 

In this project, in continuation of a PhD resreach undertaken in this research group in 2017, the synthesis and study of two new tweezer and linker molecule bearing azobenzene moiety were carried out, characterized by applying IR spectroscopy, ¹H and ¹³C {¹H} NMR, fluorescence spectroscopy, UV-visible spectroscopy, elemental analysis and X-ray crystallography. Firstly, interaction of T2 with meso-tetraphenylporphyrinato zinc(II) and aluminium tetraphenylporphyrinato were studied using the fluorescence spectroscopy. The formation constant of T2 in cis and trans isomer with ZnTPP was measured as 5.1(±0.4) ×108 and 2.0×108(±1074) dm6mol-2, respectively. The formation constant of T2 in with... 

A set of azacrown macrocyclic ligands bearing pyridine moiety (bp, 1p, 2p) were synthesized and characterized by single-crystal X-ray diffraction (SCXRD), elemental analysis, FT-IR, 1H and 13C NMR methods. The complexes of zinc tetraphenylporphyrin (ZnTPP) with the bp and 1p as the axial ligand were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H and 13C NMR, fluorescence, UV-vis, cyclic voltammetry, together with TD DFT calculations. By employing this method for ZnTPPbenz and ZnTPPH complexes elucidated that the pyridine moiety was bonded through the fifth- coordination site on the zinc metal atom. In the following study, the coordination... 

Petroleum contains a large variety of metal compounds with vanadium and nickel being the major metals. Some 6–34% of the total vanadium content is made up out of metallo-oxo-porphyrins, also referred to as petroporphyrins. Metalloporphyrins have long excited interest as oxidation and epoxidation catalysts. In the other hand the selective oxidation of sulfides to sulfoxides is of interest because of the importance of sulfoxides as synthetic intermediates in organic synthesis. A range of sulfides can be selectively oxidized to the corresponding sulfoxides in good yields using catalytic quantities of vanadyl complexes. Vanadium oxo tetraphenylporphyrin VO(TPP) catalyst is successfully applied... 

In this work heterogenization of manganese porphyrins in ZIF-8 and Mg-Al-LDHs structures is performed, via host-guest interactions, and their catalytic activities for olefins epoxidation are also investigated.A heterogenized meso-tetrakis(2,3-dihydroxyphenyl)porphyrinatomanganese(III) acetate at zeolite imidazolate framework-8 (T(2,3-OHP)PorMn@ZIF-8) is investigated in the catalytic olefin epoxidation reactions at room temperature at the first part. Heterogenization is done through a non-classical hydrogen bond proposed between T(2,3-OHP)PorMn bearing O-H groups and C-H of the 2-methylimidazolate linkers in ZIF-8 structure. The aforementioned compound characterized by X-ray powder...