Sharif Digital Repository

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... 

In the present study, the coordination chemistry of an O4N4-tetrabenza-crown ether macrocyclic ligand L1 with M2+ (M= Cu, Cd, Hg, and Pb) was investigated by employing UV-visible, 1H-NMR spectroscopy in their solutions. According to the association constants calculated by 1H-NMR titrations, the complex formation stability for these closed shell cations was found in a series of Pb > Hg > Cd, leading to the larger cation, the better accommodation with L1. Moreover, the supramolecular interaction of L1 with fullerene C60 was also assessed by UV-visible spectroscopy. Meanwhile, the structure of [Cd(1)]2+ complex was determine by X-ray crystallographic method in their solid state. A square... 

In this study, a water-soluble Aza-crown N2O2 ligand with a two-carboxylate side arm was synthesized and characterized by 1H-NMR, 13C-NMR, UV-vis, fluorescence, mass spectrometry, and elemental analysis. Unlike EDTA, this ligand is soluble in acidic solution. Fluorescence spectroscopy did not show significant selectivity except for calcium (and to some extent strontium) and copper cations. Due to the similarity of the aminocarboxylate groups with some chelating agents, the ability of this macrocyclic ligand as a scale inhibitor was investigated using the NACE-TM374 standard test method. In these tests, the new arm ligand showed significant protection against the presence of calcium sulfate.... 

One of the most common methods of producing fullerenes is electric arc vaporization of graphite. Due to the low yield and purity of the nanoparticles in this method, the synthesis and isolation of the area research is important. In this work, the production was improved in a multi-channel arc reactor in which having horizontal graphite electrodes. The influence of various operational parameters such as pressure of inert gas, spark time, interval time between two sparks, voltage and current were completely optimized. Moreover, the prominent advantage of the new reactor was increasing the number of manufacturing units, at least from one to three, which the production of fullerene was... 

The purpose of this project is to synthesis of O2N3-azacrown ligands with 17 to 21 membered ring and investigation of their interaction with C60 according to increase ring size. These macrocyclic ligands can be used in C60 purification. In this project, change in macrocyclic cavity for finding the best macrocycle with appropriate cavity to C60 size has been considered. Firstly, five O2N3-azacrown ligands were synthesized and characterized by NMR spectroscopy and elemental analysis. Interaction of these ligands were considered by electronic spectroscopy applying Benesi-Hildebrand equation. According to the results, it was found that the best macrocycle for formation of stable complex with... 

In our previous work in this laboratory, macrocycle containingO_2 N_2 and O_2 N_3- donor set with various ring size were synthesized. The intraction of macrocyles with [60]fullerene were determined. In this research, we synthesized 22-membered aza-crown macrocycle ligand containing O_4 N_2- donor set and characterized by NMRspectroscopy. The intraction of macrocycle with [60]fullerene were also investigated by UV-Visible spectroscopy. The formation constant was determined applying Benesi--Hildebrand equation. The result has been showed that O_4 N_2 macrocyle had better complexation with [60]fullerene in comparision of O_2 N_3 and O_2 N_2 donor sets. Then, the interaction of O_4 N_2 with... 

Fullerenes are molecular solid materials which are composed of 3D closed shell carbon-only structure. As soon as mass production of fullerenes was performed, the synthesis and characterization of endohedral fullerenes having at least one non-carbon element in the hollow fullerene cage, was started (in which about 30 atoms inserted in it so far). Furthermore, because of low efficiency and purity of these nano-particles, nowadays characterization of fullerenes is one of the most important research fields. In this project, we firstly optimized the fullerene production parameters in an arc discharge reactor to reach convenient efficiency. Then, the synthesis of endohedral fullerene by vaporizing... 

In this research, four N2O2–azacrown macrocyclic ligands with naphthalene pendant arms (L1-L4) were synthesized using direct synthesis. The products were characterized applying 1H and 13C {1H} NMR spectroscopy, IR and Mass spectrometry. Interaction of these ligands with [60]fullerene and Cu(II) were monitored respectively by fluorescent as well as UV-vis spectroscopy and applying Benesi-Hildebrand equation. These intercations were compared with N2O2 macrocyclic ligands in previous experiments in terms of their calculated association constants (Ka). According to our results, the presence of naphthalene pendant arm groups led to increase the interaction with [60]fullerene compared to the... 

The goal of this project was study on coordination behavior of the 14-membered macrocyclic ligand of type N2O2 aza-crown while it is attached to fullerene C60 nano-particle. For this purpose, firstly the macrocyclic ligand (Fig 3-1, L1) was synthesized and then was reacted with C60 (Fig 3-1, L2) of which the product was characterized by elemental analysis. Since the product was insoluble in any solvents, further study on its coordination chemistry was impossible. In a second procedure, the macrocyclic ligand was reacted with benzylbromide. The reaction mixture gave two macrocyclic ligands with different number of benzylic pendant groups (Fig 3-1, L3-L4). The products were separated by column... 

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... 

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... 

By considering previous experiments undertaken in our laboratory on O2Nx (x=2,3) azacrown complexes with [60]fullerene, it was found that factors such as the macroring size, type and number of the donors groups in these macrocyclic ligands had significant effects on their selectivity towards [60]fullerene complexation. In this research, three N2O2N–azacrown macrocyclic ligand having uniform distribution of nitrogen atoms in macroring was synthesized using direct synthesis and high dilution method. The products were characterized applying 1H and 13C NMR spectroscopy as well as elemental analysis. Interaction of these ligands with [60]fullerene and Cu(II) were monitored by UV-vis spectroscopy... 

Since the discovery of fullerene C60, its chemical and physical properties have been a hot topic in the field of research. For the past two decades remarkable developments achieved in the field of fullerenes chemistry. The aim of this study is comparative study of antioxidant property of fullerene C60 and its amine derivatives and the effect of transition metal complexes. At the outset the anti-oxidative property of fullerene C60 and its amine derivatives explored and it was found that by increasing the chain length of amines, the anti-oxidative property of aminofullerenes increased respectively. In next step the effect of CoSALEN complex on anti-oxidative property of fullerene was... 

New N4O6 molecular tweezers were synthesized from N2O2 benzo- and naphthodiazacrown macrocycles bearing benzylic dialdehydes as a flexible and semi-flexible spacer in a short time and at room temperature. The products were characterized by IR, 1H and 13C NMR spectroscopy as well as elemental microanalysis. The interactions of some of these tweezers with C60, Cu(II), Co(II), Ni(II), Zn(II), Hg(II) and Mn(II) were investigated by employing UV-Vis and fluorescence spectroscopy. Efficient fluorescence responses for 2NM3BD were observed in the presence of C60, Cu(II), Mn(II), Hg(II) and Zn(II). Meanwhile, the calculation of the association constants (K¬BH) employing Benesi-Hildebrand equation in... 

In the present research, the conversion of methanol to hydrocarbons was studied over a new series of mesoporous low-silica HZSM-5 (Si/Al=11) catalysts impregnated with cations such as Fe, Zn, Mo and Cr. A systematic study on the effect of stepwise modification of the catalysts for the conversion of methanol to gasoline (MTG) was undertaken in a fixed-bed tubular reactor under ambient pressure at 375 °C, feeding with weight hourly space velocity (WHSV) of 2 h−1. The catalysts were prepared in the absence and presence of cationic promoted factors, in both alkaline and neutral aqueous solutions. The final catalysts characterized by using Fourier-transform infrared, X-ray diffraction, X-ray... 

In the present study, the coordination chemistry of an amino acid azacrown macrocycle ligand bearing one carboxylic acid arm (MA1) was investigated by employing NMR spectroscopy, crystallography and computational chemistry. MA1 was synthetized by the reaction of chloroacetic acid with the parent azacrown macrocycle and its purity was confirmed with 13C and 1H NMR for the first time. A new MA1 homologue, MA3 was also successfully prepared and characterized with NMR, mass spectrometry, and elemental analysis. NMR studies showed that MA1 binds to cadmium via the carboxylate arm in solution. Crystallographic studies showed that MA1 formed a one-dimensional polymer with cadmium, wherein the... 

In this treatise, the effect of type of macrocycle ring on the final structure of the complexes which made from them was investigated. For this purpose, by changing the 15-membered benzylic macrocycle with two pyridine pendant arms (2p), which was studied in our previous experiments (the effect of the position of the nitrogen atom of the pyridine ring in the side arm and the type of metal ion in the geometry of its complexes), two new macrocycles by adding a naphthalene rings instead of benzylic ringsin in 2p and increasing the ring size from 15 to 17 members, Lpy-naph and Lpy-benz were symthesized respectively. The molecular formula and structure of Lpy-naph and Lpy-benz were confirmed by... 

The purpose of this project is the synthesis and characterization of a group of phenolic amino acidic derivatives that are studied in both solid phases as well as their solutions. For this, new phenol derivatives of serin and isoleucine amino acids were synthesized and characterized by 1H NMR , 13C NMR, IR spectroscopy as well as elemental analysis. These ligands were utilized to prepare LSF perovskite membrane. According to their XRD patterns, it was concluded that the powdered precursor prepared by serin derivative has shown better qualification and less intermediate phase in the synthesized perovskite membrane similar to the sample prepared by applying EDTA. Furthermore, in the previous... 

Co(salen)-type complexes: Co(salen), Co(salophen), Co(3,5-Brsalen), Co(Clsalen), Co(3-OMe,5-Brsalen), Co(saltmen), Co(Brsalen), Co(OMesalen) were shown to be efficient catalysts for oxidizing cumene to cumyl alcohol, methylstyrene and acetophenone. The mixture was characterized by 1H NMR and GC-Mass spectroscopy. Product s efficiency and turnover number of catalysists were determined. Proposal of the mechanism provides a rationale for the influence of ligand substitutions on the reaction. A series of experiments are reported to provide strong support for a mechanistic scheme that involves reaction of coordinated dioxygen. On the basis of these observations, the coordination of O2 to this... 

In our previous work, we have been undertake complexion of new amino phenolic ligand with Fe(III) and Co(II) in order to synthesis LSCF - and LSF - type perovskite inorganic membranes. In this study, the interactions between Co(II) and Fe(III) cations and the mentioned ligands were investigated their by cyclic voltammetry technique. In aqueous solution, it was found that chelate ring size has more prominent effect on the ligand-metal interaction than the related amino acid substitution. Accordingly, the amino phenol substituted...