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Home > Organotin Iv Complexes of O, N, O and S, S Donor Ligands Derived from Dibasic Acids for Biological Applications

Organotin Iv Complexes of O, N, O and S, S Donor Ligands Derived from Dibasic Acids for Biological Applications

Thesis Info

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Author

Ullah, Hussain

Program

PhD

Institute

Quaid-I-Azam University

City

Islamabad

Province

Islamabad.

Country

Pakistan

Thesis Completing Year

2018

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/bitstream/123456789/10711/1/Hussain%20Ullah_Chem_2018_QAU_PRR.pdf

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676726829735

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Herein we reports the synthesis of new mono and diorganotin(IV) complexes of Schiff baes/hydrazones with [O, N, O] and dithiocarbamates with [S, S] donor ligands. The methodologies described herein includes; the synthesis of five versatile Schiff bases/hydrazones ligands; N'', N''-4-bis(2-hydroxybenzylidene)oxalohydrazide(H4L1), N'', N''-4-bis(2-hydroxylbenzylidene)malonohydrazide (H4L2), N′, N′-4-bis(2- hydroxybenzylidene)succinohydrazide (H4L3), N′, N′-4-bis(2-hydroxybenzylidene)glutarohydrazide (H4L4) and N′, N′-4-bis(2-hydroxybenzylidene)adipohydrazide (H4L5). Herein the thesis also embodied another series of five dithiocarbamates ligands of the types; dipotassium-2, 2-oxalylbis(hydrazine-1-carbodithioat) (K2L1), dipotassium-2, 2-malonylbis(hydrazine-1-carbodithioate) (K2L2), dipotassium2, 2''-succinylbis(hydrazine-1-carbodithioate) (K2L3), dipotassium-2, 2''-glutaroylbis(hydrazine-1-carbodithioate) (K2L4) and dipotassium-2, 2''-adipoylbis(hydrazine-1carbodithioate) (K2L5). For the synthesis of organotin(IV) complexes the reaction between Schiff bases/ hydrazone ligands with [O, N,O] donor sites, mono- and diorganotin(IV)chlorides/oxides were carried out at various reaction conditions and obtained fifty new organotin Schiff bases/hydrazone complexes. The reaction between dithiocarbamae ligands with [S, S] binding sites, mono- and diorganotin(IV)chlorides were unsuccessful and end up with desulfurized isothiocynates. The structural and coordination chemistry of ligands with O, N, O and S, S binding mode/sites and thier organotin(IV) complexes were investigated by using FT-IR and single crystallographic studies in the solid sate. The solution chemistry of these complexes was investigated through mass spectrometry and some multinuclear (1H, 13C and 119Sn) spectal studies. The results revealed that Schiff bases/hydrazones coordinate to tin through a tridentate mode using [O, N, O] binding mode. The structural analysi of single crystal by X-ray technique showed that organotincomplexes procured from hydrazone with tridentate lignads (O, N, O), mono- and diorganotin(IV) chlorides exhibited distorted octahedral (oh) and distorted trigonal bipyramidal (tbp) geometry respectively.Based on the computational studies; the trigonal bipyramidal complexes showed a Sn···O tetrel bonding/interaction in the solid state. A computational study, in combination with the quantum theory of atoms in molecules (QTAIM) shows that the Sn···O interactions involved here are purely electrostatic in nature with little covalent character and leads to a shorter Sn···O [3.480(2 Å)] inter-atomic bond distance as compare to the reported “sum of van der Waals radii (3.92 Å)”. However, these types of interaction cannot be seen in the compounds when the phenyl /butyl groups or when the methylene spacer (-CH2-) between the two-hydrazone fragments is increased replaces the methyl groups. Finally, all the complexes were screened for anticancer activities using carbopaltin as a standard drug. The diorgantotin hydrazone complexes;wheremethyl and phenyl groups are attached to tin(IV)showed reasonable activities due tosolubility problems but the dibutyltin(IV) complexes of the hydrazone [O, N, O] ligands showed excellent activities and have been used as representative sample (compounds) against various cancer cell lines (HL-60, MCF-7 and HeLa ) obtained from human being. It is assumed that the high cytotoxic activities of the dibutyl tin(IV) complexes are due to its lipophilic character and can be compared with the activity of the standard drug (carboplatin). These results might be helpful in the rational drug designing of those complexes containing the dibutyl moiety.
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Synthesis and Characterization of Multidimensional Co and Fe Based Ferromagnetic Nanostructures

The spintronics is the developing and motivating research area that enhanced the efficiency of conventional electronics devices by the addition of spin degree of freedom such as; to decrease the consumption of electric power, improve the speed of data processing and enhance the integrated densities.This research focuses the physical and structural properties of quaternary full Heusler and binary (magnetic-nonmagnetic) alloys in the field of spintronics. As Heusler alloy nanowires (NWs) is a young research field, therefore the majority research focuses on their synthesis, magnetic properties and structural properties. The main issue is the size dependent structure, transition of phase, spin and magnetic related properties are open for the wide range of research. In the last few decades, Heusler (Half Heusler/full Heusler) family produced the revolutionary effect towards spintronics or magneto-electronics with large Curie temperature, especially at the nanoscale. 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Presently, cobalt and iron-based full-Heusler alloys focus their attention in spintronics based devices such as magnetoresistance (MR), giant magnetoresistance (GMR) and tunneling magnetoresistance (TMR) and provide maximum stability due to half-metallic nature. The Co-based Co2Mn0.5Fe0.5Sn full Heusler alloy NWs were synthesized through alternating current (AC) electrochemical deposition (ECD) in anodized aluminum oxide (AAO) templates. To approach the required results, homemade AAO templates were synthesized by two-step anodization in 5 % H3PO4 solution using 60 V at constant DC source at temperature range 1 to 5 ºC. Achieving the desired structure of full Heusler (L21) alloys NWs became possible in electrochemically by changing the AC- deposition potential from 10 to 18V by the 2V difference. The origin of band gap at Fermi level confirmed the half metallic character(100% spin polarization), thathas been measured through density functional theory (DFT) by using WIEN2k programs of full potential linearized augmented plane wave (FP-LAPW) technique. The diameter of the AAO templates and NWs was found in the range of 55 to 65nm that is confirmed from scanning electron microscope (SEM) in all synthesized Heusler alloy and binary alloy NWs. The formation of partial disorder (B2-type), full disorder (A2-type) and full order (L21) structure of Co2Mn0.5Fe0.5Sn full Heusler alloy is confirmed through X-rays diffraction (XRD) analysis that has been measured in anodic alumina along with substrate of aluminum. Hence at 16V and 18V, the presence of fundamental, even and odd supper lattice peaks confirmed the full order (L21) structure of Co2Mn0.5Fe0.5Sn full Heusler alloy NWs. The deposition of Co, Mn & Fe increases with increase in deposition voltage, whereas Sn shows decreasing order, which implies that each element has different reduction potential. The electrical measurement was examined without AAO templates, the resistivity shows decreasing order (from 160 to 40 Ωcm) to that of mobility shows opposite fashion (28 to 358 cm2/Vs) with respect to increasing in deposition potential. It means that our sample is a metallic character which reduces the electron grain boundary dispersal and a boost of the grain size. The magnetic properties illustrate that coercivity shows sharp increment (from 65 to 245Oe) at 18V owing the formation of fully order (L21) structure of Co2Mn0.5Fe0.5Sn full Heusler alloy NWs. Fe-based Fe2CoSn full Heusler alloy NWs has been synthesized with the same approach, as AC- deposition potential has taken from 9 to 17V by the increment of 2V to achieve the desired results of L21 structure with a combination of 2:1:1 ratio. 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It confirmed the full order structure (L21) of Fe2CoSn Heusler alloy NWs. Below which, A2 and B2-type disorder structure have been synthesized. Besides these, variation and Shift are observed in the intensity of diffraction peaks, that shows the influence of deposition voltage on composition, the order of chemical structure and lattice constant. The increment of the grain size shows the maximum result with the formation of L21 Heusler structure. With such specific structure of Fe2CoSn Heusler alloy NWs, the M-H loops demonstrate that coercivity attained maximum value (484 Oe) at 17V by making some defects that divide such NWs into tiny magnetics, causing the rise in magneto-crystalline anisotropy and blocking the domain walls. 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The analysis of X-ray diffraction (XRD) pattern shows that the aluminum peak are observed because of such NWs are characterized with the substrate. The XRD patterns exhibited the FeMn NWs were crystallized into body centered cubic (bcc) structure. Furthermore, the lattice parameter of FeMn NWs was decreased with addition of Mn content. The grain size shows the increasing order (from 38 to 53nm) w.r.t to increase the concentration of Mn in Fe1─XMnX bath solution that effect to decrease the dislocation density and lattice strain of the FeMn alloy NWs. Using four-probe (Hall measurement) technique, it was found that resistivity has been decreased gradually (24 to 75.5 Ω.cm) whereas conductivity declines with an increase in Mn contents by the effect of an increment of the grain size. Hence, behavior of such alloy moves toward the nonmetallic character. The M-H loops demonstrate that shape anisotropy is dominated in Fe1─XMnX alloy NWs. The increase in Mn contents in such alloy, the coercivity and squareness both shows descending order, opposite to that of grain size. Therefore, it has attributed the motion of domain walls due to the decrease the magnetic grain boundaries." xml:lang="en_US