ABSTRACT
Abstract Organometallic compounds, Bis (2,4,6,8 teramethyl-indacenyl) di Iron (1), Bis (2,4,6,8 teramethyl s-indacenyl) mono iron, mono cobalt (2), and Bis (2,6 diethyl-4,8-dimethyl-s-indacenyl) di cobalt (3) were synthesised by means of salt elimination strategy, using Fe(II) and Co(II) salts. The compounds were characterised through spectroscopic and electrochemical methods. Magnetic measurements were carried out by Physical Property Measurement System (PPMS). Mossbauer spectroscopic data reveals that in all compounds, surprisingly, Iron is in +3 oxidation state. DFT calculations have been carried out to understand the change in the oxidation state of a metal. DFT study confirms the electron transfer nature of ligand to metal. Cyclic voltametric study on these compounds shows a large separation (ΔE>800mV) between two oxidation peaks confirming the strong interaction between the metal centres. Magnetic measurements on these organometallic compounds reveals that they exhibit a ferrimagnetic behaviour at temperatures below 40 K.
Resumen En este trabajo se sintetizaron los compuestos organometálicos Bis (2,4,6,8 terametil-indacenil) férrico (1), Bis (2,4,6,8 terametil s-indacenil) ferroso, cobaltoso (2) y Bis (2,6 dietil-4,8-dimetil-s-indacenil) di cobalto (3) mediante la estrategia de eliminación de sales, utilizando sales de Fe(II) y Co(II).Los compuestos se caracterizan por métodos espectroscópicos y electroquímicos. Las mediciones magnéticas se llevaron a cabo mediante el sistema de medición de propiedades físicas (PPMS). Los datos espectroscópicos Mossbauer revelan que, en todos los compuestos, sorprendentemente, el hierro se encuentra en el estado de oxidación +3. También se realizaron cálculos DFT para comprender el cambio en el estado de oxidación de los metales. El estudio DFT confirmó la naturaleza de transferencia de electrones del ligando al metal. El estudio voltamperométrico cíclico de estos compuestos muestra una gran separación (ΔE>800mV) entre los dos picos de oxidación que confirman la fuerte interacción entre los centros metálicos. Las mediciones magnéticas de estos compuestos organometálicos revelan que presentan un comportamiento ferrimagnético a temperaturas inferiores a 40 K.
Resumo Compostos organometálicos, Bis (2,4,6,8 terametil-indacenil) di ferro (1), Bis (2,4,6,8 terametil s-indacenil) mono ferro, mono cobalto (2) e Bis (2,6 dietil-4,8-dimetil-s-indacenil) di cobalto (3) foram sintetizados por estratégia de eliminação de sal, utilizando sais de Fe(II) e Co(II). Os compostossão caracterizados por métodos espectroscópicos e eletroquímicos. As medições magnéticas foram realizadas pelo Sistema de Medição de Propriedades Físicas (PPMS). Os dados espectroscópicos Mossbauerrevelam que em todos os compostos, surpreendentemente, o ferro está em +3 estado de oxidação.Os cálculos do DFT foram realizados para entender a mudança no estado de oxidação de um metal. O estudo DFT confirma a natureza da transferência de elétrons do ligante para o metal. O estudovoltamétrico cíclico dessescompostosmostrauma grande separação (ΔE>800mV) entre dois picos de oxidação confirmando a forteinteração entre os centros metálicos. As medições magnéticas nestescompostos organometálicos revelam que eles apresentam um comportamento ferrimagnético a uma temperatura abaixo de 40 K.
ABSTRACT
ABSTRACT This study covers the evaluation of the structure and the capacity in adsorbing orthophosphate ions of kaolinites collected from sampling sites in Manaus (Brazil). The kaolinites were obtained using physical fractioning (sieving/siphoning) techniques and chemical treatment with HCl, H2SO4, H2O2 and KCl. The investigation of the kaolinite lattices involved the Hinckley and Plançon indexes determined from X-ray diffraction data, Fourier transformed infrared spectroscopy, scanning electron microscopy and Mössbauer spectroscopy. The absorption capacity of orthophosphate ions was calculated by Freundlich and Langergren isotherms. A transitional state was observed in the crystallographic structure from kaolinites because of the isomorphic substitution of Al3+ by Fe3+. This isomorphic substitution occurs accompanied by the optical pleochroism behavior, but it also reduces the mean particle sizes and increases the number of structural defects and magnetic properties of these kaolinites. Mössbauer spectroscopy showed that the substituting Fe3+ preferentially occupies octahedral sites. In the kaolinite lattices there are different octahedral sites of Al bounded by cis-OH-Fe3+ and trans-OH-Fe3+ octahedral sites. The kaolinite from the Kao1 sample has a higher number of cis-OH-Fe3+ from octahedral sites and is able to adsorb higher contents of orthophosphate ions than those from samples Kao2 and Kao3.
ABSTRACT
Mössbauer spectroscopy is an analytical tool to investigate the oxidation state and distortion in chemical bonds around iron moiety of iron containing pharmaceutical compounds (allopathic, homeopathy and ayurvedic). In the present work, Mössbauer spectroscopic studies of different parameters like; isomer shift, quadrupole splitting and line width in different unexpired and expired pharmaceutical compounds have been recorded. Changes in the value of these parameters have been observed according to nature of compound. Line width and quadrupole splitting values of the outdated allopathic samples containing ferrous ascorbate (C18H21FeO18), ferrous fumarate (C4H2FeO4) and ferric hydroxide Fe(OH)3 increased significantly as compared to respective fresh samples. This is attributed due to the weakening and distortion of bonds around iron moiety prior to change in the valence state. Ayurvedic and homeopathic iron supplements exhibited remarkable consistency of Mössbauer parameters even after long period of storage owing to the presence of stoichiometrically pure and chemically stable ferric oxide (α-Fe2O3) in loh bhasam and ferrous phosphate Fe3(PO4)2 in biochemic tablets.