Synthesis,crystal structure and magnetic properties of a new tri‐nuclear iron (II,III) complex,a precursor for the preparation of superparamagnetic Fe3O4 nanoparticles applicable in the removal of Cd2+

This study reports the structural and spectroscopic characterization of a novel metal organic compound formulated as [Fe (bpy)₃] [Fe (dipic)₂]₂.7H₂O ( 1 ) (dipic = pyridine‐2,6‐dicarboxylate and bpy = 2,2^′‐bipyridine). 1 was investigated by elemental analysis, FT‐IR spectroscopy, powder X‐ray diffraction and single crystal X‐ray diffraction (SC‐XRD), which revealed a triclinic structure of expected composition. Thermal degradation of 1 was also investigated. Complex 1 was used as a precursor to prepare superparamagnetic nanoparticles of Fe₃O₄ by thermal analysis. The obtained Fe₃O₄ was characterized by Fourier transformed infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Fe₃O₄ nanoparticles were used as a nano‐adsorbent to remove Cd²⁺ from water at room temperature. The results showed that this nano‐adsorbent is effective in removing Cd²⁺ from contaminated water sources, and that the maximal effectivity of adsorption occurs at pH = 6. Magnetic measurements of complex 1 and Fe₃O₄ nanoparticles at room temperature revealed paramagnetic and superparamagnetic behavior, respectively.     

Synthesis and characteristics of microspheres of polystyrene derivatives

Two sytrene derivatives formylstyrene and styrene sulfonylcholoride, were synthesized. Polymeric microspheres in diameters ranging from 0.1 to 2 μm were synthesized by polymerization of chlormoethylstyrene, formylstyrene, and styrene sulfonylcholoride in organic solvents, in the presence of appropriate surfactants. The kinetics of microsphere formation were studied. The molecular weight distribution of the products was determined by gel permeation chromatography. Conditions for binding various amino ligands to the microspheres were also established.     

Organotransition-Metal Metallacarboranes. 46. Multidecker Sandwiches of the Cobalt Group Metals(,)(1)

The double-decker sandwich complex CpIr(2,3-Et(2)C(2)B(4)H(4)) (1a) was prepared via deprotonation of nido-2,3-Et(2)C(2)B(4)H(6) to its mono- or dianion and reaction with (CpIrCl(2))(2) in THF and isolated as a colorless air-stable solid; the B(4)-chloro derivative 1b was also obtained. Decapitation of 1a and 1b with TMEDA afforded colorless nido-CpIr(2,3-Et(2)C(2)B(3)H(5)) (2a) and its 4-chloro derivative 2b. Chlorination of 1a by Cl(2) or N-chlorosuccinimide gave the symmetrical species CpIr(2,3-Et(2)C(2)B(4)H(3)-5-Cl) (1c), which was decapped to yield nido-CpIr(2,3-Et(2)C(2)B(3)H(4)-5-Cl) (2c). The triple-decker complexes CpIr(2,3-Et(2)C(2)B(3)H(2)-4[6]-Cl)IrCp (3), an orange solid, and dark green CpIr(2,3-Et(2)C(2)B(3)H(2)-4[6]-Cl)CoCp (5) were prepared from 2a and nido-CpCo(2,3-Et(2)C(2)B(3)H(5)) (4a), respectively, by deprotonation and reaction with (CpIrCl(2))(2) in THF. Reaction of the 2c(-) anion with Rh(MeCN)(3)Cl(3) gave the dark green tetradecker complex [CpIr(Et(2)C(2)B(3)H(2)-5-Cl)](2)RhH (6). In an attempt to prepare a heterotrimetallic Co-Rh-Ir tetradecker sandwich, a three-way reaction involving the deprotonated anions derived from CpCo(2,3-Et(2)C(2)B(3)H(4)-5-Cl) (4b) and 2c with Rh(MeCN)(3)Cl(3) was conducted. The desired species CpCo(Et(2)C(2)B(3)H(2)Cl)RhH(Et(2)C(2)B(3)H(2)Cl)IrCp (7) and the tetradeckers [CpCo(Et(2)C(2)B(3)H(2)Cl)](2)RhH (8) and 6 were isolated in small quantities from the product mixture; many other apparent triple-decker and tetradecker products were detected via mass spectroscopy but were not characterized. All new compounds were isolated via column or plate chromatography and characterized via NMR, UV-visible, and mass spectroscopy and by X-ray crystal structure determinations of 1a and 3. Crystal data for 1a: space group C2/c; a = 28.890(5) ?, b = 8.511(2) ?, c = 15.698(4) ?, beta = 107.61(2) degrees; Z = 8; R = 0.049 for 1404 independent reflections having I > 3sigma(I). Crystal data for 3: space group P2(1)/c; a = 11.775(4) ?, b = 15.546(5) ?, c = 15.500(5) ?, beta = 103.16(3) degrees; Z = 4; R = 0.066 for 2635 independent reflections having I > 3sigma(I).     

Thermally Activated Delayed Fluorescence in a Y3N@C80 Endohedral Fullerene: Time‐Resolved Luminescence and EPR Studies

The endohedral fullerene Y₃N@C₈₀ exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable‐temperature steady‐state and time‐resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y₃N@C₈₀ exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X‐ and W‐band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y₃N@C₈₀/PFO film is demonstrated opening the possibility for red‐emitting fullerene‐based organic light‐emitting diodes (OLEDs).     

A systematic theoretical investigation of the valence excited states of the diatomic molecules B2, C2, N2 and O2

A quantitative survey on the performance of multireference (MR), configuration interaction with all singles and doubles (CISD), MRCISD with the Davidson correction and MR-average quadratic coupled cluster (AQCC) methods for a wide range of excited states of the diatomic molecules B₂, C₂, N₂ and O₂ is presented. The spectroscopic constants r _e, ω_e, T _e and D _e for a total of 60 states have been evaluated and critically compared with available experimental data. Basis set extrapolations and size-extensivity corrections are essential for highly accurate results: MR-AQCC mean-errors of 0.001 ?, 10 cm⁻¹, 300 cm⁻¹ and 300 cm⁻¹ have been obtained for r _e, ω_e, T _e and D _e, respectively. Owing to the very systematic behavior of the results depending on the basis set and the choice of method, shortcomings of the calculations, such as Rydberg state coupling or insufficient configuration spaces, can be identified independently of experimental data. On the other hand, significant discrepancies with experiment for states which indicate no shortcomings whatsoever in the theoretical treatment suggest the re-evaluation of experimental results. The broad variety of states included in our survey and the uniform quality of the results indicate that the observed systematics is a general feature of the methods and, hence, is molecule-independent. Received: 12 June 2000 / Accepted: 1 September 2000 / Published online: 21 December 2000     

Switchable solvent based liquid phase microextraction of palladium coupled with determination by flame atomic absorption spectrometry

A switchable solvent-based micro-extraction method for pre-concentration and separation of ultratrace palladium was developed prior to its flame atomic absorption spectrometric detection. Reverse change of hydrophilicity of N,N-dimethylcyclohexylamine (DMA) was achieved by reaction with carbonated water. The hydrophilic bicarbonate salt of the protonated DMA was used as extractant for palladium complexed with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). Formation of the hydrophobic form of switchable solvent from hydrophilic form of switchable solvent phase was achieved by addition of sodium hydroxide into the extractant-sample solution. The effect of key parameters affected extraction recovery was studied and optimised by using Plackett–Burman design, central composite design and three dimension (3D) surfaces response. The calibration plot was linear in the range 0.015–1.6 mg L^?1 of palladium with a correlation coefficient of 0.999. The limit of detections values of palladium for liquid and solid samples were 4.28 μg L^?1 and 0.54 µg g^?1, respectively. The pre-concentration factor was 37.5. The accuracy was confirmed by determination of palladium in certified reference material. The procedure was also applied for determination of palladium content of real samples as automotive catalytic converter, roadside dust, sea water and river water.