ABSTRACT
Porous anodic aluminum oxide (PAAO), sometimes referred to as nanoporous anodic alumina, serves as a cost-effective template for nanofabrication in many fields of science and engineering. However, production of ultrathin PAAO membranes with precise thickness in the optical sub-wavelength range remains challenging because of difficulties regarding process control at the initial stage of anodic oxidation. In this study, we demonstrate a technique for consistently manufacturing PAAO with the targeted thickness. An electrochemical cell with an optical window was designed for reflectance spectroscopy of PAAO during anodization. Real-time fitting of spectra to a transfer-matrix model enabled continuous monitoring of the thickness growth of the PAAO layer. Automation software was designed to terminate the anodization process at preset PAAO thickness values. While the concept was illustrated using the widely used method of anodization in a 0.3 M oxalic acid electrolyte with a 40 V potential, it can be readily customized for other protocols. PAAO layers with effective thickness below 300 nm could be produced with a few nanometers accuracy using single-crystal aluminum substrates. The results were confirmed using spectroscopic ellipsometry. The method for controlling the thickness during anodization eliminates the necessity of sample sectioning for electron microscopy and is particularly valuable for the small-scale production of PAAO-based functional optical coatings.
ABSTRACT
The novel bis-chelating carbacylamidophosphate type ligand, tetramethyl[pyridine-2,6-diyldi(iminocarbonyl)]diamidophosphate (H2L), and its sodium salt, NaHL, have been synthesized and their structural properties have been investigated. Coordination compounds of lanthanides [Ln(HL)2NO3]·i-PrOH (Ln = Eu3+, Tb3+) were obtained for the first time, isolated in the individual state and characterized by means of IR and NMR spectroscopies, electrospray ionization mass spectrometry (ESI-MS), potentiometric titration, and elemental, thermal gravimetric and X-ray diffraction analyses. It was shown that H2L behaves like a scorpionate type ligand and in a mono-deprotonated form coordinates in a tridentate manner via the oxygen atoms of phosphoryl and carbonyl groups with formation of a mononuclear metal complex. The protonation constants of H2L and stability constants of Eu3+ and Tb3+ complexes have been determined. According to the results of X-ray diffraction analysis the H2L and [Ln(HL)2NO3]·i-PrOH molecules have monomeric structure but NaHL is a dimer. The Hirshfeld surface and fingerprint plots of the compounds have been used to analyze various hydrogen bonds and intermolecular interactions displayed in the crystal structure.
ABSTRACT
A series of new anionic lanthanide(III) complexes with the general formula NEt4[LnL4] (1-Ln; HL = dimethyl[(4-methylphenyl)sulfonyl]amidophosphate; Ln = La, Nd, Eu), were synthesized and characterized by IR, UV-vis, and NMR spectroscopies, the differential scanning calorimetry method, thermogravimetric and X-ray analysis, and photoluminescence measurements. Single-crystal structures of NEt4[EuL4] (1-Eu) were determined at 293 and 100 K and evidenced the single-crystal-to-single-crystal phase transition. Both phases are in the monoclinic crystal system in centrosymmetric groups of the same Laue class. The room temperature structure is in C2/c (No. 15), while low-temperature structure is in the P21/c (No. 14) space groups. The coordination environment geometry around the central europium(III) ion is a distorted square antiprism in both polymorphs, while the peripheral methoxy and tolyl groups show different orientations. This phenomenon indicates the occurrence of a thermally driven second-order phase transition during the cooling-heating process. The europium(III) complex exhibits an unusual emission spectrum, clearly dominated by the 5D0-7F4 bands, and an emission decay time equaling 3.5 ms, being among the highest values known for europium coordination compounds.
