New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

New inorganic–organic hybrid structures based on metal complexes have become of increasing interest over the last few decades in the search for new materials. Many different polypyridyl metal complexes have been investigated. Recently, a strong increase in interest regarding 2,2′:6′,2″‐terpyridine has been observed. In particular, octahedral bis‐2,2′:6′,2″‐terpyridine metal complexes offer the advantages of increased symmetry and, in the case of ruthenium(III )/ruthenium(II ) complexation, an entrance to a directed complexation technique. Apart from the combination with polymeric systems, ordered inorganic–organic structures on surfaces are becoming better understood concurrently with the development of sophisticated nanotechnology characterization techniques. There are many ongoing efforts that include terpyridine complex structures, especially concerning photophysical processes such as solar light to energy conversion. This review deals with the incorporation of terpyridine complexes into polymeric structures such as poly(ethylene glycol), poly(styrene), dendrimers, biomacromolecules, micelles, and resins, as well as the combination of terpyridine complexes with surfaces for electrocatalytic, photophysical, and self‐assembly purposes.     

Mesogenic lanthanoid metal complexes of a non-mesogenic Schiff-base, N,N′-di-(4-hexadecyloxysalicylidene)-l′,8′-diamino-3′,6′-dioxaoctane

A non-mesogenic Schiff-base, N,N′-di-(4-hexadecyloxysalicylidene)-l′,8′-diamino-3′,6′-dioxaoctane, H₂dhdsdd (H₂L²), was synthesized, structure studied by elemental analyses and mass, NMR and IR spectra and ligated to some Ln^III metal ions that yielded mesogenic (SmA/N) Ln^III complexes of the general composition, [Ln₂(L²H₂)₃(NO₃)₄](NO₃)₂, where Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Ho. IR and NMR spectral data imply a bi-dentate bonding of the Schiff-base in its zwitterionic form (as L²H₂) to the Ln^III ions through two phenolate oxygens, rendering the overall geometry around Ln^III to distorted mono-capped octahedron.     

New 3-((2′:2″,5″:2-terthiophene)-3″-yl) acrylic acid as active layer for organic field-effect transistor

Most functionalized thiophenes are difficult to electropolymerize due to nucleophilicity that will attack the radical cation inhibiting polymerization. However, we have successfully electrodeposited a newly synthesized functionalized terthiophene monomer 3-((2′:2″,5″:2-terthiophene)-3″-yl) acrylic acid (TAA) as an active layer of a organic field-effect transistor (OFET). The polymer was then oxidized in order to increase its conductivity. Various oxidizing potentials were experimented and their effect on the OFET's charge mobility was examined. A mobility of 0.25 cm² (V s)⁻¹ is achieved with an oxidizing potential of 0.9 V after vacuum drying.     

Crystal structure of the orthorhombic U2-Al4Mg4Si4 precipitate in the Al–Mg–Si alloy system and its relation to the β′ and β″ phases

The atomic structure of a common precipitate in the Al–Mg–Si system has been determined. It is isotypic with TiNiSi (space group Pnma) and contains four units of MgAlSi in a unit cell of size a = 0.675 nm, b = 0.405 nm, c = 0.794 nm. EDS analyses support the composition. A model was based on the atomic structure of the β′ precipitate, electron diffraction and high-resolution transmission electron microscopy (HRTEM) images. A quantum mechanical refinement of the model removed discrepancies between simulated and experimental diffraction intensities. Finally, a multi-slice least square refinement confirmed the structure. The structural relation with β″ is investigated. A similar Mg–Si plane also existing in β″ and β′, can explain most coherency relations between the precipitate phases and with matrix.     

The inhibition of 4-(2′-amino-5′-methylphenylazo) antipyrine on corrosion of mild steel in HCl solution

The effect of 4-(2′-amino-5′-methylphenylazo) antipyrine (AMPA) on the corrosion of mild steel in a 2 M HCl solution was studied using weight loss and potentiodynamic polarization techniques. All of the data reveal that AMPA acts as an inhibitor in the acid environment; furthermore, polarization data show that the compound behaves as a mixed-type inhibitor. It was found that the inhibition efficiency increases with an increase in AMPA concentration but decreases with an increase in temperature. Flory–Huggins adsorption isotherm and El Awady thermodynamic–kinetic model fit the experimental data of the studied compound. Thermodynamic parameters for corrosion and adsorption processes were obtained from experimental data of the temperature studies.     

Spectral characterization of electroluminescent devices containing functionalized dipyrido[3,2-a:2′,3′-c]phenazine complexes

A series of functionalized dipyrido[3,2-a:2′,3′-c]phenazine complexes with copper(I), rhenium(I), ruthenium(II) and iridium(III) have been synthesized and used as dopants in OLEDs. The ruthenium-based complexes are the most efficient appearing blue in colour, the copper complexes give devices that appear white in emission. In most cases the emission colour is a mixture of emission from the metal complex and from the matrix (PVK).     

Electrosynthesis and charge-transport properties of poly(3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene)

Polythiophene containing 3,4-ethylenedioxythiophene (EDOT), poly(3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene), was synthesized by electrochemical oxidation of the corresponding monomer, 3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene, in acetonitrile. The resulting polymer was soluble in DMSO and THF, and was characterized by ¹H NMR and mass spectroscopies, and GPC. The electrical conductivity of the oxidized polymer film was found to be comparable to those for polythiophene and poly(methylthiophene) despite of its short π-conjugation length.     

Investigations of MX and γ′/γ″ precipitates in the nickel-based superalloy 718 produced by electron beam melting

Samples with a composition similar to the nickel-based superalloy Inconel alloy 718 were produced by electron beam melting of prealloyed powder and investigated with respect to type and composition of the strengthening precipitates. The matrix consists of γ grains orientated in nearly the same direction, almost like a single crystal. Coarse precipitates (<2 μm), mostly of the (Ti,Nb)(C,N,B) type with B1 structure, are aligned along the growth direction. TEM and APFIM investigations of the γ matrix revealed very fine γ″ precipitates of around 5–10 nm in size. Additionally, at small angle grain boundaries, coarser γ″ precipitates of 50–100 nm in size have been observed. The 0 01 γ//0 0 1 γ″ and {1 0 0} γ//{1 0 0} γ″ orientation relationship between γ and γ″, known from literature [M. Sundararaman, P. Mukhopadhyay, Mater. Charact. 31 (1993) 191–196], was confirmed. Some γ′ precipitates of 2–5 nm in size were observed by means of FIM.