Intermarriage of Halide Perovskites and Metal-Organic Framework Crystals

This Review examines how the intermarriage of perovskite and metal-organic framework crystals brings new paradigms for material design and functionality. The strategic combination of halide perovskites and metal–organic frameworks (MOFs) has generated a new family of porous composite materials that will enable new applications, including optoelectronic, catalysis, sensing, and data encryption. This Review surveys the current progress of this exciting new area. Fundamental aspects, including perovskite nucleation and growth, heterojunction electron–hole transfer, electronic structure, and luminescence within confined spaces, are highlighted, with suggestions of approaches by which guest confinement within MOFs can be synthetically designed. We further address the underlying principles and discuss the new insights and tools for the manipulation of these composite materials for the development of synthetic microporous semiconducting composites, as well as new strategies for host–guest interfacial engineering.     

A simplified fuzzy model to mimic a nonlinear system, applied to aplasma source

This paper develops a fuzzy model to simulate the behaviour of a nonlinear system, in particular a plasma source, with a view to developing a control system for processing plasmas employing a helicon source. Genetic algorithms are employed to optimize fuzzy rules related to the parameters of the fuzzy model which contain a set of variable zeros and poles of the nonlinear system as well as its time delay. A practical application of the fuzzy model is to estimate the electron number density of a low-temperature plasma. Based on the membership functions of the input and output, a set of fuzzy rules by which the variable zeros and poles are identified is derived and optimized using a genetic algorithm. The principal reason for investigating the proposed fuzzy model is the subsequent computer-aided design of a fuzzy controller to control the nonlinear system. Two experimental results are presented to validate the fuzzy model method. One shows a computer simulation and the other predicts the real-time behaviour of the plasma source as its input parameters are varied     

Novel red phosphors for solid state lighting; the system BixLn1−xVO4; Eu/Sm (Ln=Y, Gd)

Solid solutions of vanadates of formula Bi_xLn_1−xVO₄ (Ln=Y, Gd) doped with Eu³⁺ or Sm³⁺ ions have been synthesized by solid-state reactions. Intense red/orange-red luminescence is obtained in these samples on excitation in the broad charge-transfer band in the near UV. The excitation in the Eu³⁺ levels leads to much less intense red emission. These materials could find applications as red phosphors for solid-state white lighting devices utilizing GaN-based excitation in the near UV.     

Metal-driven ligand assembly in the synthesis of cyclodextrin [2] and [3]rotaxanes

Cyclodextrin [2] and [3]rotaxanes have been synthesised by use of a metal-driven ligand formation methodology. The kinetically stable cobalt(III) complexes formed act as either linking or capping groups, the function being selected by manipulation of the reaction conditions to promote the formation of either 2:1 or 1:1 complexes, respectively. In all cases, mixtures of isomers containing different alpha-cyclodextrin orientations were observed. All three orientational isomers of the [3]rotaxane were isolated and structurally characterized by 2D NMR.     

Two coordination polymers created via in situ ligand synthesis involving C-N and C-C bond formation

We report the synthesis and crystal structures of two transition metal-based coordination polymers comprising ligand molecules not included in the original reaction mixtures but instead formed in situ during hydrothermal treatment. Zinc meso-iminodisuccinate hydrate (I), Zn(2)(C(8)H(7)NO(8)).0.57H(2)O, formed from zinc acetate and L-aspartic acid, and tetraaquanickel(II) 5,10-dioxo-5,10-dihydro-4,9-dioxa-pyrene-2,7-dicarboxylate (II), Ni(H(2)O)(4)(C(16)H(4)O(8)), formed from nickel acetate and 5-hydroxyisophthalic acid. We show that the formation of I takes place via a fumaric acid intermediate, while the formation of II requires the formation of a new C-C bond. The structure of I consists of weakly interacting sheets, while the structure of II consists of strongly hydrogen-bonded chains. Crystal data: for I, P2(1)/n (14), a = 10.073 A, b = 9.894 A, c = 12.053 A, beta = 105.605 degrees, V = 1156.87(13) A(3), Z = 4; for II, P1 (2), a = 5.011 A, b = 6.526 A, c = 12.305 A, alpha = 76.868 degrees, beta = 84.988 degrees, gamma = 87.619 degrees, V = 390.3(4) A(3), Z = 1.     

Extreme Flexibility in a Zeolitic Imidazolate Framework: Porous to Dense Phase Transition in Desolvated ZIF‐4

Desolvated zeolitic imidazolate framework ZIF‐4(Zn) undergoes a discontinuous porous to dense phase transition on cooling through 140 K, with a 23 % contraction in unit cell volume. The structure of the non‐porous, low temperature phase was determined from synchrotron X‐ray powder diffraction data and its density was found to be slightly less than that of the densest ZIF phase, ZIF‐zni. The mechanism of the phase transition involves a cooperative rotation of imidazolate linkers resulting in isotropic framework contraction and pore space minimization. DFT calculations established the energy of the new structure relative to those of the room temperature phase and ZIF‐zni, while DSC measurements indicate the entropic stabilization of the porous room temperature phase at temperatures above 140 K.     

Review of technetium chemistry research conducted at the University of Nevada Las Vegas

The chemistry of technetium is being explored at the University of Nevada Las Vegas. Our goal is to investigate both the applied and fundamental aspects of technetium chemistry, with a special emphasis on synthesis, separations, and materials science. The synthetic chemistry focuses on metal–metal multiple bonding, oxides and halides. Synthesis and characterizations of (n-Bu₄N)₂Tc₂X₈, Tc₂(O₂CCH3)₄X₂ (X = Cl, Br), TcO₂, Bi₂Tc₂O₇, Bi₃TcO₈, TcBr₃ and TcBr₄ have been performed. The applied chemistry is related to the behavior of Tc in the UREX process. Separation of U/Tc has been conducted using anion exchange resin and metallic Tc waste form synthesized and characterized.     

Travelling Modes in Wave-Heated Plasma Sources

This paper describes a theoretical and experimental study of surface- and helicon-wave-heated plasma sources in which standing waves are set up in the cavity between the closed end plate to a plasma vessel and a wave launcher while travelling waves propagate from the opposite side of the launcher into a region which is long compared with the attenuation distance of the waves. We model the situation as a lossy transmission line of finite length coupled at the launcher to a lossy transmission line of infinite extent. RF power applied to the launcher divides in the ratio of the input impedances of the two transmission lines. For a conducting end plate, the power delivered to the travelling waves is a maximum when the cavity length is an odd number of 1/4 wavelengths long for which its input impedance is a maximum. Similarly, for an insulated end plate, the power delivered to the travelling waves is a maximum for a cavity with a length equal to an integer number of half wavelengths for which its input impedance is again a maximum.