Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two-Step Iron(II) Spin Crossover Switchable by Temperature,Light, and Pressure

A two-step hysteretic Fe^II spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)₂][Re(CN)₈]}⋅H₂O ( 1 ) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged Fe^II-Re^V square grid sheets bonded by Cs⁺ ions. The presence of two non-equivalent Fe^II sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs⁺, [Re^V(CN)₈]³⁻ ions, and 3-CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin-transition phenomenon could be tuned by an external pressure giving the room-temperature range of SCO, as well as by visible-light irradiation, inducing an efficient recovery of the high-spin Fe^II state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable Fe^II SCO effect.     

A New Cationic Fluorescent Probe for HSO3− Based on Bisulfite Induced Aggregation Self-Assembly

In comparison with the numerous studies that have centered on developing molecular frameworks for the functionalization of fluorescent materials, less research has addressed the influence of the side chains, despite such appendages contributing significantly to the properties and applications of fluorescent materials. In this work, a new series of cationic fluorescent probes with AIE characteristics have been developed, which exhibit unique sensitivity for charge-diffusion anions, namely HSO₃⁻, via the interactions of ions and the cooperation of the controllable hydrophobicity. The impact of the alkyl chain length attached at the cationic probes suggested that the fluorescent intensity and sensitivity of the probes could be partially enhanced by adjusting their aggregation tendency through the action of the hydrophobic effect under aqueous conditions. DLS and SEM images indicated that different particle sizes and new morphologies of the probes were formed in the anion-recognition-triggered self-assembly process, which could be attributed to the composite effect of electrostatic actions, Van der Waals forces and π-π stacking.     

Chemical tuning by 5-Methyl and N-Methyl-substitution in heptanuclear complexes effects multistability investigated by Mössbauer spectroscopy

The precursors [Fe^(III)(^N???R???L)Cl] (^N???R???LH₂=N,N′-bis(2′-hydroxy- 5′-methyl-benzyliden)-1,7-diamino-4-R-4-azaheptane, R ?=? H, methyl(Me)) are high-spin (S?=?5/2) complexes. The Lewis-acidic precursors are combined with Lewis- Base-bridging-units [M(CN) _x ] ^y??? (M = Fe^(II), Ru^(II), Co^(III)) to form heptanuclear star-shaped [M{CN-Fe^(III)(^N???R???L)} _x ]Cl _y molecular switches. The star-shaped compounds are high-spin systems at room temperature. On cooling to 20 K some of the compounds exhibit multistability, i.e. several iron(III) centers within a molecule switch to the low-spin state as shown by Mössbauer spectroscopy.     

Optimizing a phase gate using quantum interference

A controlled interference is proposed to reduce, by two orders of magnitude, the decoherence of a quantum gate for which the gate fidelity is limited by coupling to states other than the /0> and /1> qubit states. This phenomenon is demonstrated in an ultracold neutral atom implementation of a phase gate using qubits based on motional states in individual wells of an optical lattice.     

Recursion relations for the extended Krylov subspace method

The evaluation of matrix functions of the form f(A)v, where A is a large sparse or structured symmetric matrix, f is a nonlinear function, and v is a vector, is frequently subdivided into two steps: first an orthonormal basis of an extended Krylov subspace of fairly small dimension is determined, and then a projection onto this subspace is evaluated by a method designed for small problems. This paper derives short recursion relations for orthonormal bases of extended Krylov subspaces of the type K^m,mi+1(A)=span{A^-m+1v,…,A^-1v,v,Av,…,A^miv}, m=1,2,3,…, with i a positive integer, and describes applications to the evaluation of matrix functions and the computation of rational Gauss quadrature rules.     

Existence and uniqueness of rectilinear slit maps

We consider a generalization of the parallel slit uniformization in which the angle of inclination of each image slit is assigned independently. Koebe proved that for domains of finite connectivity there is, up to a normalization, a unique rectilinear slit map achieving any given angle assignment. Koebe's theorem is partially extended to domains of infinite connectivity. A uniqueness result is shown for domains of countable connectivity and arbitrary angle assignments, and an existence result is proved for arbitrary domains under the assumption that the angle assignment is continuous and has finite range. In order to prove the existence result a new extremal length tool, called the crossing-module, is introduced. The crossing-module allows greater freedom in the family of admissible arcs than the classical module. Several results known for the module are extended to the crossing-module. A generalization of Jenkins' module condition for the parallel slit problem is given for the rectilinear slit problem in terms of the crossing-module and it is shown that rectilinear slit maps satisfying this crossing-module condition exist.

     

Simulation from Wishart Distributions with Eigenvalue Constraints

Abstract

This article provides an efficient algorithm for generating a random matrix according to a Wishart distribution, but with eigenvalues constrained to be less than a given vector of positive values. The procedure of Odell and Feiveson provides a guide, but the modifications here ensure that the diagonal elements of a candidate matrix are less than the corresponding elements of the constraint vector, thus greatly improving the chances that the matrix will be acceptable. The Normal hierarchical model with vector outcomes and the multivariate random effects model provide motivating applications.     

Reaction of silanes in supercritical CO2 with TiO2 and Al2O3

Infrared spectroscopy was used to investigate the reaction of silanes with TiO2 and Al2O3 using supercritical CO2 (Sc-CO2) as a solvent. It was found that contact of Sc-CO2 with TiO2 leads to partial removal of the water layer and to the formation of carbonate, bicarbonate, and carboxylate species on the surface. Although these carbonate species are weakly bound to the TiO2 surface and can be removed by a N2 purge, they poison the surface, resulting in a lower level of reaction of silanes with TiO2. Specifically, the amount of hexamethyldisilazane adsorbed on TiO2 is about 10% of the value obtained when the reaction is performed from the gas phase. This is not unique to TiO2, as the formation of carbonate species also occurs upon contact of Al2O3 with Sc-CO2 and this leads to a lower level of reaction with hexamethyldisilazane. This is in contrast to reactions of silanes on SiO2 where Sc-CO2 has several advantages over conventional gaseous or nonaqueous methods. As a result, caution needs to be applied when using Sc-CO2 as a solvent for silanization reactions on oxides other than SiO2.