Graphene as a reversible spin manipulator of molecular magnets

One of the primary objectives in molecular nanospintronics is to manipulate the spin states of organic molecules with a d-electron center, by suitable external means. In this Letter, we demonstrate by first principles density functional calculations, as well as second order perturbation theory, that a strain induced change of the spin state, from S=1→S=2, takes place for an iron porphyrin (FeP) molecule deposited at a divacancy site in a graphene lattice. The process is reversible in the sense that the application of tensile or compressive strains in the graphene lattice can stabilize FeP in different spin states, each with a unique saturation moment and easy axis orientation. The effect is brought about by a change in Fe-N bond length in FeP, which influences the molecular level diagram as well as the interaction between the C atoms of the graphene layer and the molecular orbitals of FeP.     

On the extendedness of eigenstates in a hierarchical lattice: A critical view

We take a critical view at the basic definition of extended single particle states in a non-translationally invariant system. For this, we present the case of a hierarchical lattice and incorporate long range interactions that are also distributed in a hierarchical fashion. We show that it is possible to explicitly construct eigenstates with constant amplitudes (normalized to unity) at every lattice point for special values of the electron-energy. However, the end-to-end transmission, corresponding to the above energy of the electron in such a hierarchical system depends strongly on a special correlation between the numerical values of the parameters of the Hamiltonian. Keeping the energy and the distribution of the amplitudes invariant, one can transform the lattice from conducting to insulating simply by tuning the numerical values of the long range interaction. The values of these interactions themselves display a fractal character.     

Physics of interferometric gravitational wave detectors

The Caltech-MIT joint LIGO project is operating three long-baseline interferometers (one of 2 km and two of 4 km) in order to unambiguously measure the infinitesimal displacements of isolated test masses which convey the signature of gravitational waves from astrophysical sources. An interferometric gravitational wave detector like LIGO is a complex, non-linear, coupled, dynamic system. This article summarizes various interesting design characteristics of these detectors and techniques that were implemented in order to reach and maintain its operating condition. Specifically, the following topics are discussed: (i) length sensing and control, (ii) alignment sensing and control and (iii) thermal lensing which changes the performance and operating point of the interferometer as the input power to LIGO is increased.     

Palladium(II)‐Catalyzed meta‐CH Olefination: Constructing Multisubstituted Arenes through Homo‐Diolefination and Sequential Hetero‐Diolefination

Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium‐catalyzed synthesis of divinylbenzenes by meta‐C? H olefination of sulfone‐based arenes. Successful sequential olefinations in a position‐selective manner provided a novel route for the synthesis of hetero‐dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5‐trialkenylated compounds can be generated upon successful removal of the directing group.     

Understanding guest and pressure‐induced porosity through structural transition in flexible interpenetrated MOF by Raman spectroscopy

Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)_0.5 · DMF(H₂O)_0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO₂ and its librational mode at 149 cm⁻¹ suggests cooperative adsorption of CO₂ in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd.     

Phenanthroline-fluorescein molecular hybrid as a ratiometric and selective fluorescent chemosensor for Cu2+ via FRET strategy: synthesis,computational studies and in vitro applications

A FRET-based chemosensor L containing donor phenanthroline and acceptor fluorescein moiety was designed, synthesised and characterised for the ratiometric fluorescent detection of Cu²⁺ in organo-aqueous solution. Probe L showed high selectivity and excellent sensitivity towards Cu²⁺ ions by exhibiting both colorimetric and fluorometric changes due to opening of the spirolactum ring of fluorescein upon complexation with Cu²⁺. In presence of Cu²⁺ ions, probe L formed L-Cu²⁺ complex in 1:1 stoichiometric fashion which is established on the basis of Job’s plot and mass spectroscopy. We also performed DFT computational studies to know the binding nature and coordination feature of the complex. Furthermore, fluorescence imaging studies revealed that probe L was cell permeable and could be used to detect intracellular Cu²⁺ in living cells.     

Quantum mechanical generalized phase-shift approach to atom-surface scattering: a Feshbach projection approach to dealing with closed channel effects

We have developed a new method for solving quantum dynamical scattering problems, using the time-independent Schr?dinger equation (TISE), based on a novel method to generalize a "one-way" quantum mechanical wave equation, impose correct boundary conditions, and eliminate exponentially growing closed channel solutions. The approach is readily parallelized to achieve approximate N(2) scaling, where N is the number of coupled equations. The full two-way nature of the TISE is included while propagating the wave function in the scattering variable and the full S-matrix is obtained. The new algorithm is based on a "Modified Cayley" operator splitting approach, generalizing earlier work where the method was applied to the time-dependent Schr?dinger equation. All scattering variable propagation approaches to solving the TISE involve solving a Helmholtz-type equation, and for more than one degree of freedom, these are notoriously ill-behaved, due to the unavoidable presence of exponentially growing contributions to the numerical solution. Traditionally, the method used to eliminate exponential growth has posed a major obstacle to the full parallelization of such propagation algorithms. We stabilize by using the Feshbach projection operator technique to remove all the nonphysical exponentially growing closed channels, while retaining all of the propagating open channel components, as well as exponentially decaying closed channel components.     

A vanadium (VO2+) metal-organic framework: selective vapor adsorption, magnetic properties, and use as a precursor for a polyoxovanadate

The reaction of VOSO(4) with 2-carboxyethylphosphonic acid (H(2)-CEP) in presence of piperazine (PIP) produces a 3D inorganic-organic hybrid framework, {(H(2)PIP)(0.5)[VO(CEP)]·H(2)O} (1) with bidirectional channels occupied by the H(2)PIP cations and H(2)O molecules. The PO(3)(2-) unit of CEP connects three V(IV) centers to generate a 1D ladder, which is further linked to four such ladders by the CEP linkers to form a 3D hybrid framework. The dehydrated framework, {(H(2)PIP)(0.5)[VO(CEP)]} (1') shows selective and gated adsorption behavior with H(2)O but not with methanol and ethanol. Very interestingly, when 1 is treated with an aqueous solution of LiNO(3)/NaNO(3), the framework breaks down and results in a new polyoxovanadate (POV) cluster, [H(5)(H(2)PIP)(3)][V(V)(12)V(IV)(2)O(38)(PO(4))]·8H(2)O (2) at pH ≈ 2.1. The cluster has been characterized by single-crystal X-ray diffraction, (31)P NMR, EPR, and magnetic studies. The temperature-dependent magnetic susceptibility measurement suggests antiferromagnetic ordering in 1 with T(N) ≈ 3.8 K.     

N-Heterocyclic carbene-mediated oxidative esterification of aldehydes: ester formation and mechanistic studies

An unexpected N-heterocyclic carbene-catalyzed esterification of α,β-unsaturated aldehydes including aromatic aldehydes with reactive cinnamyl bromides in the presence of air oxygen or MnO(2) as an oxidant is described. In the presence of oxygen, halogenated and electron-deficient aldehydes react smoothly to furnish esters in good yields. Great efforts have been made on mechanistic studies to deduce a plausible mechanism, based on the experimental results and isotopic labeling experiment.