Complexes of Co(II) and Zn(II) with N-(Thio)phosphorylthioureas AdNHC(S)NHP(O)(OiPr)2 and MeNHC(S)NHP(S)(OiPr)2

The reaction of the potassium salt of the N-(thio)phosphorylated thioureas AdNHC(S)NHP(O)(OiPr)₂ (HL^I , Ad = Adamantyl) and MeNHC(S)NHP(S)(OiPr)₂ (HL^II ) with Co(II) and Zn(II) in aqueous EtOH leads to [ML^I,II ₂] chelate complexes. They were investigated by UV-vis, ¹H and ³¹P NMR spectroscopy, and microanalysis. The molecular structures of [ML^I ₂] were elucidated by single crystal X-ray diffraction analysis. The metal centers in both complexes are found to be in a distorted-tetrahedral O₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated L^I ligands. The photoluminescence properties of [ZnL^II ₂] are also reported.     

A Composite of Complex and Chemical Hydrides Yields the First Al‐Based Amidoborane with Improved Hydrogen Storage Properties

The first Al‐based amidoborane Na[Al(NH₂BH₃)₄] was obtained through a mechanochemical treatment of the NaAlH₄–4 AB (AB=NH₃BH₃) composite releasing 4.5 wt % of pure hydrogen. The same amidoborane was also produced upon heating the composite at 70 °C. The crystal structure of Na[Al(NH₂BH₃)₄], elucidated from synchrotron X‐ray powder diffraction and confirmed by DFT calculations, contains the previously unknown tetrahedral ion [Al(NH₂BH₃)₄]^?, with every NH₂BH₃^? ligand coordinated to aluminum through nitrogen atoms. Combination of complex and chemical hydrides in the same compound was possible due to both the lower stability of the Al?H bonds compared to the B?H ones in borohydride, and due to the strong Lewis acidity of Al³⁺. According to the thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TGA–DSC–MS) studies, Na[Al(NH₂BH₃)₄] releases in two steps 9 wt % of pure hydrogen. As a result of this decomposition, which was also supported by volumetric studies, the formation of NaBH₄ and amorphous product(s) of the surmised composition AlN₄B₃H_(0–3.6) were observed. Furthermore, volumetric experiments have also shown that the final residue can reversibly absorb about 27 % of the released hydrogen at 250 °C and p(H₂)=150 bar. Hydrogen re‐absorption does not regenerate neither Na[Al(NH₂BH₃)₄] nor starting materials, NaAlH₄ and AB, but rather occurs within amorphous product(s). Detailed studies of the latter one(s) can open an avenue for a new family of reversible hydrogen storage materials. Finally, the NaAlH₄–4 AB composite might become a starting point towards a new series of aluminum‐based tetraamidoboranes with improved hydrogen storage properties such as hydrogen storage density, hydrogen purity, and reversibility.     

New Developments and Applications of Handheld Raman,Mid-Infrared,and Near-Infrared Spectrometers

Abstract: Recently, miniaturization of Raman, mid-infrared (IR), and near-infrared (NIR) spectrometers has made substantial progress. Though mid-infrared systems are based exclusively on attenuated total reflection (ATR) measurements, near-infrared spectrometers operate in the diffuse reflection or transmission mode. The reduction in size, however, must not be accompanied by deterioration in measurement performance, and portable instrumentation will only have a real impact on quality and process control if Raman, IR, and NIR spectra of comparable quality to laboratory spectrometers can be obtained.

In the present communication, a short overview on the building principles of novel handheld systems will be provided and the results of qualitative and quantitative analyses of selected liquid and solid sample systems obtained with these Raman, Fourier transform infrared (FTIR), and NIR spectrometers will be evaluated in terms of their comparability with laboratory instruments and their suitability for on-site and field measurements.     

J-inner matrix functions, interpolation and inverse problems for canonical systems, I: Foundations

This is the first of a planned sequence of papers on inverse problems for canonical systems of differential equations. It is devoted largely to foundational material (much of which is of independent interest) on the theory of assorted classes of meromorphic matrix valued functions. Particular attention is paid to the structure of J-inner functions and connections with bitangential interpolation problems and reproducing kernel Hilbert spaces. Some new characterizations of regular, singular and strongly regular J-inner functions in terms of the associated reproducing kernel Hilbert spaces are presented.D. Z. Arov wishes to thank the Weizmann Institute of Science for hospitality and support; H. Dym wishes to thank Renee and Jay Weiss for endowing the chair which supports his research.     

Calibrating a nanoindenter for very shallow depth indentation using equivalent contact radius

Nanoindenter tips are usually modelled as axisymmetric cones, with calibration involving finding a fitting function that relates contact area to contact depth. For accurate calibration of shallow depth indentation, this is not ideal because it means that deeper indents tend to dominate the fitting function. For an axisymmetric object, it is always possible to define an equivalent contact radius (which, in the case, of nanoindentation is linearly related to the reduced modulus) and to obtain a fitting function that relates this equivalent contact radius to indentation depth. The equivalent contact radius approach is used here to provide shallow depth calibration of a nanoindenter tip at three separate times. The advantage of the equivalent contact radius methodology is that it provides a clearer physical interpretation of the changes in tip shape than a conventional area-based fit. We also show that the minimum depth for a reliable hardness measurement is obtainable and increases as the tip blunts with age but that consistent measurements of very near surface elastic moduli can be made if the blunting of the tip over time is fully accounted for in the tip area function calibration.     

On the path-Zagreb matrix

The definition of the path-Zagreb matrix for (chemical) trees PZ and its generalization to any (molecular) graph is presented. Additionally, the upper bound of , where G _n is a graph with n vertices is given.     

On the anti-Kekulé number of leapfrog fullerenes

The Anti-Kekulé number of a connected graph G is the smallest number of edges that have to be removed from G in such way that G remains connected but it has no Kekulé structures. In this paper it is proved that the Anti-Kekulé number of all fullerenes is either 3 or 4 and that for each leapfrog fullerene the Anti-Kekulé number can be established by observing finite number of cases not depending on the size of the fullerene.     

On decompositions of leapfrog fullerenes

It is shown that given a fullerene F with the number of vertices n divisible by 4, and such that no two pentagons in F share an edge, the corresponding leapfrog fullerene Le(F) contains a long cycle of length 3n − 6 missing out only one hexagon.     

Two canonical passive state/signal shift realizations of passive discrete time behaviors

A discrete time invariant linear state/signal system Σ with a Hilbert state space and a Kren signal space has trajectories (x(),w()) that are solutions of the equation , where F is a bounded linear operator from into with a closed domain whose projection onto is all of . This system is passive if the graph of F is a maximal nonnegative subspace of the Kren space . The future behavior of a passive system Σ is the set of all signal components w() of trajectories (x(),w()) of Σ on with x(0)=0 and . This is always a maximal nonnegative shift-invariant subspace of the Kren space , i.e., the space endowed with the indefinite inner product inherited from . Subspaces of with this property are called passive future behaviors. In this work we study passive state/signal systems and passive behaviors (future, full, and past). In particular, we define and study the input and output maps of a passive state/signal system, and the past/future map of a passive behavior. We then turn to the inverse problem, and construct two passive state/signal realizations of a given passive future behavior , one of which is observable and backward conservative, and the other controllable and forward conservative. Both of these are canonical in the sense that they are uniquely determined by the given data , in contrast earlier realizations that depend not only on , but also on some arbitrarily chosen fundamental decomposition of the signal space . From our canonical realizations we are able to recover the two standard de Branges–Rovnyak input/state/output shift realizations of a given operator-valued Schur function in the unit disk.