Triazoles and tetrazoles: Prime ligands to generate remarkable coordination materials

The current great interest in preparing functional metal-organic materials is inevitably associated with tremendous research efforts dedicated to the design and synthesis of new families of sophisticated multi-nucleating ligands. In this context, the N-donor triazole and tetrazole rings represent two categories of ligands that are increasingly used, most likely as the result of the recent dramatic development of “click chemistry” and Zeolitic Imidazolate Frameworks (ZIFs). Thus, azole-based complexes have found numerous applications in coordination chemistry.In the present review, we focus on the utilization of 1,2,3-triazole, 1,2,4-triazole and tetrazole ligands to create coordination polymers, metal complexes and spin-crossover compounds, reported to the end of 2009. In the first instance, we present a compendium of all the relevant ligands that have been employed to generate coordination polymers and Metal-Organic Frameworks (MOFs). Due to the huge amount of reported MOFs and coordination polymers bearing these azole rings, three representative examples for each category (therefore nine in total) are described in detail. The second section is devoted to the use of the bridging abilities of these azole ligands to prepare metal complexes (containing at least two metal centers). Given the large number and the great structural diversity of the polynuclear compounds found in the literature, these have been grouped according to their nuclearity. Finally, in the last section, the triazole- and tetrazole-containing coordination compounds exhibiting spin-crossover properties are presented.     

Local virial and tensor theorems

We show that for any wave function and potential the local virial theorem can always be satisfied 2K(r) = r·ΔV by choosing a particular expression for the local kinetic energy. In addition, we show that for each choice of local kinetic energy there are an infinite number of quasi-probability distributions which will generate the same expression. We also consider the local tensor virial theorem.     

Size-selective molecular transport through silica colloidal nanopores

Diffusion rate of dye-labelled PAMAM dendrimers through free-standing silica colloidal crystals was studied as a function of the dendrimer generation and nanopore size to determine the transport selectivity.     

Adaptive panel representation for oblique collision of two vortex rings

In this article, we use a hierarchical panel method for representing vortex sheet surface motion in 3D flow to investigate the oblique collision of two vortex rings. The particles representing the sheet are advected by a regularized Biot-Savart integral with smoothed Rosenhead-Moore kernel. The particle velocities are evaluated by an adaptive treecode algorithm based on Taylor expansions in Cartesian coordinates. The method allowed us to consider late stages of a vortex rings collision, producing a funnel region. Vorticity iso-surfaces evolution is also investigated.     

Thermal fluctuations in pinned elastic systems: field theory of rare events and droplets

Using the functional renormalization group (FRG) we study the thermal fluctuations of elastic objects (displacement field u, internal dimension d) pinned by a random potential at low temperature T, as prototypes for glasses. A challenge is how the field theory can describe both typical (minimum energy T = 0) configurations, as well as thermal averages which, at any non-zero T as in the phenomenological droplet picture, are dominated by rare degeneracies between low lying minima. We show that this occurs through an essentially non-perturbative thermal boundary layer (TBL) in the (running) effective action Γ [u] at T > 0 for which we find a consistent scaling ansatz to all orders. The TBL describes how temperature smoothes the singularities of the T = 0 theory and contains the physics of rare thermal excitations (droplets). The formal structure of this TBL, which involves all cumulants of the coarse grained disorder, is first explored around d = 4 using a one-loop Wilson RG. Next, a more systematic exact RG (ERG) method is employed, and first tested on d = 0 models where it can be pushed quite far. There we obtain precise relations between TBL quantities and droplet probabilities (those are constrained by exact identities which are then checked against recent exact results). Our analysis is then extended to higher d, where we illustrate how the TBL scaling remains consistent to all orders in the ERG and how droplet picture results can be retrieved. Since correlations are determined deep in the TBL (by derivatives of Γ [u] at u = 0), it remains to be understood (in any d) how they can be retrieved (as u = 0⁺ limits in the non-analytic T = 0 effective action), i.e., how to recover a T = 0 critical theory. This formidable “matching problem” is solved in detail for d = 0, N = 1 by studying the (partial) TBL structure of higher cumulants when points are brought together. We thereby obtain the β-function at T = 0, all ambiguities removed, displayed here up to four loops. A discussion of the d > 4 case and an exact solution at large d are also provided.     

Distinctive field dependence of the longitudinal muon polarization for Mu* in polycrystalline silicon

A distinctive longitudinal magnetic field dependence of the muon polarization for anomalous muonium in polycrystalline semiconductor targets has been predicted. The polarization exhibits a cusp,i.e., a discontinuous jump in the slope from negative to positive. Measurements of the longitudinal polarization for polycrystalline silicon in fields up to 0.5 T, and temperatures 53 and 200 K have been made at LAMPF. A cusp in the field dependence indeed occurs at 0.345 T, in excellent agreement with the prediction. No cusp is observed at 200 K because Mu^* has been thermally ionized.     

Positive dependence in Markov chains

A general notion of positive dependence among successive observations in a finite-state stationary process is studied, with particular attention to the case of a stationary ergodic Markov chain. This dependence condition can be expressed as a positivity condition on the joint probability matrices of pairs of observations. Some useful conditions equivalent to positive dependence are obtained for reversible chains, but shown not to be equivalent for nonreversible chains.