Molecular Tuning in Diaryl-Capped Pyrrolo [2,3-d:5,4-d′] bisthiazoles: Effects of Terminal Aryl Unit and Comparison to Dithieno[3,2-b:2′,3′-d]pyrrole Analogues

A series of six conjugated oligomers consisting of a central pyrrolo[2,3-d:5,4-d′]bisthiazole (PBTz) end-capped with either thienyl, furyl, or phenyl groups have been prepared from N-alkyl-and N-aryl-pyrrolo[2,3-d:5,4-d′]bisthiazoles via Stille and Negishi cross-coupling. The full oligomeric series was thoroughly investigated via photophysical and electrochemical studies, in parallel with density functional theory (DFT) calculations, in order to correlate the cumulative effects of both aryl end-groups and N-functionalization on the resulting optical and electronic properties. Through comparison with the analogous dithieno[3,2-b:2′,3′-d]pyrrole (DTP) materials, the effect of replacing DTP with PBTz on the material HOMO energy and visible light absorption is quantified.This research was funded by MICINN (project PID2019-110305GB-I00) and by Junta de Andalucía (P09FQM-4708 and P18-FR-4559). Partial funding for open access charge: Universidad de Málag

Totally asymmetric exclusion process with long-range hopping

Generalization of the one-dimensional totally asymmetric exclusion process (TASEP) with open boundary conditions in which particles are allowed to jump $l$ sites ahead with the probability $p_l\sim 1/l^{\sigma+1}$ is studied by Monte Carlo simulations and the domain-wall approach. For $\sigma>1$ the standard TASEP phase diagram is recovered, but the density profiles near the transition lines display new features when $1<\sigma<2$. At the first-order transition line, the domain-wall is localized and phase separation is observed. In the maximum-current phase the profile has an algebraic decay with a $\sigma$-dependent exponent. Within the $\sigma \leq 1$ regime, where the transitions are found to be absent, analytical results in the continuum mean-field approximation are derived in the limit $\sigma=-1$.Comment: 10 pages, 9 figure

Critical behaviour of the 1D q-state Potts model with long-range interactions

The critical behaviour of the one-dimensional q-state Potts model with long-range interactions decaying with distance r as $r^{-(1+\sigma)}$ has been studied in the wide range of parameters $0 < \sigma \le 1$ and $\frac{1}{16} \le q \le 64$. A transfer matrix has been constructed for a truncated range of interactions for integer and continuous q, and finite range scaling has been applied. Results for the phase diagram and the correlation length critical exponent are presented.Comment: 20 pages plus 4 figures, Late

Invaded cluster algorithm for a tricritical point in a diluted Potts model

The invaded cluster approach is extended to 2D Potts model with annealed vacancies by using the random-cluster representation. Geometrical arguments are used to propose the algorithm which converges to the tricritical point in the two-dimensional parameter space spanned by temperature and the chemical potential of vacancies. The tricritical point is identified as a simultaneous onset of the percolation of a Fortuin-Kasteleyn cluster and of a percolation of "geometrical disorder cluster". The location of the tricritical point and the concentration of vacancies for q = 1, 2, 3 are found to be in good agreement with the best known results. Scaling properties of the percolating scaling cluster and related critical exponents are also presented.Comment: 8 pages, 5 figure

Low coordinate NHC-Zinc-Hydride Complexes Catalyze Alkyne C-H Borylation and Hydroboration using Pinacolborane

Organozinc compounds containing sp, sp², and sp³ C–Zn moieties undergo transmetalation with pinacolborane (HBPin) to produce Zn–H species and organoboronate esters (RBPin). This Zn–C/H–B metathesis step is key to enabling zinc-catalyzed borylation reactions, and it is used in this work to develop both terminal alkyne C–H borylation and internal alkyne hydroboration. These two conversions can be combined in one pot to achieve the zinc-catalyzed conversion of terminal alkynes to 1,1-diborylated alkenes without isolation of the sensitive (to protodeboronation) alkynyl boronate ester intermediates. Mechanistic studies involving the isolation of intermediates, stoichiometric experiments, and DFT calculations all support mechanisms involving organozinc species that undergo metathesis with HBPin. Furthermore, zinc-catalyzed hydroboration can proceed via a hydrozincation step, which does not require any exogenous catalyst in contrast to all previously reported alkyne hydrozincations. Bulky <i>N</i>-heterocyclic carbenes (NHCs) are key for effective catalysis as the NHC steric bulk enhances the stability of the NHC–Zn species present during catalysis and provides access to low-coordinate (NHC)­Zn–H cations that are electrophilic yet Brønsted basic. This work provides an alternative approach to access synthetically desirable pinacol–organoboronate esters using earth-abundant metal-based borylation catalysts

On the thermodynamics of first-order phase transition smeared by frozen disorder

The simplified model of first-order transition in a media with frozen long-range transition-temperature disorder is considered. It exhibits the smearing of the transition due to appearance of the intermediate inhomogeneous phase with thermodynamics described by the ground state of the short-range random-field Ising model. Thus the model correctly reproduce the persistence of first-order transition only in dimensions d > 2, which is found in more realistic models. It also allows to estimate the behavior of thermodynamic parameters near the boundaries of the inhomogeneous phase.Comment: 4 page