Simultaneously Probing Two Ultrafast Condensed‐Phase Molecular Symmetry Breaking Events by Two‐Dimensional Infrared Spectroscopy

In condensed phases, a highly symmetric gas‐phase molecule lowers its symmetry under perturbation of the solvent, which is vital to a variety of structural chemistry related processes. However, the dynamical aspects of solvent‐mediated symmetry‐breaking events remain largely unknown. Herein, direct evidence for two types of solvent‐mediated symmetry‐breaking events that coexist on the picosecond timescale in a highly symmetric anion, namely, hexacyanocobaltate, is presented: 1) an equilibrium symmetry‐breaking event in which a solvent‐bound species having lowered symmetry undergoes a population exchange reaction with the symmetry‐retaining species; 2) a dynamic symmetry‐breaking event that is composed of many dynamic population‐exchange reactions under fluctuating solvent interactions. Ultrafast two‐dimensional infrared spectroscopy is used to simultaneously observe and dynamically characterize these two events. This work opens a new window into molecular symmetry and structural dynamics under equilibrium and non‐equilibrium conditions.     

Dimers linked by type‐I C—F...F—C contacts in (Z)‐3‐methyl‐4‐[2‐(4‐methylphenyl)hydrazinylidene]‐1‐(pentafluorophenyl)‐1H‐pyrazol‐5(4H)‐one

The title compound, C₁₇H₁₁F₅N₄O, is described and compared with two closely related analogues in the literature. There are two independent molecules in the asymmetric unit, linked by N—H...O hydrogen bonds and π–π interactions into dimeric entities, presenting a noticeable noncrystallographic C₂ symmetry. These dimers are in turn linked by a medium‐strength type‐I C—F...F—C interaction into elongated tetramers. Much weaker C—H...F contacts link the tetramers into broad two‐dimensional substructures parallel to (101).     

Q‐symmetry and conditional Q‐symmetries for Drinfel'd–Sokolov–Wilson system

We study in this paper the Q‐symmetry and conditional Q‐symmetries of Drinfel'd–Sokolov–Wilson equations. The solutions which we obtain in this paper take the form of convergent power series with easily computable components. Copyright © 2014 John Wiley & Sons, Ltd.     

Dirac reduction for nonholonomic mechanical systems and semidirect products

This paper develops the theory of Dirac reduction by symmetry for nonholonomic systems on Lie groups with broken symmetry. The reduction is carried out for the Dirac structures, as well as for the associated Lagrange–Dirac and Hamilton–Dirac dynamical systems. This reduction procedure is accompanied by reduction of the associated variational structures on both Lagrangian and Hamiltonian sides. The reduced dynamical systems obtained are called the implicit Euler–Poincaré–Suslov equations with advected parameters and the implicit Lie–Poisson–Suslov equations with advected parameters. The theory is illustrated with the help of finite and infinite dimensional examples. It is shown that equations of motion for second order Rivlin–Ericksen fluids can be formulated as an infinite dimensional nonholonomic system in the framework of the present paper.     

Quantum McKay Correspondence for Disc Invariants of Toric Calabi–Yau 3-orbifolds

We announce a result on quantum McK ay correspondence for disc invariants of outer legs in toric Calabi–Yau 3-orbifolds, and illustrate our method in a special example [C3/Z5(1, 1, 3)].     

Residual symmetry reductions and interaction solutions of the (2+1)-dimensional Burgers equation

In nonlinear physics,it is very difficult to study interactions among different types of nonlinear waves.In this paper,the nonlocal symmetry related to the truncated Painleve′expansion of the(2+1)-dimensional Burgers equation is localized after introducing multiple new variables to extend the original equation into a new system.Then the corresponding group invariant solutions are found,from which interaction solutions among different types of nonlinear waves can be found.Furthermore,the Burgers equation is also studied by using the generalized tanh expansion method and a new Ba¨cklund transformation(BT)is obtained.From this BT,novel interactive solutions among different nonlinear excitations are found.     

Is Electrostatics Sufficient to Describe Hydrogen‐Bonding Interactions?

The stability and geometry of a hydrogen‐bonded dimer is traditionally attributed mainly to the central moiety A?H???B, and is often discussed only in terms of electrostatic interactions. The influence of substituents and of interactions other than electrostatic ones on the stability and geometry of hydrogen‐bonded complexes has seldom been addressed. An analysis of the interaction energy in the water dimer and several alcohol dimers—performed in the present work by using symmetry‐adapted perturbation theory—shows that the size and shape of substituents strongly influence the stabilization of hydrogen‐bonded complexes. The larger and bulkier the substituents are, the more important the attractive dispersion interaction is, which eventually becomes of the same magnitude as the total stabilization energy. Electrostatics alone are a poor predictor of the hydrogen‐bond stability trends in the sequence of dimers investigated, and in fact, dispersion interactions predict these trends better.     

Symmetry-Breaking Charge-Transfer Chromophore Interactions Supported by Carbon Nanodots

Carbon dots (CDs) and their derivatives are useful platforms for studying electron-donor/acceptor interactions and dynamics therein. Herein, we couple amorphous CDs with phthalocyanines (Pcs) that act as electron donors with a large extended π-surface and intense absorption across the visible range of the solar spectrum. Investigations of the intercomponent interactions by means of steady-state and pump-probe transient absorption spectroscopy reveal symmetry-breaking charge transfer/separation and recombination dynamics within pairs of phthalocyanines. The CDs facilitate the electronic interactions between the phthalocyanines. Thus, our findings suggest that CDs could be used to support electronic couplings in multichromophoric systems and further increase their applicability in organic electronics, photonics, and artificial photosynthesis.     

σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

In this work, the largest heterometallic supertetrahedral clusters, [Zn₆Ge₁₆]⁴⁻ and [Cd₆Ge₁₆]⁴⁻, were directly self-assembled through highly-charged [Ge₄]⁴⁻ units and transition metal cations, in which 3-center–2-electron σ bonding in Ge₂Zn or Ge₂Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time-dependent HRESI-MS spectra show that the larger clusters grow from smaller components with a single [Ge₄]⁴⁻ and ZnMes₂ units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M₆Ge₁₆]⁴⁻ (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.