Relationship between Reactivity Ratios and Configuration for Donor—Acceptor Type Copolymers

For binary copolymers from an acrylic monomer (acceptor type, M¹) and an aromatic-substituted monomer (donor type, M₂) a linear relation between log (r₂/r¹) and the probability of “coisotactic” alternating addition is observed. This can be a proof for the influence of monomer polarity on the copolymer configuration.     

Synthesis and anion binding of 2-arylazo-meso-octamethylcalix[4]pyrroles

2-Arylazo-5,5,10,10,15,15,20,20-octamethylcalix[4]pyrroles (azo-OMCPs) have been synthesised by the reaction of calix[4]pyrrole with aryldiazonium chloride in 15–45% yields. The solution-state binding studies of the synthesised hosts were investigated by absorption spectroscopy and ¹H NMR in DMSO and CDCl₃, respectively. These receptors, appended with electron-donating and electron-withdrawing groups, displayed enhanced affinity and selectivity for fluoride anion. Well-defined colour change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO solution of azo-OMCPs. Detailed NMR studies in CDCl₃ revealed that azo-OMCPs with nitro and chloro groups have higher binding affinity for fluoride ion.

     

Photophysics of Push–Pull Distyrylfurans,Thiophenes and Pyridines by Fast and Ultrafast Techniques

Time‐resolved transient absorption and fluorescence spectroscopy with nano‐ and femtosecond time resolution were used to investigate the deactivation pathways of the excited states of distyrylfuran, thiophene and pyridine derivatives in several organic solvents of different polarity in detail. The rate constant of the main decay processes (fluorescence, singlet–triplet intersystem crossing, isomerisation and internal conversion) are strongly affected by the nature [locally excited (LE) or charge transfer (CT)] and selective position of the lowest excited singlet states. In particular, the heteroaromatic central ring significantly enhances the intramolecular charge‐transfer process, which is operative even in a non‐polar solvent. Both the thiophene and pyridine moieties enhance the S₁→T₁ rate with respect to the furan one. This is due to the heavy‐atom effect (thiophene compounds) and to the ¹(π,π)*→³(n,π)* transition (pyridine compounds), which enhance the spin‐orbit coupling. Moreover, the solvent polarity also plays a significant role in the photophysical properties of these push–pull compounds: in fact, a particularly fast ¹LE*→¹CT* process was found for dimethylamino derivatives in the most polar solvents (time constant, τ≤400 fs), while it takes place in tens of picoseconds in non‐polar solvents. It was also shown that the CT character of the lowest excited singlet state decreased by replacing the dimethylamino side group with a methoxy one. The latter causes a decrease in the emissive decay and an enhancement of triplet‐state formation. The photoisomerisation mechanism (singlet/triplet) is also discussed.     

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.