Analyzing excited-state processes and optical signatures of a ratiomeric fluorine anion sensor: a quantum look

Recently, the spectroscopic signatures of a benzoselenadiazole derivative have been investigated in the framework of designing a new ratiometric fluoride sensor(Saravanan et al., Org Lett, 2014, 16: 354–357). It was suggested that this sensor is undergoing excited-state intramolecular proton transfer. In this work, we provide a new look at these experimental data, using a state-of-the-art time-dependent density functional theory approach to mimic the spectroscopic signatures. New insights about the nature of the excited-state processes are obtained.     

Mathematical working space and paradigms as an analysis tool for the teaching and learning of analysis

ZDM – Mathematics Education - Mathematical working space (MWS) is a model that is used in research in mathematics education, particularly in the field of geometry. Some MWS elements are...     

Combination of nitroxide‐mediated polymerization and SET‐LRP for the synthesis of high molar mass branched and star‐branched poly(n‐butyl acrylate) characterized by size exclusion chromatography and rheology

Branched and star‐branched polymers were successfully synthesized by the combination of two successive controlled radical polymerization methods. A series of linear and star poly(n‐butyl acrylate)‐co‐poly(2‐(2‐bromoisobutyryloxy) ethyl acrylate) statistical copolymers, P(nBA‐co‐BIEA)_x, were first synthesized by nitroxide‐mediated polymerization (NMP at T > 100 °C). The subsequent polymerization of n‐butyl acrylate by single electron transfer‐living radical polymerization (SET‐LRP at T = 25 °C), initiated from the brominated sites of the P(nBA‐co‐BIEA)_x copolymer, produced branched or star‐branched poly(n‐butyl acrylate) (PnBA). Both types of polymerizations (NMP and SET‐LRP) exhibited features of a controlled polymerization with linear evolutions of logarithmic conversion versus time and number‐average molar masses versus conversion for final M_n superior to 80,000 g mol^?1. The branched and star‐branched architectures with high molar mass and low number of branches were fully characterized by size exclusion chromatography. The Mark–Houwink Sakurada relationship and the analysis of the contraction factor (g′ = ([η]_branched/[η]_linear)_M) confirmed the elaboration of complex PnBA. The zero‐shear viscosities of the linear, star‐shaped, branched, and star‐branched polymers were compared. The modeling of the rheological properties confirmed the synthesis of the branched architectures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Non‐Pincer‐Type Mononuclear Scandium Alkylidene Complexes: Synthesis,Bonding, and Reactivity

The first non‐pincer‐type mononuclear scandium alkylidene complexes were synthesized and structurally characterized. These complexes exhibited short Sc?C bond lengths and even one of the shortest reported to date (2.1134(18) Å). The multiple character of the Sc?C bond was highlighted by a DFT calculation. This was confirmed by experimental reactivity study where the complex underwent [2+1] cycloaddition with elemental selenium and [2+2] cycloaddition with imine. DFT calculation also revealed a strong nucleophilic behavior of the alkylidene complex that was experimentally demonstrated by the C?H bond activation of phenylacetylene.