Modeling the spectral properties of poly(x-phenylenediamine) conducting polymers using a combined TD-DFT and electrostatic embedding approach.

The absorption spectra of polymers derived from ortho, meta and para phenylenediamines (o-PDA, m-PDA and p-PDA) have been simulated combining periodic density functional theory (DFT) calculations with time-dependent DFT simulations. These latter have been carried out on finite clusters embedded in a set of point charges devised to exactly reproduce the electrostatic potential of the periodic chains. The results are compared with those obtained for solvated o-PDA, m-PDA and p-PDA oligomers of increasing sizes extracted from the periodic structures. The electronic transitions involved have been investigated by a qualitative analysis based on isodensity maps completed by a quantitative analysis based on the density-based index (DCT ). For poly-(o)- and poly-(p)- phenylenediamines the agreement with the experimental data is achieved already by modeling solvated dimers whereas the inclusion of long-range electrostatic effects is mandatory for poly-(m)-phenylenediamine highlighting the importance of an accurate treatment of the electrostatic environment when a finite cluster approach is considered.

Copper-Catalyzed Synthesis of Terminal vs. Fluorine-Substituted N-Allenamides via Addition of Diazo Compounds to Terminal Ynamides.

A copper-mediated coupling reaction between ynamides and diazo-compounds to produce N-allenamides is reported for the first time. This method enables facile and rapid access to terminal N-allenamides by using commercially available TMS-diazomethane with wide functional group compatibility on the nitrogen. Furthermore, the ubiquity of molecules containing a fluorine moiety in medicine, in agricultural, and material science requires the continuous search of new building blocks, including this unique surrogate. The CuI/diazo protocol was successfully applied to the synthesis of fluorine-substituted N-allenamides. DFT calculations provided insights in the mechanism involved.

One-Pot anti-Michael Regio- and Stereoselective Hydroamination of Activated N-Allenamides.

N-Allenamides, substituted by an ester at the γ-position, were obtained through addition of terminal ynamides with ethyl diazoacetate under copper catalysis for the first time. Regio- and stereoselective hydroamination of those activated N-allenamides provided exclusively E-configured captodative enamimes through a one-pot anti-Michael addition. Numerous ynamides as well as various secondary amines were adapted in this process.

Modeling UV-Vis spectra of low dimensional materials using electrostatic embedding: The case of CdSe.

We present a generalization of a self-consistent electrostatic embedding approach (SC-Ewald) devised to investigate the photophysical properties of 3D periodic materials, to systems in one- or two-dimensional (2D) reduced periodicity. In this approach, calculations are carried out on a small finite molecular cluster extracted from a periodic model, while the crystalline environment is accounted for by an array of point charges which are fitted to reproduce the exact electrostatic potential (at ground or the excited state) of the infinite periodic system. Periodic density functional theory (DFT) calculations are combined with time dependent DFT calculations to simulate absorption and emission properties of the extended system under investigation. We apply this method to compute the UV-Vis. spectra of bulk and quantum-confined 0D quantum dots and 2D extended nanoplatelets of CdSe, due to their relevance as sensitizers in solar cells technologies. The influence of the size and shape of the finite cluster model chosen in the excited state calculations was also investigated and revealed that, although the long-range electrostatics of the environment are important for the calculation of the UV-Vis, a subtle balance between short- and long-range effects exists. These encouraging results demonstrate that this self-consistent electrostatic embedding approach, when applied in different dimensions, can successfully model the photophysical properties of diverse material classes, making it an attractive low-cost alternative to far more computationally demanding electronic structure methods for excited state calculations.

Direct Synthesis of CF2H-Substituted 2-Amidofurans via Copper-Catalyzed Addition of Difluorinated Diazoacetone to Ynamides.

The significance of molecules containing difluoromethyl groups is driven by their potential applications in pharmaceutical and agrochemical science. Methods for the incorporation of lightly fluorinated groups such as CF2H have been less well developed. Here we report the use of difluorinated diazoacetone as a practical reagent for the direct synthesis of CF2H-substituted 2-amidofurans through addition to ynamides. These newly designed difluorinated amidofurans were elaborated to create new nitrogen-containing frameworks that would be challenging to obtain otherwise.