Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT

Understanding the structure and properties of MgCl2/TiCl4/ID nanoclusters is a key to uncover the origin of Ziegler-Natta catalysis. In this work MgCl2/TiCl4 nanoplatelets derived by machine learning and DFT calculations have been used to model the interaction with ethyl-benzoate EB (as internal donor) with available exposed sites of binary TixCly/MgCl2 systems. The influence of vicinal Ti2Cl8 and coadsorbed TiCl4 on energetic, structural and spectroscopic behaviour of EB has been considered. The adsorption of homogeneous-like TiCl4EB and TiCl4(EB)2 at the various surface sites have been also simulated. Calculations have been carried out by employing B3LYP-D2 and M06 functionals. The adducts have been characterized by computing IR and Raman spectra that have been found to provide specific fingerprints useful to identify surface species; IR spectra have been successfully compared to available experimental data.

Spectroscopic Behaviour of Two Novel Azobenzene Fluorescent Dyes and Their Polymeric Blends

Two novel symmetrical bis-azobenzene red dyes ending with electron-withdrawing or donor groups were synthesized. Both chromophores display good solubility, excellent chemical, and thermal stability. The two dyes are fluorescent in solution and in the solid-state. The spectroscopic properties of the neat crystalline solids were compared with those of doped blends of different amorphous matrixes. Blends of non-conductive and of emissive and conductive host polymers were formed to evaluate the potential of the azo dyes as pigments and as fluorophores. Both in absorbance and emission, the doped thin layers have CIE coordinates in the spectral region from yellow to red. The fluorescence quantum yield measured for the brightest emissive blend reaches 57%, a remarkable performance for a steadily fluorescent azo dye. A DFT approach was employed to examine the frontier orbitals of the two dyes.

The binding modes of VIVO2+ ions in blood proteins and enzymes

Herein, we report a combined approach of full DFT and MM techniques to unveil the binding sites and modes of VIVO2+ ions with important blood proteins and enzymes and to explain their spectroscopic behaviour.

Tuning the electrochemiluminescent properties of iridium complexes of N-heterocyclic carbene ligands

A series of electrochemiluminescent iridium(iii) N-heterocyclic carbene complexes have been prepared to tune electrochemical and spectroscopic behaviour.

Assessment of the relevance of GaPc substituted with azido-polyethylene glycol chains for photodynamic therapy. Design, synthetic strategy, fluorescence, singlet oxygen generation, and pH-dependent spectroscopic behaviour

New synthetic route and PDT potential of symmetrically and asymmetrically substituted Ga(iii)Pcs with terminal azides.

A comparative study of the electrochemical and the spectroscopic behaviour of trisbipyrazyl ruthenium [Ru(bpz)32+]

Identification of the molecular orbitals in Ru(bpz)32+ involved in charge transfer reactions by means of spectroscopic and electrochemical measurements.