2,2/-Bipyridyl Chelated Ru(II)-Annulated NHC Complex of 1-Methyl-2-Pyridin-2-Yl-2H-Imidazo[1,5-a]Pyridin-4-Ylidene: Synthesis, Structure, Optical Properties, and DFT Interpretation

Abstract

This article depicts the synthesis of Ru(II)-NHC complex, [Ru(bpy)(NHC)(CH 3 CN) 2 ][PF 6 ] 2 (2); [NHC = 1-methyl-2-(pyridyl)imidazo[1,5-a]pyridine-2-yiledene, bpy = 2,2 ' -bipyridine] via Ag(I)-carbene trans-metallation process. X-ray diffraction studies of the compound 2 elucidate the triclinic crystal system of single crystal with a distorted octahedral geometry. To insight into the structure and optoelectronic properties, density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies were performed, and the absorption spectra were of intra-ligand charge transfer transitions (ILCT) character along with large contribution of (metal-ligand charge transfer (MLCT) transition in complexes. The compound 2 is fluorescent active and it is expected that the source of fluorescence is due to the presence of 2,2 ' -bipyridine fluorophore. Hirshfeld model studies were also performed of the crystal structure to illustrate the nature of intermolecular interactions present in the structure in the crystalline environment, and the molecule possess several C-H…Fweak H-bonding interactions. The molecule paves the way towards a new pro-apoptotic and antimicrobial compound against various cancer cells and is also a useful pre-catalyst for different types of hydrogenation reactions.

Systematic Mapping of Electrocatalytic Descriptors for Hybrid and Non-Hybrid Molybdenum Dichalcogenides with Graphene Support for Cathodic Hydrogen Generation

“…In the computational section of this work, atomistic modeling studies have been performed with periodic plane-wave density functional theory (DFT) to delve into the surface–electrochemistry of hydrogen binding (also known as chemisorption or adsorption). DFT study has become a powerful tool to provide critical insights into structural, electronic, optical, reactive, and energetic properties of materials and systems. − Binding energetics, which are considered major descriptors for catalytic performance but are difficult to attain with experimental measurement, have been calculated with DFT. The critical role of binding energy is stated by the Sabatier principle; that is, for ideal catalysis, the binding energy of key intermediates should be neither too strong nor too weak to ensure optimal catalysis. − In the case of HER, the well-established interpretation of the Sabatier principle is that for an optimal reaction rate, the binding free energy of hydrogen to the electrocatalyst surface should be zero. ,, In the computational part of this study, the conventional criterion of Δ G b ≈ 0 has been considered as the measure to establish the most suitable binding sites for HER catalysis.…”

Modeling of Batch Organic Dye Adsorption Using Modified Metal‐Organic Framework‐5

“…To gain further understanding of the features of dye and adsorbent for their surface contact, computational analysis is intended to be a complimentary tool. Recently, many theoretical and simulation approaches have been carried out to study adsorption mechanisms as well as the behavior of dyes with respect to the adsorbent surface [39][40][41][42][43]. In addition, many factors influence the rate of dye adsorption [44][45][46].…”