π‑Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study

Abstract

The novel tetrahedral 10-(4-carboxyphenyl)-2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl- 5H-di-pyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-4-ium-5-uide [NՈNBF2] BODIPY complex was prepared in a very good yield and via one-pot synthesis. The desired [NՈNBF2] has been used as a model complex for XRD/HSA interactions and DFT/B3LYP/6-311G(d,p) computations. The tetrahedral geometry around the boron center was demonstrated by DFT optimization and XRD-crystallography. The 1H, 11B, and 19F-NMR spectra were used also to support the high symmetrical BODIPY via π‑extended phenomena. Moreover, the values of the DFT-calculated structural bond lengths/angles and DFT-IR were matched to the corresponding experimental XRD and IR parameters, respectively. The crystal lattice interactions were correlated to Hirshfeld surface analysis (HSA) calculations. Calculations of the Mulliken Atomic Charge (MAC), Natural Population Analysis (NPA), Global reactivity descriptors (GRD), and Molecular Electrostatic Potential (MEP) quantum parameters were performed to support the XRD/HSA interactions result. Analysis of the predicted Density of States (DOS), molecular orbital, and time-dependent density functional theory (TD-DFT) calculations have been combined to explain the experimental UV-vis spectra and electron transfer behavior in [NՈNBF2] complex using MeOH and other four solvents.