Insight into structure-property relationship of organometallic terpyridine wires: Combined theoretical and experimental study

Abstract

Recent development in combined theoretical and experimental analysis methods offer an attractive opportunity to investigate organometallic materials. The selection of optimally combined characterization techniques allows for an effective description and even prediction of structure-property relationship occurring in terpyridine (TPY) molecules. In this work, secondary ion mass spectrometry (SIMS), quantitative and qualitative characterization, hand-in-hand, with density functional theory (DFT) calculations, can aid analysis of the chemical stability and reactivity of organic compounds. A case study was based on the characterization of [M-(TPY)2]2+ complexes (M: Co/Fe) with specific organic and organometallic architectures. The SIMS mass spectra showed the step-by-step molecules fragmentation and the quantitative SIMS analysis allowed to predict its direction. Analysis of electron density, electrostatic potential visualization, and calculated bonds length and HOMO-LUMO energetic gap were employed to confirm the differences between the bond-breaking mechanism depending on the metal atom bound to the terpyridine. The combined DFT/SIMS approach was successfully used to assess the chemical stability of various isomers of the TPY compounds, and to determine the possible fragmentation pathways depending largely on the metal centre present within the TPY structure.