Four new luminescent-organic frameworks exhibiting highly sensing of nitroaromatics: An experimental and computational insight

Sensing mechanism elucidation of a chemosensor based on a metal‐organic framework selective to explosive aromatic compounds

“…Regarding this, Bauer et al [ 23 ] pointed out the importance of the design of LMOFs based on closed‐shell metal ions, also taking into account that it is possible to tune the linker‐centered emission by modifying the structure of the linker. This fact is mostly studied as this type of MOFs is unlikely to emit metal light as the Zn‐based and Cd‐based LMOFs reported by Lu et al [ 24 ] Based on these premises, Lustig et al [ 25 ] developed a series of LMOFs with ligand‐centered emission. They performed the modification of the linkers (tetrakis[4‐carboxyphenyl] ethylene) by both fluorination and elongation.…”

“…From these results, researchers have proposed that the most probable PET mechanism is due to electron transfer from the conduction band (CB) of the MOF to the lowest unoccupied molecular orbital (LUMO) of NACs. [24,28] Nevertheless, as most of the theoretical reports deal with the computations of the MOF and analyte separately, which have limited the analysis to an orbital energy comparison between both structures, it becomes imperative to address the study of host-guest systems to design MOFs as sensors. This is a remarkable topic in the literature due to their role in changes on the photophysical properties that govern the recognition mechanisms of analytes.…”

“…In this sense, the energy decomposition scheme proposed by Morokuma-Ziegler was demonstrated to provide valuable information in this regard, as well as natural orbitals for chemical valence (NOCV) calculations to characterize the charge transfer channels. [33,34] 2 | COMPUTATIONAL DETAILS According to Zhong-Min [35] and Lu, [24] from the point of view of the molecular orbitals, MOFs can be treated as discrete molecular systems. This fact is especially applicable in LMOFs based on d 10 metal because they present narrow band gaps energies and highly localized electronic states.…”

Sensing Mechanism Elucidation of a Chemosensor Based on a Metal-Organic Framework (MOF) Selective to Explosive Aromatic Compounds

“…This fact is mostly studied since this type of MOFs are unlikely metal light emisor, as the Zn-based and Cd-based LMOFs reported by W. Liu and co-workers. 22 Based on these premises, Lustig et al (2016) 23 developed a series of LMOFs with ligand-centered emission. They performed the modification of the linkers (tetrakis(4-carboxyphenyl) ethylene) by both fluorination and elongation.…”

“…According to Zhong-Min (2014) 34 and Lu (2019) 22 from the point of view of the molecular orbitals, MOFs can be treated as discrete molecular systems. This fact is especially applicable in LMOFs based on d 10 metal, due that they present narrow band gaps energies and highly localized electronic states.…”