Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

Abstract

Lanthanide-based crystalline coatings have a great potential for energy-conversion devices, but until now luminescent surface-anchored materials were difficult to fabricate. Thin films, called lanthanides surface-mounted metal–organic frameworks (SURMOFs) with tetrasubstituted halide (fluorine, chlorine, and bromine) terephthalic acid derivative linkers as a basic platform for optical devices, exhibit a high quantum yield of fluorescence visible to the naked eyes under ambient light. We show that we can tune the luminescent properties in thin films by halide substitution, which affords control over the molecular structure of the material. We rationalize the mechanism for the modulation of the photophysical properties by “antenna effect”, which controls the energy transfer and quantum yields using experimental and theoretical techniques for chelated lanthanides as a function of the type of atom substitutions at the phenyl rings and the resulting dihedral angle between phenyl rings in the linkers and carboxylate groups.

Lanthanide-MOFs as multifunctional luminescent sensors

“…Among the multifunctional ligands, organic moieties with a π-conjugated system can effectively sensitize Ln 3+ ions through the antenna effect, resulting in enhanced overall luminous intensity. 18…”

Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation

“…Lanthanide-based coordination polymers attract great interest. − Indeed, because of the unique optical , and magnetic properties of the lanthanide ions, they present great interest in various technological fields such as molecular thermometry, − chemical sensing, − light and display, , or the fight against counterfeiting, − for instance. Therefore, the quest for highly luminescent lanthanide-based coordination polymers is a continuous concern. ,− Because lanthanide ions present no structuring effect, most of the reported studies focus their attention on the choice of the ligand. ,,− This synthetic strategy offered very luminescent coordination polymers with high quantum yields. − Some recent works suggest that an extended inorganic sublattice surrounded by ligands that act both as antennas and as spacers is relevant as far as highly luminescent coordination polymers are targeted. − …”

Thin Films of Lanthanide Stearates as Modifiers of the Q-Sense Device Sensor for Studying Insulin Adsorption

“…The use of this protein as a drug is still an extremely common procedure in improving the quality of life for patients with diabetes. The questions of searching for chromatographic methods for specific isolation and determination are still important. − Thin-film materials containing lanthanide atoms, as an example of nanotechnology, are actively used in many fields. − Also, materials containing lanthanide atoms are being actively studied as materials for bioorganic sensors, − including for determining the activity of insulin and analytical applications in the analysis of insulin content in complex systems. ,− Taking into account all of the problems associated with the production and application of such materials for proteomics, the purpose of this work is to demonstrate the possibility of using films containing lanthanide ions for insulin adsorption.…”