A theoretical chemistry-based strategy for the rational design of new luminescent lanthanide complexes: an approach from a multireference SOC-NEVPT2 method

Abstract

Theoretical methods of the SOC-NEVPT2 type combined with a molecular fragmentation scheme have proven to be a powerful tool that allows explaining the luminescence sensitization mechanism in Ln (III) coordination...

The role of substituted pyridine Schiff bases as ancillary ligands in the optical properties of a new series of fac-rhenium(i) tricarbonyl complexes: a theoretical view

“…The luminescence properties of organometallic Re( i ) tricarbonyl complexes are crucially affected by relativistic effects. 47,76 In a non- or scalar-relativistic picture, triplet states are three-fold degenerate. 43,77 The spin–orbit effect on this degeneracy can be quantified by the zero-field splitting (ZFS) resulting from the dipolar interaction between magnetic moments of unpaired electrons ( Fig.…”

Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study

“…The luminescence properties of Re­(I) tricarbonyl complexes are crucially affected by relativistic effects. , Moreover, those effects can strongly influence heavy elements’ chemical and physical properties of complexes . In this sense, for a good description of the photophysical properties in Re­(I) complexes, a detailed analysis of the electronic configuration of the ground and excited states is necessary (Figure A).…”

“…2−5 Although biocompatibility must be empirically determined directly by working with cell models, due to their complexity, photophysical properties can be predicted using quantum chemical calculations with a good approximation to experimental data. 11,15,16 In this work, we present a relativistic theoretical analysis of two series of fac-[Re(CO) 3 (N,N)PSB] 1+ complexes to predict the role of the IHB in the ancillary ligand concerning their photophysical behavior. N,N corresponds to 2,2′-bipyridine (bpy) (series A) or 4,4′-bis(ethoxycarbonyl)-2,2′-bipyridine (deeb) (series B) (Figure 1).…”

“…As stated, the suitability of Re­(I) tricarbonyl complexes as good fluorophores for imagery is mainly based on two fundamental properties: (1) biocompatibility (e.g., low cytotoxicity and good cell uptake) and (2) modulable photophysical properties for fluorescence microscopy, especially the emission range. − Although biocompatibility must be empirically determined directly by working with cell models, due to their complexity, photophysical properties can be predicted using quantum chemical calculations with a good approximation to experimental data. ,, In this work, we present a relativistic theoretical analysis of two series of fac -[Re­(CO) 3 (N,N)­PSB] 1+ complexes to predict the role of the IHB in the ancillary ligand concerning their photophysical behavior. N,N corresponds to 2,2′-bipyridine ( bpy ) (series A) or 4,4′-bis­(ethoxycarbonyl)-2,2′-bipyridine ( deeb ) (series B) (Figure ).…”