Effect of Pyrrolidinedithiocarbamate Ligand on the Luminescence Properties of Heteroligand Samarium and Europium Complexes: Experimental and Theoretical Study.

The photophysical properties of two isostructural heteroligand lanthanide complexes of general formula Ln(pdtc)3(phen) (pdtc = pyrrolidinedithiocarbamate anion, phen = 1,10-phenanthroline), Ln = Sm3+ (1), Eu3+ (2)) were studied in solid state and dichloromethane (DCM) solution. The two lanthanide complexes were investigated by experimental techniques for structural (single-crystal X-ray diffraction analysis of 1, powder XRD, TG-DTA) and spectroscopic [electron paramagnetic resonance (EPR), infrared (IR), ultraviolet-visible (UV-vis), photoluminescence (PL)] characterization. DFT/TDDFT/ωB97xD and multireference SA-CASSCF/NEVPT2 calculations with perturbative spin-orbit coupling corrections were applied to construct the Jablonski energy diagrams and to discuss the excited state energy transfer mechanism with competing excited state processes and possible sensitized mechanism of metal-centered emission. The first excited state (S1) involved in the excited state energy transfer L(antenna)-to-Ln was predicted to have interligand (pdtc-to-phen) charge transfer character in contrast to the previously predicted ligand-to-metal charge transfer character. The theoretical consideration showed similar relaxation paths and luminescence quenching channels and appropriate Donor*(phen)-Acceptor*(Ln3+) energy gap for 1 and 2. The experimental measurements in the solid state, however, showed efficient luminescence and good ability to convert UV to visible light only for the Sm(pdtc)3(phen) complex. The minor emission of 2 was explained by partial reduction of Eu3+, confirmed by EPR and calculated electron density distribution data.

Investigation of the Sensing Properties of Lanthanoid Metal-Organic Frameworks (Ln-MOFs) with Terephthalic Acid.

The solvothermal synthesis of LnCl3.nH2O with terephthalic acid (benzene-1,4-dicarboxylic acid, H2BDC) produced metal-organic frameworks (LnBDC), [Ln2(BDC)3(H2O)4]∞, where Ln = Sm, Eu, Tb, and Dy. The materials obtained were characterized by a number of physico-chemical techniques. The influence of the ionic radius of the lanthanides on the microstructural characteristics of the Ln-MOFs was evaluated by performing Rietveld refinement. The MOFs obtained were tested as fluorescent sensors for numerous cations and anions in water. The highly luminescent EuBDC and TbBDC demonstrated multi-responsive luminescence sensing functions to detect Ag(I), Fe(III), Cr(III), and Cr(VI), which are essential for their environmental applications. By applying the non-linear Stern-Volmer equation, the fluorescent quenching mechanism was determined. The stability of the obtained materials in water in a wide pH range (acidity pH = 4 and alkalinity pH = 9 solutions) was confirmed.

Molecular Design of Luminescent Complexes of Eu(III): What Can We Learn from the Ligands.

The luminescent metal-organic complexes of rare earth metals are advanced materials with wide application potential in chemistry, biology, and medicine. The luminescence of these materials is due to a rare photophysical phenomenon called antenna effect, in which the excited ligand transmits its energy to the emitting levels of the metal. However, despite the attractive photophysical properties and the intriguing from a fundamental point of view antenna effect, the theoretical molecular design of new luminescent metal-organic complexes of rare earth metals is relatively limited. Our computational study aims to contribute in this direction, and we model the excited state properties of four new phenanthroline-based complexes of Eu(III) using the TD-DFT/TDA approach. The general formula of the complexes is EuL2A3, where L is a phenanthroline with -2-CH3O-C6H4, -2-HO-C6H4, -C6H5 or -O-C6H5 substituent at position 2 and A is Cl- or NO3-. The antenna effect in all newly proposed complexes is estimated as viable and is expected to possess luminescent properties. The relationship between the electronic properties of the isolated ligands and the luminescent properties of the complexes is explored in detail. Qualitative and quantitative models are derived to interpret the ligand-to-complex relation, and the results are benchmarked with respect to available experimental data. Based on the derived model and common molecular design criteria for efficient antenna ligands, we choose phenanthroline with -O-C6H5 substituent to perform complexation with Eu(III) in the presence of NO3¯. Experimental results for the newly synthesized Eu(III) complex are reported with a luminescent quantum yield of about 24% in acetonitrile. The study demonstrates the potential of low-cost computational models for discovering metal-organic luminescent materials.

Luminescent Complexes of Europium (III) with 2-(Phenylethynyl)-1,10-phenanthroline: The Role of the Counterions.

New antenna ligand, 2-(phenylethynyl)-1,10-phenanthroline (PEP), and its luminescent Eu (III) complexes, Eu(PEP)2Cl3 and Eu(PEP)2(NO3)3, are synthesized and characterized. The synthetic procedure applied is based on reacting of europium salts with ligand in hot acetonitrile solutions in molar ratio 1 to 2. The structure of the complexes is refined by X-ray diffraction based on the single crystals obtained. The compounds [Eu(PEP)2Cl3]·2CH3CN and [Eu(PEP)2(NO3)3]∙2CH3CN crystalize in monoclinic space group P21/n and P21/c, respectively, with two acetonitrile solvent molecules. Intra- and inter-ligand π-π stacking interactions are present in solid stat and are realized between the phenanthroline moieties, as well as between the substituents and the phenanthroline units. The optical properties of the complexes are investigated in solid state, acetonitrile and dichloromethane solution. Both compounds exhibit bright red luminescence caused by the organic ligand acting as antenna for sensitization of Eu (III) emission. The newly designed complexes differ in counter ions in the inner coordination sphere, which allows exploring their influence on the stability, molecular and supramolecular structure, fluorescent properties and symmetry of the Eu (III) ion. In addition, molecular simulations are performed in order to explain the observed experimental behavior of the complexes. The discovered structure-properties relationships give insight on the role of the counter ions in the molecular design of new Eu (III) based luminescent materials.

Synthesis, crystal structure and physico-chemical properties of 3,3'-[(4-hydroxyphenyl)methyl] bis-(4-hydroxy-2H-chromen-2-one).

The compound 3,3'-[(4-Hydroxyphenyl)methyl]bis-(4-hydroxy-2H-chromen-2-one) was synthesized by the Knoevenagel reaction. Crystals, suitable for X-ray data collection, were grown by slow evaporation from an ethanol solution. The product 3,3'-[(4-Hydroxyphenyl)methyl]bis-(4-hydroxy-2H-chromen-2-one) · ethanol crystallizes in the monoclinic system, space group P2(1)/n. The ultraviolet/visible absorption spectra in different solvents were recorded. Sensitivity of the compound to solvent polarity and hydrogen bonding with protic (ethanol, H(2)O) and aprotic (dimethylsulfoxide, acetonitrile) solvents was detected. Based on (1)H-NMR spectroscopy as well as on potentiometric and UV/vis titration experiments the acid dissociation constants for 3,3'-[(4-Hydroxyphenyl)methyl]bis-(4-hydroxy-2H-chromen-2-one) were estimated.