Lanthanide nitrato complexes bridged by the bis-tridentate ligand 2,3,5,6-tetra(2-pyridyl)pyrazine: Syntheses, crystal structures, Hirshfeld surface analyses, luminescence properties, DFT calculations, and magnetic behavior.

Six dinuclear lanthanide(III) nitrato complexes [Ln(NO3)3(H2O)]2(µ-tppz) (where tppz = 2,3,5,6-tetra(2-pyridyl) pyrazine and Ln(III) = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), and Dy (6)) with bis-tridentate N-heterocyclic 2,3,5,6-tetra(2-pyridyl)pyrazine as bridging ligand have been solvothermally synthesized and characterized via elemental analysis, infrared spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction, and powder X-ray diffraction. The 3-D Hirshfeld surface and 2-D fingerprint plots show that the main interactions in 1-6 are the O⋯H/H⋯O intermolecular interactions with relative contributions of about 62%. Although the poor lanthanide(III)-centered luminescence properties clearly point to the efficiency of nonradiative quenching processes (presence of water molecules in the coordination sphere of the lanthanide(III) ions), the ligand tppz is better suited to sensitize the lanthanide(III)'s emissions of EuIII and NdIII than SmIII, TbIII, and DyIII. Finally, the magnetic data of DyIII comple×6 reveals antiferromagnetic coupling between DyIII ions.

Solid-state luminescence properties, Hirshfeld surface analysis and DFT calculations of mononuclear lanthanide complexes (Ln = EuIII, GdIII, TbIII, DyIII) containing 4'-phenyl-2,2':6',2″-terpyridine.

Four mononuclear lanthanide complexes containing 4'-phenyl-2,2':6',2″-terpyridine (ptpy), [Ln(NO3)3(ptpy) (H2O)] (Ln = Eu (1), Gd (2), Tb (3), Dy (4)), were solvothermally synthesized and characterized via elemental analysis, infrared spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction, and powder X-ray diffraction. Hirshfeld surfaces and the solid-state luminescence properties of the complexes were investigated. The 3-D Hirshfeld surface and 2-D fingerprint plots show that the main interactions are the O H/H O intermolecular interactions in 1-4. Solid-state luminescence investigation reveals that GdIII complex 2 displays a ligand-centered emission and the EuIII, TbIII and DyIII complexes 1, 3 and 4 show the characteristic lanthanide-centered luminescence upon UV excitations. The EuIII and TbIII complexes exhibit red (CIE: 0.6549, 0.3447) and green (CIE: 0.3760, 0.5412) luminescence in the solid state with quantum yields of 16.8% and 0.8% and lifetimes of 0.545 and 0.043 ms, respectively. Density functional theory (DFT) calculations were conducted to unravel the HOMO-LUMO energy gaps of the structures of ptpy and complexes 1 and 3.

Cellular membrane-targeting ruthenium complexes as efficient photosensitizers for broad-spectrum antibacterial activity.

A ruthenium complex [Ru(phen)2(phen-5-amine)-C14] (Ru-C14) with broad-spectrum antibacterial activity was designed and synthesized; positively charged Ru-C14 could target bacteria via electrostatic interactions and showed high binding effectiveness to cell membranes. In addition, Ru-C14 could act as a photosensitizer. Under 465 nm light irradiation, Ru-C14 could generate 1O2, thus disrupting the bacterial intracellular redox balance and leading to bacterial death. Ru-C14 also exhibited minimum inhibitory concentration values of 6.25 µM against Escherichia coli and 3.125 µM against Staphylococcus aureus; these values are lower than those of streptomycin and methicillin. This work combined the merits of cell membrane targeting and photodynamic therapy for antibacterial activity. The findings might open up a new avenue for effective anti-infection treatment and other medical applications.