Metal-mediated tunability of MOF-based optical modulators.

We report on the design of 1D MOFs based on a nopinane-annelated organic ligand and Co(II) or Ni(II), the variation of which allows tuning the optical modulation bandwidth. Structural and time-resolved analysis revealed the optical modulation mechanism, the rates and its endurance, thereby enriching the list of sustainable MOFs for tunable optical modulators.

Efficient emission of Zn(II) and Cd(II) complexes with nopinane-annelated 4,5-diazafluorene and 4,5-diazafluoren-9-one ligands: how slight structural modification alters fluorescence mechanism.

Zinc(II) and cadmium(II) chlorido complexes with an ,-chelating nopinane-annelated 4,5-diazafluoren-9-one ligand (LO) were synthesized. While the zinc(II) complex is mononuclear and adopts a tetrahedral ZnNCl coordination geometry, its cadmium(II) analogue features a 1D polymeric structure due to the bridging coordination of chlorido ligands with Cd ions having an octahedral CdNCl coordination geometry. The photophysical properties of the oxygen-containing LO ligand and its zinc(II) and cadmium(II) complexes were studied in solution and in the solid state and matched against the properties of its oxygen-free 4,5-diazafluorene congener L and its complexes of the same metal ions.

Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis, Structure, Magnetic and Catalytic Properties.

The reactions of CuX (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuXL] (X = Cl (), Br (), L = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b']diquinolin-12(2H)-one) and [(CuX)L]n (X = Cl (), Br (), L = (1R,3R,8R,10R,1'R,3'R,8'R,10'R)-2,2,2',2',9,9,9',9'-Octamethyl-1,1',2,2',3,3',4,4',7,7',8,8',9,9',10,10'-hexadecahydro-1,3:1',3':8,10:8',10'-tetramethano-12,12'-bi(cyclopenta [1,2-b:5,4-b']diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds , and were determined by X-ray diffraction (XRD) analysis.

Chiral -Symmetric Diimines with 4,5-Diazafluorene Units.

A synthetic approach to a new group of stable chiral -symmetric diimines with the 4,5-diazafluorene core has been developed based on condensation of dipinodiazafluorene with aromatic diamines. The chemical structures of new compounds were proven by spectroscopic methods and X-ray crystallography. All the compounds form solvates with organic solvents (chloroform, benzene, 1,4-dioxane) and water.