Synthesis, Structure, and Spectral-Luminescent Properties of Peripherally Fluorinated Mg(II) and Zn(II) Octaphenyltetraazaporphyrins

Abstract

The cyclization of di-(2,6-difluorophenyl)maleindinitrile with magnesium(II) and zinc(II) acetates in boiling ethylene glycol is applied to synthesize Mg(II) and Zn(II) complexes of the octa-(2,6-difluorophenyl)tetraazaporphyrin. The compounds are identified by UV–Vis, 1H NMR, and mass spectrometry methods. A comparative analysis is performed of the spectral-luminescent properties of magnesium and zinc octaaryltetraazaporphyrinates and their dependence on the number and position of the fluorine atoms in the macrocycle phenyl fragments. The DFT method is used to optimize the geometry of the synthesized complexes. Machine learning methods and QSPR are applied to predict the Soret band wavelength in the UV–V is spectra of the complexes described.

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 ) complexes establish one of the most important classes of emissive compounds. 71–121 Earlier, we synthesized a series of mononuclear zinc( ii ) and cadmium( ii ) complexes with hybrid ligands containing a 2,2′-bipyridine moiety and natural terpene (+)-limonene or (+)-3-carene moieties and demonstrated that they exhibit luminescence with the quantum yield increasing in the following order: free ligand < cadmium( ii ) complex < zinc( ii ) complex. 122 The complexes with the limonene derivative demonstrate excitation wavelength–dependent emission with nanosecond and microsecond lifetimes of the excited states.…”