Chelating Complexes of Diethylzinc and ZnCl2 with 2,2‐Bipyridine and 1,6,7,12,13,18‐Hexaazatrinaphthylene (HATN) as Ligands

The 1,6,7,12,13,18‐hexaazatrinaphthylene (HATN) complex [(Et₂Zn)₃(μ₃‐HATN)] was synthesized and characterized by IR spectroscopy, UV/Vis spectroscopy, elemental analysis and ESI‐MS spectrometry. Attempts to prepare ZnCl₂ complexes of HATN leads only to the mononuclear [(Cl₂Zn)(HATN)] derivative, characterized by X‐ray diffraction, IR‐ and UV/Vis‐spectroscopy as well as ESI‐MS spectrometry. The bright red 2,2′‐bipyridine (bipy) complex [(Et₂Zn)(bipy)] ( 1 ) was synthesized and characterized by X‐ray diffraction and NMR spectroscopy. The UV/Vis‐spectra of the HATN‐complexes show absorptions in regions of far longer wavelengths than the corresponding 2,2′‐bipyridine or 1,10‐phenantroline complexes. Consequently the π*‐LUMO of HATN ( 5 ) is lower in energy than the π*‐LUMO of 2,2′‐bipyridine ( 2 ) or 1,10‐phenanthroline (phen).