Supramolecular D⋯A-layered structures based on germanium complexes with 2,3-dihydroxynaphthalene and ,'-bidentate ligands.

The concept of using redox-active ligands, which has become extremely widespread in organometallic chemistry, is often considered from 'their effect on the metal center properties' point of view and 'how to modify the ligands'. In this paper, we present the reverse side of this effective approach - a dramatic change of redox properties of ligands under the influence of a redox-inert metal. Germanium derivatives based on 2,3-dihydroxynaphthalene (1) and ,'-bidentate ligands, namely 2,2'-bipyridine (2) and 1,10-phenanthroline (3), were obtained and characterized by CV, UV-vis spectroscopy, DFT calculations and in the case of 3 X-ray diffraction. It was shown that the HOMO of the complexes is almost completely located on the naphthalene fragment while the LUMO is on the ,-ligands. At the same time, there are no boundary molecular orbitals on the germanium atom, but it forms the axial part of the molecule holding two opposite motifs together. Moreover, it sharply affects the level of HOMO and LUMO. Derivatives 2 and 3 are more easily oxidized compared to 2,3-dihydroxynaphthalene by 0.31-0.34 V (7-8 kcal mol) and are more easily reduced compared to ,-donors by 1.08-1.15 V (25-26.5 kcal mol). All this together makes it possible to form a system with a narrow HOMO/LUMO gap (∼2 eV). The crystal structure of 3 consists of alternating monomolecular easily oxidizing and easily reducing layers formed due to intermolecular interactions, in particular π-stacking. In addition, in contrast to 1 that starts to decompose noticeably at the temperatures from 200 °C, 2 and 3 have an extremely high thermal stability. They remain stable with no signs of decomposition and melting up to 400 °С. We believe that this approach to the formation of the supramolecular structure may present prospects for obtaining new functional materials.