Monomeric and dimeric red/NIR-fluorescent dipyrrin-germanium complexes: facile monomer-dimer interconversion driven by acid/base additions

Highly coordinate germanium complexes of the N2O2-type tetradentate dipyrrin ligand have been synthesized. X-ray crystallographic analysis revealed the pentacoordinate structure of dimeric germanium complex 2 (=(Ge)2O) and the hexacoordinate structure of monomeric complex 3 (=Ge(OMe)(HOMe)). The dimer 2 was easily hydrolyzed in a solution to give monomer 4, though the corresponding siloxane (Si)2O did not react under the same conditions. The addition of DBU to a solution of 4 gave dimer 5, and neutralization by adding acetic acid regenerated the monomer 4, providing the facile and reversible interconversion between the monomer and dimer. The dipyrrin germanium complexes showed an intense absorption and fluorescence near the NIR region, which is more red-shifted than the silicon complexes.