From ligand exchange to reaction intermediates: what does really happen during the synthesis of emissive complexes?

In situ monitoring of the formation of emissive complexes is essential to enable the development of rational synthesis protocols, to provide accurate control over the generation of structure-related properties (such as luminescence) and to facilitate the development of new compounds. In situ luminescence analysis of coordination sensors (ILACS) utilizes the sensitivity of the spectroscopic properties of lanthanide ions to their coordination environment to detect structural changes during crystallization processes. Here, ILACS was utilized to monitor the formation of [Eu(bipy)(NO)] (bipy = 2,2'-bipyridine) during co-precipitation synthesis.

In situ ligand exchange-mediated 0D/1D transformation of a polyoxovanadate.

The antimonato-polyoxovanadate {Ni(en)}[VSbO(HO)]·ca.15HO was utilized as a synthon for the solvothermal in situ generation of the new compound {Ni(phen)}[{Ni(en)}VSbO(HO)]·19HO, a rearrangement induced by ligand metathesis. While in the precursor structure cations and anions are isolated, the solid-state structure of the product is characterized by 1D chains consisting of alternating [VSbO(HO)] cluster shells and [Ni(en)] units covalently linked to neighboring clusters via terminal oxygen atoms.