Unlocking Metal Coordination of Diborylamides through Ring Constraints

A cyclic lithium diborylamide compound was synthesized and crystallographically characterized, revealing strong Li-N bonding in sharp contrast to previous linear diborylamides. Two iron(II) diborylamide complexes were also synthesized, including a...

Well-organised two-dimensional self-assembly controlled by in-situ formation of a Cu(II)-coordinated rufigallol derivative: a scanning tunnelling microscopy study

The two-dimensional self-assembly of rufigallol derivatives and their metal coordination were studied by scanning tunnelling microscopy. Ex-situ Cu(II)-coordinated rufigallol derivatives exhibited columnar structures with some defects, whereas regular and linear...

Deep X-Ray Lithography on "Sol-Gel" Processed Noble Metal Mesoarchitectured Films

Noble metal coordination xerogels films (mesostructured with block-copolymers) exibit solubility switch during X-ray irradiation. Differently from other sol-gel systems, this is attributed to the film deconstruction during irradiation. These materials...

Solar energy conversion using first row d-block metal coordination compound sensitizers and redox mediators

The use of renewable energy is essential for the future of the Earth, and solar photons are the ultimate source of energy to satisfy the ever-increasing global energy demands....

Metal Coordination Properties of a Chromophoric Desferrioxamine (DFO) Derivative: Insight on the Coordination Stoichiometry and Thermodynamic Stability of Zr4+ Complexes

Desferrioxamine (DFO) is the current “gold standard” chelator for 89Zr4+, which is used to label monoclonal antibodies for applications in immunopositron emission tomography. Recently, controversial data have been reported regarding the speciation and the stability of the complexes formed by DFO with Zr4+ in solution. To shed some light on this point, we studied the coordination properties in solution ofa chromophoric DFO derivative bearing a substituted pyrimidine residue (DFO–Pm) toward several metal ions (Zr4+, Cu2+, Zn2+, Mg2+, Ca2+, Na+, K+). Potentiometric titrations showed that DFO–Pm and pristine DFO form complexes with very similar stoichiometry and stability. DFO–Pm, which can consequently be taken as a model system for DFO, provides a photochemical response to metal coordination that can be used to further define the complexes formed. In the critical case of Zr4+, spectrophotometric measurements allowed the verification of the formation of 1:1 and 2:3 complexes that, together with 2:2 complexes form the coordination model that was obtained through the use of our potentiometric measurements. Additionally, mass spectrometry measurements verified the formation of 1:1 and 2:3 complexes and showed that 1:2 species can be easily generated through the fragmentation of the 2:3 species. In conclusion, the results obtained with DFO–Pm validate the complexation model of Zr4+/DFO composed of 1:1, 2:2, and 2:3 metal-to-ligand complexes. Convergences and conflicts with other works are addressed.