Oligonuclear copper complexes of a bioinspired pyrazolate-bridging ligand: synthesis, structures, and equilibria in solution.
The synthesis of a new bioinspired dinucleating ligand scaffold based on a bridging pyrazolate with appended bis[2-(1-methylimidazolyl)methyl]aminomethyl chelate arms is reported. This ligand forms very stable copper complexes, and a series of different species is present in solution depending on the pH. Interconversions between these solution species are tracked and characterized spectroscopically, and X-ray crystallographic structures of three distinct complexes that correspond to the species present in solution from acidic to basic pH have been determined. Overall, this provides a comprehensive picture of the copper coordination chemistry of the new ligand system. Alterations in the protonation state are accompanied by changes in nuclearity and pyrazolate binding, which cause pronounced changes in color and magnetic properties. Antiferromagnetic coupling between the copper(II) ions is switched on or off depending on the pyrazole binding mode.
Prokofieva
Angelina
A
Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, D-37077 Göttingen, Germany.
Prikhod'ko
Alexander I
AI
Enyedy
Eva Anna
EA
Farkas
Etelka
E
Maringgele
Walter
W
Demeshko
Serhiy
S
Dechert
Sebastian
S
Meyer
Franc
F
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009841:Oligonucleotides / Q000138:chemical synthesis*; D011199:Potentiometry; D011522:Protons; D011720:Pyrazoles / Q000737:chemistry*; D012996:Solutions
D008024:Ligands; D009841:Oligonucleotides; D011522:Protons; D011720:Pyrazoles; D012996:Solutions; D003300:Copper