Facile One‐Pot Route toward Water‐Soluble Lanthanide–Copper–Glycinehydrox­imate 15‐Metallacrown‐5 Complexes

Abstract

Among the Ln[15MC CuRha -5] metallacrowns (MC; Rha = R-substituted hydroximate ligands), the simple glycinehydroximate (Glyha) complex is presented as the primary model for studying various aspects of the guest interaction with the Ln III ion. We report a one-pot synthesis of several glycinehydroximate LnL[15MC CuGlyha -5] derivatives in the presence of calcium compounds. The complexes with biden-II Glyha -5](NO 3 ) 2 (3), and biden-[a] G.A. Razuvaev 5202 tate lactate Gd(CH 3 CHOCOO)[15MC Cu II Glyha -5]Cl 2 [4(Gd)]have been prepared and characterized by X-ray analysis. The lactate was chosen as an example of the essential oxyanions that exist as metabolites in all living organisms. We examined the lanthanide-induced NMR spectroscopy shifting ability of a series of lactate 4(Ln) metallacrown complexes (Ln = La, Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, or Dy). The corresponding Gd III complex was characterized by 1 H NMR spectroscopy relaxometric techniques in aqueous media. II Glyha -5](NO 3 ) 2 can be easily prepared by a onepot method in the presence of calcium compounds. [15] Herein, we have developed this synthetic strategy when pre-Scheme 2. Synthetic pathway to nitrate 1.

pH‐Responsive Switching Properties of a Water‐Soluble Metallamacrocyclic Phenylalaninehydroximate La(III)–Cu(II) Complex: Insight into Tuning Protonation Ligand States

“…Following a previously described synthetic procedure for water‐soluble 15‐MC‐5 metallacrowns, we took the most frequently used two‐step methodology with some modification. In the first step, α‐phenylalaninehydroxamic acid and LaCl 3 were mixed in water and, in the second step, Cu(OAc) 2 was added to this solution (Schemeà).…”

“…It should be pointed out that the observed ligand‐field bands in visible region near 550 nm have provided the potential ability to obtain useful diagnostic information concerning the structures of transition metal ion‐peptide complexes . The blue water‐soluble polynuclear aminohydroximate metallamacrocyclic Cu(II)‐Ln(III) complexes show an intense absorption band at 575 nm with ε ≈ 400 M –1 cm –1 , . As seen in the schematic representation (Schemeà) the protonation of aminohydroximate ligands can lead to reversible electron redistribution within the MC molecule with the corresponding change in color.…”

Polynuclear Aminohydroximate Metallamacrocyclic Cu(II)‐Ce(III) Complexes: A Facile Route to Intricate Nanostructures of Copper and Cerium Oxides

“…The synthesis of Cu(II)‐Ce(III) 15‐metallacrown‐5 complexes was performed using a modified procedure reported early , …”

Preparation and Thermal Decomposition of Ln(III)-Cu(II) Polynuclear Metallamacrocyclic Compounds Based on Glycinehydroxamic Acid

“…Синтез Ln(H 2 O) 4 [15MC CuGlyha -5]Cl 3 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Y, Dy) проводили в воде при комнатной температуре при перемешивании глицингидроксамовой кислоты, ацетата меди и соответствующего хлорида лантаноида в течение 1.5-2 часов согласно разработанной ранее методике. [18,19] Термическое разложение комплексов изучали ТГА-ДСК-МС методом на установке, состоящей из термического анализатора STA 449 F1 Jupiter и масс-спектрометра QMS 403D Aeolos (NETZSCH, Germany). Измерения выполнены в атмос-фере гелия в интервале температур 20-600 °С при скорости нагрева 5 °C⋅мин -1 и скорости потока газа 30 мл⋅мин -1 .…”