The first water-soluble polynuclear metallamacrocyclic Sr(ii)–Cu(ii) complex based on simple glycinehydroximate ligands

Abstract

Experimental and theoretical studies of a new strontium metallacrown reveal the specific central ion influence on molecular and electronic structures of metallamacrocycles.

Structural and Magnetic Properties of a {GdCu5}2 Metallacrown Dimer with a Disulfonate Linker

“…The structure of the 15-metallacrown-5 fragments [GdCu 5 (GlyHA) 5 ] 3 + in complex 1 (Figure 2) is similar to that of several previously reported glycinehydroxamate Ln(III)-Cu(II) 15-metallacrowns-5, [52,53,[70][71][72] and discussion of structural features of 1 will thus be limited to supramolecular interactions of the [GdCu 5 (GlyHA) 5 ] 3 + cation with anions, sodium cations, and their solvating molecules. Details of the structural features of the metallamacrocyclic core {GdCu 5 } 3 + itself are given in the Supplementary Information section.…”

“…Details of the structural features of the metallamacrocyclic core {GdCu 5 } 3 + itself are given in the Supplementary Information section. The structural character-istics (i. e. Cu-O eq , Cu-N eq , Gd-O eq bond distances, Cu-Cu and Gd-Cu separations, and deviations of non-hydrogen atoms from the Cu1-Cu5 metallamacrocyclic plane) of [GdCu 5 (GlyHA) 5 ] 3 + unit in the complex 1 are typical for {LnCu 5 } 3 + 15-metallacrowns-5 [42][43][44][45][60][61][62][63][64][70][71][72][73] and are given in Tables 1 and S2.…”

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns

“…Energies of copper(II) bonds with the oxime and carbonyl oxygen atoms are closer: 35.9–40.4 and 46.3–47.0 kcal/mol, respectively. In general, the bonding situation in the hydroximate chelates of the [M(15-MC Cu(II)Tyrha -5)] 3+ complexes is similar to that in the 15-metallacrowns-5 analyzed by us earlier with use of QTAIM in conjunction with the hybrid functionals τ-HCTHhyb [ 33 ] and M06 [ 29 , 42 , 43 ]. This makes the SR-PBE/rL2 calculations appropriate for description of the hydroximate 15-metallacrowns-5.…”

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

“…For pH values below 3.3 no change of absorbance could be detected and free copper species predominate. At the same time, unlike the Ca(II)–Cu(II) and Sr(II)–Cu(II) [15‐MC‐5] complexes the absorption band at about 640 nm typical of Cu[12‐MC‐4] disassembly species, does not appear. Such a behavior agrees with the earlier potentiometric and calorimetric studies of various Ln(III)–Cu(II) [15‐MC‐5] systems in acidic solutions evidenced only containing the Ln ions solution species .…”