Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas [Cu­(H2O)­(2,2′-bpy)­(H2L)]2·H4L·4H2O (1), [{Cu­(H2O)­(2,2′-bpy)­(H3L)}2(H2L)]·2H2O (2), [Cu­(H2O)­(1,10-phen)­(H2L)]2·6H2O (3), [Cu­(2,2′-bpy)­(H2L)]n·nH2O (4), [Cu­(1,10-phen)­(H2L)]n·3nH2O (5), and [{Cu­(2,2′-bpy)­(MoO3)}2(L)]n·2nH2O (6) have been synthesized starting
from p-xylylenediphosphonic acid (H4L)
and 2,2′-bipyridine (2,2′-bpy) or 1,10-phenanthroline
(1,10-phen) as secondary linkers and characterized by single crystal
X-ray diffraction analysis, IR spectroscopy, and thermogravimetric
(TG) analysis. All the complexes were synthesized by hydrothermal
methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents
a new class of simple building unit (SBU) in the construction of coordination
architectures in metal phosphonate chemistry. The initial pH of the
reaction mixture induced by the secondary linker plays an important
role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal
synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self-assembly of the compounds
based on the solubility of the phosphonic acid H4L. Two-dimensional
coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture,
comprise Cu-dimers as nodes, organic (H2L) and inorganic
(Mo4O12) ligands as linkers. The void space-areas,
created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest
species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal
the antiferromagnetic interactions between the two Cu­(II) ions in
the eight-membered ring, observed in their crystal structures. A density
functional theory (DFT) calculation correlates the conformation of
the Cu-dimer ring with the magnitude of the exchange parameter based
on the torsion angle of the conformation.