The Dimeric Pyramidal Cu₂O₆(H₂O)₂ Unit – A Structural Invariant of a Homologous Series of Copper‐Layered Phosphonates

Abstract

Two new layered copper hybrid materials, namely, the copper thiophene‐2,5‐diphosphonate [Cu2(H2O)2(O3P–C4H2S–PO3)] (Pnma; a = 7.525 Å, b = 18.292 Å, c = 7.520 Å) and the copper 3‐fluorophenylphosphonate Cu(H2O)PO3–C6H4F (P21/c; a = 14.305 Å, b = 7.550 Å, c = 7.479 Å, β = 92.32°), have been synthesized. These compounds belong to the large homologous Cu(H2O)PO3R/[Cu2(H2O)2(O3P–R–PO3)] series, the structure of which is dictated by the presence of isolated dimeric pyramidal Cu2O6(H2O)2 units. The role of the Cu/H2O molar ratio of 1 in the stabilization of such a structure is discussed in connection with the Jahn–Teller effect of the copper cation. The study of the magnetic behavior of polycrystalline samples of the two compounds has revealed antiferromagnetic coupling between the copper ions. The interactions within the dimeric unit were estimated by the Bleaney–Bowers law with the spin Hamiltonian H = –JSCu1SCu2 + gβHS: J = –6.27 cm–1 for [Cu(H2O)PO3]2C4H2S, and J = –6.07 cm–1 for Cu(H2O)PO3–C6H4F.

Phosphonic acid: preparation and applications

“…These coordination properties were used to design molecular hybrid materials [ 64 ] also identified as metal organic framework (MOF) or coordination polymers that are synthesized by reaction with a metallic salts (e.g., copper [ 65 ], lanthanides [ 66 ]) under hydrothermal conditions [ 67 – 68 ] or by insertion of phosphonic acid in low dimensional inorganic materials like layered double hydroxide (LDH) [ 69 ] or layered simple hydroxide (LSH) [ 70 ]. These materials prepared from phosphonic acids were assessed for numerus applications, including nuclear fuel stewardship and separations of actinides [ 71 ], porosity [ 72 – 74 ], bactericidal properties [ 75 ], inorganic salt release [ 76 ], luminescence [ 77 – 78 ], protonic conduction [ 79 – 80 ], materials with magnetic properties [ 81 – 82 ], or were spread off in polymers to produce nanocomposites [ 83 – 84 ]. Of note, despite the non-chiral nature of compound 13 ( Fig.…”

A new series of magnetic and luminescent layered hybrid materials obtained from thianthrene phosphonic acid: M(H2O)PO3-S2C12H7 (M = Cu, Zn) and M(H2O)2(PO2OH-S2C12H7)2 (M = Mn, Co)

“…6b). 48 Its inorganic framework is composed of isolated Cu 2 O 6 (H 2 O) 2 copper( ii ) dimers connected by the fully deprotonated PO 3 C tetrahedra of the phosphonic function. The Cu–O distances range from 1.925(3) Å to 2.384(3) Å, the P–O distances from 1.517(3) Å to 1.534(3) Å, and the P–C distance is equal to 1.800(4) Å.…”

M(H2O)(PO3C10H6OH)·(H2O)0.5 (M = Co, Mn, Zn, Cu): a new series of layered metallophosphonate compounds obtained from 6-hydroxy-2-naphthylphosphonic acid

“…34,35 In a few cases, magneto-electric coupling was observed. [36][37][38] Since the properties of hybrid materials are influenced by the functionalization of organic precursors and after considering the incorporation of carboxylic acids 9 or halogen atoms into organic precursors 38,39 in addition to one or several phosphonic acid functions, 40 we investigate herein the conception of metal-phosphonate hybrids featuring phenol functions. Actually, only a few metal-phosphonate materials possessing phenol functions were previously reported in the literature.…”