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The Dimeric Pyramidal Cu 2 O 6 (H 2 O) 2 Unit – A Structural Invariant of a Homologous Series of Copper‐Layered Phosphonates
Author(s) -
Bloyet Clarisse,
Roger Mélissa,
Rueff JeanMichel,
Raveau Bernard,
Lohier JeanFrançois,
Rogez Guillaume,
Jaffrès PaulAlain
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600613
Subject(s) - chemistry , copper , homologous series , crystallography , dimer , antiferromagnetism , crystal structure , ion , stereochemistry , physics , organic chemistry , condensed matter physics
Two new layered copper hybrid materials, namely, the copper thiophene‐2,5‐diphosphonate [Cu 2 (H 2 O) 2 (O 3 P–C 4 H 2 S–PO 3 )] ( Pnma ; a = 7.525 Å, b = 18.292 Å, c = 7.520 Å) and the copper 3‐fluorophenylphosphonate Cu(H 2 O)PO 3 –C 6 H 4 F ( P 2 1 / 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(H 2 O)PO 3 R/[Cu 2 (H 2 O) 2 (O 3 P–R–PO 3 )] series, the structure of which is dictated by the presence of isolated dimeric pyramidal Cu 2 O 6 (H 2 O) 2 units. The role of the Cu/H 2 O 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 = – JS Cu1 S Cu2 + gβHS : J = –6.27 cm –1 for [Cu(H 2 O)PO 3 ] 2 C 4 H 2 S, and J = –6.07 cm –1 for Cu(H 2 O)PO 3 –C 6 H 4 F.