Premium
Molecular Structures and Magnetic Properties of Strongly Antiferromagnetically Coupled Binuclear Copper(II) Complexes [CU 2 REP(μ‐X)(Y) 2 ]
Author(s) -
Chyn JongPyng,
Shieh KuanJiunn,
Chou JehLi,
Wang Yu,
Lee GeneHsiang,
Chen CheuPyeng
Publication year - 1991
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199100091
Subject(s) - chemistry , triclinic crystal system , crystallography , diamagnetism , electron paramagnetic resonance , copper , monoclinic crystal system , square pyramidal molecular geometry , antiferromagnetism , magnetic susceptibility , crystal structure , nuclear magnetic resonance , magnetic field , condensed matter physics , physics , organic chemistry , quantum mechanics
The molecular structures of binuclear copper(II) complexes [Cu 2 REP(μ‐OH)(ClO 4 ) 2 ] (4) and [Cu 2 REP(μ‐Cl)Cl 2 ] (5), in which REP = deprotonated 2,6‐bis(1′‐(4′‐(2″‐pyridyl)‐2′‐thiabutyl))‐4‐methylphenol, have been characterized by single‐crystal X‐ray diffraction. The former crystallizes in the triclinic space group Pl̄ with a = 10.156(3), b = 12.631(3), c = 25.128(10) Å, α = 92.03(3), β = 96.84(3), γ = 108.02(2),° and Z − 2. Complex 5 crystallizes in the monoclinic space group C2/c with a = 12.166(2), b = 11.825(2), c = 18.240(4) Å, β = 100.97(2)°, and Z =4. All copper ions are pentacoordinated with ligation to a sulfur, a nitrogen, and the bridging phenolato oxygen of the REP ligand, the exogenous bridge, and a counteranion. The coordination geometry of each copper of the binuclear copper sites is square pyramidal in both 4 and 5. Magnetic susceptibility measurements in the temperature range 6–300 K reveal a strong antiferromagnetic spin exchange in 5 (exchange integral 2J = −460 cm −1 ). A diamagnetic behavior is observed for 4 according to a similar cryomagnetic investigation. The diamagnetism of 4 is further confirmed by measurements of magnetic susceptibility through Evan's method at room temperature. Complex 4 has no EPR signal. The powder EPR spectrum of 5 shows the typical triplet state characteristics with Δm = ±1 transitions at g = 2.15 and a weaker Δm = 2 transition at half field with g = 4.24.