A series of bi- or mononuclear hexacoordinate iron(III) complexes, [Fe(L)][Fe(bpb)(CN)2]·CH3OH·0.5H2O (1), [Fe(L)] [Co(bpb)(CN)2]·CH3OH (2) [(Fe (L))2(4,4’-bipy)](BPh4)2 (3), [Fe(L)(py)](BPh4) (4) and [Fe(L)(dmap)](BPh4) (5) (bpb = 1,2-bis(pyridine-2-carboxamido)benzenate, L = N,N’-bis(2-hydroxybenzyliden)-1,7-diamino-4-azaheptane, dmap = 4-dimethylaminopyridine), have been prepared with the pentadentate Schiff base iron(III) compound as assemble precursor and characterized by element analysis, IR and X-ray diffraction. Single crystal structural determination revealed the neutral cyanide-bridged binuclear entity for complexes 1 and 2 and the cationic di- or mononuclear structure for complexes 3–5 with the positive charge(s) balanced by BPh4 – ion(s). The experimental study and theoretical simulation of the magnetic property discovered the ferromagnetic coupling between the Fe(III) ions bridged by cyanide group in complex 1 and the always high spin state of the Fe(III) ion coordinated to the Schiff base ligand in both complexes 1 and 2. The temperature dependent magnetic susceptibility investigation over complexes 3–5 showed the occurrence of the thermo-induced gradual complete spin crossover (SCO) property at about 115, 170 and 200 K, respectively.
Three new cyanide-bridged heterometallic complexes {{[Cu(S,S-Chxn)2][Fe(bbp)(CN)3]}2·2 H2O}
n
(1), {{[Cu(R,R-Chxn)2][Fe(bbp)(CN)3]}2·2 H2O}
n
(2) and {{[Cu(Cycam)][Fe(bbp)(CN)3]}·CH3OH·2 H2O}
n
(3) (bbp = bis(2-benzimidazolyl)pyridine dianion, Chxn = 1,2-diaminocyclo hexane, cyclam = 1,4,8,11-tetraazacyclodecane) have been assembled from the rarely used mer-tricyanidoiron(III) building block [PPh4]2[Fe(bbp)(CN)3] and three copper(II) compounds. The complexes have been characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. For the chiral enantiomers 1 and 2, the circular dichroism (CD) spectrum was also investigated. X-ray structural analyses revealed that the structures of the cyanide-bridged Fe-Cu complexes 1 and 2 are characterized by two crystallographically independent but structurally very similar homochiral neutral chains, each consisting of the repeating units {[Cu(S,S-Chxn)2][Fe(bbp)(CN)3]} (1) or {[Cu(R,R-Chxn)2][Fe(bbp)(CN)3]} (2). The crystal structure of 3 likewise is build up of chains consisting of {[Cu(Cyclam)][Fe(bbp)(CN)3]} building blocks. The temperature-dependent magnetic susceptibility and field dependent magnetization of the complexes showed antiferromagnetic interactions in complex 1 between the Fe(III) and Cu(II) ions, while complex 3 is ferromagnetic, indicating that the magnetic coupling through cyanide linkage is very sensitive to the structure parameters around the paramagnetic metal ions. These results have been further confirmed by fitting of the experimental data using a uniform chain model, leading to the coupling constants J = −6.35 cm−1, g = 2.08, R = 4.42 × 10−4 and J = 1.24 cm−1, g = 2.09, R = ∑(χ
obsd
T − χ
cald
T)2/∑(χ
obsd
T)2 = 4.67 × 10−4 for complexes 1 and 3, respectively.
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