Cyanide-bridged complexes based on dinuclear Cu(Ⅱ)-M(Ⅱ) [M=Pb and Cu] building blocks: Synthesis, cr

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Four cyanide-bridged heterometallic complexes {[CuPb(L 1 )][Fe III (bpb)(CN) 2 ]} 2 ·(ClO 4 ) 2 ·2H 2 O·2CH 3 CN (1), {[CuPb(L 1 )] 2 [Fe II (CN) 6 ](H 2 O) 2 }·10H 2 O (2), {[Cu 2 (L 2 )][Fe III (bpb)(CN) 2 ] 2 }·2H 2 O·2CH 3 OH (3) and {[Cu 2 (L 2 )] 3 [Fe III (CN) 6 ] 2 (H 2 O) 2 }·10H 2 O (4) have been synthesized by treating K[Fe III (bpb)(CN) 2 ] [bpb 2-=1,2-bis(pyridine-2-carboxamido)benzenate] and K 3 [Fe III (CN)] 6 with dinuclear compartmental macrocyclic Schiff-base complexes [CuPb(L 1 )] (ClO 4 ) 2 or [Cu 2 (L 2 )]·(ClO 4 ) 2 , in which H 2 L 1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2:1:1 and H 2 L 2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1:1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [FeⅢ (bpb)(CN) 2 ]- and [CuPb(L 1 )] 2+ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe(CN)6] 4- anion sandwiched in two [CuPu(L 1 )] 2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu 2 (L2)] 2+ segment and two terminal cyanide-containing blocks [FeⅢ (bpb)(CN)2 ]- . Octanuclear compound 4 is built from two [Fe(CN)6]3- anions sandwiched in the three [Cu 2 L 2 ] 2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2. Four cyanide-bridged heterometallic complexes {[CuPb (L 1)] [Fe III (bpb) (CN) 2]} 2 · (ClO 4) 2 · 2H 2 O · 2CH 3 CN 1)] 2 [Fe II (CN) 6] (H 2 O) 2} · 10H 2 O (2), {[Cu 2 (L 2)] [Fe III (bpb) (CN) 2] 2} 2H 2 O · 2CH 3 OH and {[Cu 2 (L 2)] 3 [Fe III (CN) 6] 2 (H 2 O) 2} · 10H 2 O (4) have been synthesized by treating K [Fe III (bpb) (CN) 2] [bpb 2- = 1,2-bis (pyridine-2-carboxamido) benzenate] and K 3 [Fe III (CN)] 6 with dinuclear compartmental macrocyclic Schiff- (ClO 4) 2 or [Cu 2 (L 2)] · (ClO 4) 2, which of H 2 L 1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2: 1: 1 and H 2 L 2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1: 1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [Fe III (bpb) (CN) 2] - and [CuPb (L 1)] 2+ units. Complex 2 is of a ne utral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe (CN) 6] 4-anion sandwiched in two [CuPu (L 1)] 2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu 2 (L2)] 2+ segment and two terminal cyanide-containing blocks [Fe Ⅲ (bpb) (CN) 2] two [Fe (CN) 6] 3- anions sandwiched in the three [Cu 2 L 2] 2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.
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