2015
DOI: 10.1021/acs.inorgchem.5b00039
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A New Family of Ni4 and Ni6 Aggregates from the Self-Assembly of [Ni2] Building Units: Role of Carboxylate and Carbonate Bridges

Abstract: Carboxylato (R = (t)Bu and Et) and carbonato bridges have been utilized for nickel(II)-based aggregates [Ni4(μ-H2L)2(μ3-OH)2(μ1,3-O2CBu(t))2](NO3)2·H2O·2DMF (1·H2O·2DMF), Ni4(μ-(hy)HL)2(μ3-OMe)2(μ1,1-N3)2(μ1,3-O2CEt)2]·4H2O (2·4H2O), and Ni6(μ4-L)(μ3-L)2(μ6-CO3)(H2O)8](ClO4)·9H2O (3·9H2O). Building blocks [Ni2(μ-H2L)](3+), [Ni2(μ-(hy)HL)](3+), and [Ni2(μ-L)](+) originating from [Ni2(μ-H2L)](3+) have been trapped in these complexes. The complexes have been characterized by X-ray crystallography, magnetic measur… Show more

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Cited by 47 publications
(35 citation statements)
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“…In contrast a very small spin density is observed in the broken‐symmetry state on phenoxido oxygen and azido/isocyanato nitrogen atom (–0.015 e and 0.008 e in 1 ; –0.013 and 0.005 e in 2 ) indicating a polarization competition between the two nickel atoms with α and β spin density, respectively. [28a] It is evident from the values in the Table that the sign of spin density in broken‐symmetry state on the bridging phenoxido atom (O4), in both the complexes, is negative and is the same to the sign to the sign of the Ni2 center. For the bridging azido/isocyanato (N6) atom, in both the complexes, the sign of the spin density of broken‐symmetry state is the same (positive) as that of Ni1.…”
Section: Resultsmentioning
confidence: 99%
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“…In contrast a very small spin density is observed in the broken‐symmetry state on phenoxido oxygen and azido/isocyanato nitrogen atom (–0.015 e and 0.008 e in 1 ; –0.013 and 0.005 e in 2 ) indicating a polarization competition between the two nickel atoms with α and β spin density, respectively. [28a] It is evident from the values in the Table that the sign of spin density in broken‐symmetry state on the bridging phenoxido atom (O4), in both the complexes, is negative and is the same to the sign to the sign of the Ni2 center. For the bridging azido/isocyanato (N6) atom, in both the complexes, the sign of the spin density of broken‐symmetry state is the same (positive) as that of Ni1.…”
Section: Resultsmentioning
confidence: 99%
“…This shows that the bridging phenoxido atom is mainly affected by the delocalization from Ni2, while for the bridging azido/isocyanato atom (N6), the delocalization from Ni1 is predominant. [28b] Spin polarization favours ferromagnetic coupling, whereas spin delocalization favors antiferromagnetic interaction. [28b] Obviously, in these dinuclear complexes, the effect of spin polarization competition results in a ferromagnetic interaction.…”
Section: Resultsmentioning
confidence: 99%
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“…The interest in polynuclear Ni(II) coordination chemistry was first captured when the first Ni(II)-based SMM, a Ni 12 complex, was reported in 2001 by Cadiou et al [24]. Ever since, there have been a number of homometallic polynuclear Ni II CCs with high nuclearities including, Ni 5 [7,25], Ni 6 [26], Ni 7 [27,28], Ni 8 [29][30][31][32], Ni 9 [33,34], Ni 11 [35], Ni 12 [7], Ni 13 [36], Ni 14 [37], Ni 20 [38], Ni 21 [39], Ni 24 [40] and Ni 26 [41], and many of these display interesting magnetic properties including ferromagnetic, ferrimagnetic coupling, diamagnetism and SMM behaviour.…”
Section: Introduction and Reviewmentioning
confidence: 99%
“…For a long time, numerous chemists from different disciplines have redirected their efforts to Schiff-base complexes due to their potential application in photocatalysis [4], bioscience [5] and magnetic properties [6]. As part of our work, a novel zinc(II) complex with a Salen-type bisoxime ligand was synthesized and characterized by X-ray diffraction.…”
Section: Discussionmentioning
confidence: 99%