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Issue 20, 2018
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Anion coordination directed synthesis patterns for [Ni4] aggregates: structural changes for thiocyanate coordination and ligand arm hydrolysis

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Abstract

The coordination reactivity of ligand H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) toward nickel(II) ions in the presence of two different anions resulted in cubane and fused dicubane types of tetranuclear coordination aggregates. In the first case, utilization of two carboxylate (R = Me and Et in RCO2) anions led to cubane type Ni4O4 aggregates [Ni4(H4L1)23-OH)21,3-O2CCH3)2](NO3)(CH3COO)·3H2O (1) and [Ni4(H4L1)23-OH)21,3-O2CC2H5)2](NO3)(C2H5COO)·CH3CN·1.5H2O (2). Whereas the use of thiocyanate anions triggered single imine arm hydrolysis of H5L1 and gave partial dicubane type Ni4N2O4 aggregates [Ni4(H2L2)2(HAMP)21,1-NCS)2](NO3)2 (3a) and [Ni4(H2L2)2(HAMP)21,1-NCS)2]Cl2·CH3OH·H2O (3b) (H2L2 = 3-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-2-hydroxy-5-methylbenzaldehyde). Liberated 2-amino-2-methyl-1,3-propanediol from imine arm hydrolysis was successfully trapped in 3a and 3b for the growth and stabilization of different molecular architectures. Mass spectral evidence established that two types of dinuclear fragments Ni2(H4L1) and Ni2(H2L2), from the originally used and partially hydrolyzed ligand anions have been self-assembled for two types of NiII based coordination aggregates. Two sets of complexes were characterized by elemental analysis, FT-IR and optical spectroscopy, variable temperature magnetic measurements, and single crystal X-ray analysis. The magnetic behavior examined through the temperature interval of 1.9–300 K with experimental and theoretical corroboration support the exchange pathways within the two types of [Ni4] coordination aggregates.

Graphical abstract: Anion coordination directed synthesis patterns for [Ni4] aggregates: structural changes for thiocyanate coordination and ligand arm hydrolysis

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Publication details

The article was received on 01 Jul 2018, accepted on 03 Sep 2018 and first published on 04 Sep 2018


Article type: Paper
DOI: 10.1039/C8NJ03269F
Citation: New J. Chem., 2018,42, 16717-16728
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    Anion coordination directed synthesis patterns for [Ni4] aggregates: structural changes for thiocyanate coordination and ligand arm hydrolysis

    M. Das, R. Herchel, Z. Trávníček, V. Bertolasi and D. Ray, New J. Chem., 2018, 42, 16717
    DOI: 10.1039/C8NJ03269F

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