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2020-05-09

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cc-by (c) Perlepe, Panagiota S. et al., 2020
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/173733

Rare nuclearities in Ni(II) cluster chemistry: an unprecedented {Ni12} nanosized cage from the use of N-naphthalidene-2-amino-5-chlorobenzoic acid.

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https://doi.org/10.3390/inorganics8050032

Resum

The self-assembly reaction between NiI2, benzoic acid (PhCO2H) and the Schiff base chelate, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in the presence of the organic base triethylamine (NEt3), has resulted in the isolation and the structural, spectroscopic, and physicochemical characterization of the dodecanuclear [Ni12I2(OH)6(O2CPh)5(nacb)5(H2O)4(MeCN)4]I (1) cluster compound in ~30%yield. Complex 1 has a cage-like conformation, comprising twelvedistorted, octahedral NiII ions that are bridged by five 3-OH􀀀, one -OH􀀀, an I􀀀 in 55% occupancy, five PhCO2􀀀 groups (under the 1: 1: , 1: 2: 3 and 2: 2: 4 modes), and the naphthoxido and carboxylato O-atoms of five doubly deprotonated nacb2􀀀 groups. The overall {Ni12} cluster exhibits a nanosized structure with a diameter of ~2.5 nm and its metallic core can be conveniently described as a series of nine edge- or vertex-sharing {Ni3} triangular subunits. Complex 1 is the highest nuclearity coordination compound bearing the nacbH2 chelate, and a rare example of polynuclear NiII complex containing coordinating I􀀀 ions. Direct current (DC) magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the NiII ions, while photophysical studies of 1 in the solid-state showed a cyan-to-green centered emission at 520 nm, upon maximum excitation at 380 nm. The reported results demonstrate the rich coordination chemistry of the deprotonated nacb2􀀀 chelate in the presence of NiII metal ions, and the ability of this ligand to adopt a variety of di erent bridging modes, thus fostering the formation of high-nuclearity molecules with rare, nanosized dimensions and interesting physical (i.e., magnetic and optical) properties.

Matèries

Complexos metàl·lics, Química de l'estat sòlid, Propietats magnètiques

Matèries (anglès)

Metal complexes, Solid state chemistry, Magnetic properties

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Articles publicats en revistes (Química Inorgànica i Orgànica)

Citació

PERLEPE, Panagiota S., et al. Rare nuclearities in Ni(II) cluster chemistry: an unprecedented {Ni12} nanosized cage from the use of N-naphthalidene-2-amino-5-chlorobenzoic acid. Inorganics. 2020. Vol. 8(5), num. 32. ISSN 2304-6740. [consulted: 19 of August of 2026]. Available at: https://hdl.handle.net/2445/173733

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