Rare Nuclearities in Ni(II) Cluster Chemistry: An Unprecedented {Ni12} Nanosized Cage from the Use of N-Naphthalidene-2-Amino-5-Chlorobenzoic Acid
| Autor: | Luís Cunha-Silva, Albert Escuer, Vlasoula Bekiari, Panagiota S. Perlepe, Konstantinos N. Pantelis, Theocharis C. Stamatatos |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Metal ions in aqueous solution
Cluster chemistry polynuclear metal complexes molecular magnetism 010402 general chemistry 01 natural sciences Coordination complex Solid state chemistry Inorganic Chemistry chemistry.chemical_compound Deprotonation Metal complexes Magnetic properties lcsh:Inorganic chemistry Molecule single-crystal X-ray crystallography chemistry.chemical_classification Schiff base 010405 organic chemistry Propietats magnètiques Magnetic susceptibility Complexos metàl·lics lcsh:QD146-197 0104 chemical sciences Química de l'estat sòlid N-naphthalidene-2-amino-5-chlorobenzoic acid Crystallography chemistry Octahedron schiff base ligands emission studies nickel(II) |
| Zdroj: | Inorganics, Vol 8, Iss 32, p 32 (2020) Dipòsit Digital de la UB Universidad de Barcelona Inorganics Volume 8 Issue 5 |
| ISSN: | 2304-6740 |
| Popis: | 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 twelve distorted, octahedral NiII ions that are bridged by five &mu 3-OH&minus one &mu OH&minus an I&minus in 55% occupancy, five PhCO2&minus groups (under the &eta 1:&eta 1:&mu &eta 2:&mu 3 and &eta 2:&eta 4 modes), and the naphthoxido and carboxylato O-atoms of five doubly deprotonated nacb2&minus 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&minus 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&minus chelate in the presence of NiII metal ions, and the ability of this ligand to adopt a variety of different bridging modes, thus fostering the formation of high-nuclearity molecules with rare, nanosized dimensions and interesting physical (i.e., magnetic and optical) properties. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|